CN105728046A - Ruthenium metallic olefin metathesis catalyst and preparation and application methods thereof - Google Patents
Ruthenium metallic olefin metathesis catalyst and preparation and application methods thereof Download PDFInfo
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- CN105728046A CN105728046A CN201610178631.1A CN201610178631A CN105728046A CN 105728046 A CN105728046 A CN 105728046A CN 201610178631 A CN201610178631 A CN 201610178631A CN 105728046 A CN105728046 A CN 105728046A
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- Prior art keywords
- catalyst
- olefin metathesis
- solvent
- ruthenium metal
- metathesis catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 41
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 title abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 31
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 21
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 41
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 24
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 21
- 230000006837 decompression Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000003863 metallic catalyst Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000007239 Wittig reaction Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 241001597008 Nomeidae Species 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000005945 translocation Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 cyclic olefins Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 0 CC(C)Oc1c(C=C[C@]2(C3C(*(CC4)c5c(C)cc(C)cc5C)*4c4c(C)cc(C)cc4C)I3C2N)cc(*)cc1*I Chemical compound CC(C)Oc1c(C=C[C@]2(C3C(*(CC4)c5c(C)cc(C)cc5C)*4c4c(C)cc(C)cc4C)I3C2N)cc(*)cc1*I 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011984 grubbs catalyst Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 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 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ALKXQBXCBNKMAQ-UHFFFAOYSA-N CC(C)Oc(c(C=C)c1)c(C)cc1C(C(F)(F)F)=O Chemical compound CC(C)Oc(c(C=C)c1)c(C)cc1C(C(F)(F)F)=O ALKXQBXCBNKMAQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NKEBTMYDYTUPMH-UHFFFAOYSA-N Cc(cc(cc1C=O)[N+]([O-])=O)c1OCc1ccccc1 Chemical compound Cc(cc(cc1C=O)[N+]([O-])=O)c1OCc1ccccc1 NKEBTMYDYTUPMH-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- AVFIYMSJDDGDBQ-UHFFFAOYSA-N Parthenium Chemical compound C1C=C(CCC(C)=O)C(C)CC2OC(=O)C(=C)C21 AVFIYMSJDDGDBQ-UHFFFAOYSA-N 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000011987 hoveyda–grubbs catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
-
- 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
- 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
Abstract
The invention provides a ruthenium metallic olefin metathesis catalyst, and preparation and application methods thereof. According to the invention, easily prepared commercialized substituted salicylaldehyde in the market is taken as a raw material for preparing a series of olefin ligand ruthenium catalysts with different substituent groups. The activity of the catalyst is determined by the different substituent groups. Multiple choices are supplied to the application of the catalyst in catalyzing the open loop translocation polymerization reaction of dicyclopentadiene.
Description
Technical field
This invention relates to the preparation method of preparation method and the application of a kind of olefin metathesis catalyst, particularly a kind of metal ruthenium catalyst and the application in catalyst dicyclopentadiene ring opening metathesis polymerization thereof.
Background technology
In recent decades, the research of olefin metathesis reaction obtains rapid development at the substantial worth in the field such as medicine, pesticide and material because of its synthetic product.And ring-opening metathesis polymerization (Ring-openingmetathesispolymerization is called for short ROMP) reaction is a kind of important kind of olefin metathesis reaction, because of the feature of its active polymerization, get growing concern for.Research and development along with novel active ROMP catalyst so that this living polymerization can carry out under the temperate condition such as room temperature, normal pressure.
At present, the research in this field is concentrated mainly on the ROMP catalysts of synthesizing efficient and prepares multi-functional new material aspect (Macromolecules based on ROMP reaction, 2012,45,4447-4453), researcheres utilize ROMP reaction to investigated large quantities of novel high polymer material with excellent properties, such as polydicyclopentadiene, polynorbornene and polycyclic octene etc..
The catalyst of olefin metathesis reaction creates various different type through development for many years, and carbene catalyst is the most important ROMP catalyst of current research and development.In this kind of catalyst, most important and to apply maximum be Schrock catalyst (Macromol.RapidCommun.2012,33,1399-1403) with Grubbs catalyst (Macromolecules, 2012,45,2963-2971) Hoveyda-Grubbs catalyst, Grela catalyst and the ZhanShi catalyst modified and by Grubbs catalyst are carried out.
Summary of the invention
It is contemplated that the salicylide selecting the replacement of simple in construction is that initiation material reaction obtains required alkene part easily, obtained alkene part carries out ligand exchange again with catalyst precarsor can access corresponding New Ruthenium metallic catalyst.
Such catalyst can react by promoting olefin metathesis efficiently, for the ring opening metathesis polymerization synthetic polymer of various cyclic olefins.
The method raw material is easy to get, simple to operate, process stabilizing, environmental friendliness, is suitable for amplifying and produces, for preparing alkynol part and ruthenium carbone catalyst and utilizing this olefin metathesis catalyst to prepare polymer to provide a kind of well thinking and method.
Specifically, ruthenium metal olefin metathesis catalyst provided by the invention, it is characterised in that for the compound shown in following structure:
Wherein, R1For alkyl, aryl；R2For hydrogen；R3For CONMe2、SO2CF3、COCF3。
Or, R1For alkyl, aryl；R2For alkyl, alkoxyl, aryl；R3For CONMe2、SO2CF3、COCF3、NO2。
Further, ruthenium metal olefin metathesis catalyst provided by the invention, also have a structure in which feature, namely, for the compound shown in following structure:
Wherein, R2For hydrogen；R3For CONMe2、SO2CF3、COCF3。
Or, R2For alkyl, alkoxyl, aryl；R3For CONMe2、SO2CF3、COCF3、NO2。
Preferably, R is worked as2During for H, R3For CONMe2,SO2CF3,COCF3；
Or work as R2For Me, Et, i-Pr, t-Bu, OMe, OEt；R3For CONMe2、SO2CF3、COCF3、NO2。
In addition; the preparation method that present invention also offers above-mentioned ruthenium metal olefin metathesis catalyst; it is characterized in that: be initiation material by salicylaldehyde derivatives; after being substituted the reaction acquisition protected salicylaldehyde derivatives of hydroxyl; carrying out Wittig and be obtained by reacting the alkene part of correspondence, above-mentioned alkene part reacts with catalyst precarsor and finally gives final catalyst.
Concrete reaction equation is as follows:
In above-mentioned course of reaction, substitution reaction can be that hydroxyl reacts with the ether that becomes of halogenated hydrocarbons, it is also possible to for other for hydroxyl carries out the reaction protected.
In above-mentioned course of reaction, catalyst precarsor generally selects the compound of the similar structures such as catalyst precarsor Grubbs2nd.
Concrete technology step is as follows:
Step one, salicylaldehyde derivatives, solvent, highly basic and halogenated alkane are put into reactor, be stirred at room temperature uniformly；
Above-mentioned halogenated hydrocarbons is the halogenated alkyl hydrocarbon within 10 or aryl halide selected from carbon number.
One or more in potassium carbonate, cesium carbonate, triethylamine, diisopropyl ethyl amine, potassium tert-butoxide, sodium tert-butoxide, sodium hydride of above-mentioned highly basic；It preferably is selected from the inorganic base such as potassium carbonate, cesium carbonate or the organic base such as triethylamine, diisopropyl ethyl amine.
In this step, the mol ratio of above-mentioned salicylaldehyde derivatives, alkyl halide and highly basic is 1:1-2:0.1-1；
One or more in oxolane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, ether, methyl tertiary butyl ether(MTBE), normal hexane, normal heptane, petroleum ether, toluene, chlorobenzene, dichloromethane of above-mentioned solvent；Preferably being selected from oxolane, DMF, N,N-dimethylacetamide and dimethyl sulfoxide etc., the mass ratio of solvent and salicylaldehyde derivatives is preferably 5-10:1；
Step 2, react at the temperature of 60-70 DEG C to salicylaldehyde derivatives reaction complete；In this step, it is preferable that in being slowly heated in reactor, temperature reaches 60-70 DEG C, is continually maintained in this thermotonus until raw material reaction is complete.
Step 3, addition organic solvent, extract after repeatedly through water, the concentrated protected salicylaldehyde derivatives of acquisition hydroxyl；In this step, after judging reaction end by means such as GC or TLC monitorings, substantial amounts of organic solvent is added in reactor, (one or more in esters solvent, ether solvent, chloroform, dichloromethane, chlorobenzene, benzene, toluene of this organic solvent, preferred ester solvent, as: ethyl acetate etc.), then organic facies is repeatedly washed with water.The salicylaldehyde derivatives of isopropyl protection is obtained after being finally spin-dried for by organic layer dry solvent.
Step 4, the product of step 3 is joined in reactor together with solvent, be stirred at room temperature uniformly；
One or more in oxolane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, ether, methyl tertiary butyl ether(MTBE), normal hexane, normal heptane, petroleum ether, toluene, chlorobenzene, dichloromethane of above-mentioned solvent；Preferably being selected from ether solvent, such as ether, methyl tertiary butyl ether(MTBE) or oxolane etc., the mass ratio of the salicylide of solvent and the protection of substrate isopropyl is 10-15:1.
Step 5, addition triphenylphosphine Celfume, be cooled to less than 0 DEG C；
The mol ratio of the protected salicylaldehyde derivatives of above-mentioned hydroxyl, triphenylphosphine Celfume and highly basic is 1:1-1.2,
Step 6, be dividedly in some parts in above-mentioned reactant liquor highly basic make Wittig reaction occur, be maintained at 0 DEG C be carried out below Wittig reaction；The temperature of reaction preferably remains in-10～0 DEG C；
One or more in potassium carbonate, cesium carbonate, triethylamine, diisopropyl ethyl amine, potassium tert-butoxide, sodium tert-butoxide, sodium hydride of above-mentioned highly basic；It preferably is selected from potassium tert-butoxide, sodium tert-butoxide, sodium hydride etc.；
The mol ratio of the protected salicylaldehyde derivatives of above-mentioned hydroxyl and highly basic is 1:1.2-1.5；
Step 7, (judge reaction end by means such as GC or TLC monitorings) after completion of the reaction when the protected salicylaldehyde derivatives of hydroxyl, after being evaporated by solvent, add water；
After product is extracted by step 8, employing organic solvent, concentrated, decompression distillation obtains alkene part；
One or more in esters solvent, ether solvent, chloroform, dichloromethane, chlorobenzene, benzene, toluene of above-mentioned organic solvent, it is preferable that the halogenated hydrocarbons such as chloroform, dichloromethane, chlorobenzene；
During the Methods For Purification that above-mentioned employing decompression is distilled, it is preferable that condition is as follows: system vacuum is 2-5mmHg, boiling point 60-80 DEG C.
Step 9, by catalyst precarsor (such as Grubbs2ndAnd the compound of similar structures), alkene part and solvent add to stirring and dissolving in reactor；
The structure of above-mentioned catalyst precarsor can for the compound shown in following structure:
One or more in oxolane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, ether, methyl tertiary butyl ether(MTBE), normal hexane, normal heptane, petroleum ether, toluene, chlorobenzene, dichloromethane of above-mentioned solvent；It preferably is selected from normal hexane, normal heptane, petroleum ether, toluene, chlorobenzene, oxolane and dichloromethane etc., it is most preferred that toluene and dichloromethane；Affiliated solvent and the ratio of catalyst precarsor are between 3mL:1g to 10mL:1g, and optimized ratio is 5mL:1g.
The mol ratio of above-mentioned catalyst precarsor and alkene part is 1:1-2.5, it is most preferred that for 1:1.2-1.5.
Step 10, addition metallic catalyst stirring, react complete to catalyst precarsor reaction at the temperature of 30-50 DEG C；General reactions duration is 2-10 hour, it is possible to GC result judges terminal.
This metallic catalyst is preferably cuprous class or ferrous class catalyst, it is most preferred that for Hydro-Giene (Water Science)..The consumption of this catalyst is the 5%-50% of reaction raw materials (catalyst precarsor and alkene part) gross mass.
Step 11, cooled, filter, concentration, recrystallization obtain target product.
In above-mentioned steps, concrete post-processing approach can be: after catalyst precarsor has reacted, before precipitating out final catalyst, need to be cooled to system 0-20 DEG C place a few hours after, again the contaminant filter being wherein settled out is removed, then decompression is distilled off solvent therein again, and addition good solvent and poor solvent obtain end product solid after carrying out crystallize.
Above-mentioned good solvent can be the aromatic hydrocarbons such as the esters such as dichloromethane, chloroform, ethyl acetate, the ethers such as ether, petroleum ether, the alkane such as normal hexane, hexamethylene, toluene, benzene, chlorobenzene；
Poor solvent can be the alcohols such as methanol, ethanol and isopropanol；
The volume ratio of above-mentioned good solvent and poor solvent is between 1:5 to 1:20, it is most preferred that volume ratio is 1:10；
The ratio of crystallize solvent for use cumulative volume and used catalyst precursor is at 5mL-20ml:1g；
Precipitate out recrystallization temperature required during end product crystal between 0-30 DEG C；
The crystallize time is between 1 hour to 5 hour.
It addition, present invention also offers the application process of above-mentioned ruthenium metal olefin metathesis catalyst, it is characterised in that: above-mentioned ruthenium metal olefin metathesis catalyst is applied in ring opening metathesis polymerization；
Wherein, the monomer of above-mentioned ring opening metathesis polymerization is dicyclopentadiene and derivant thereof.
Further, the application process of ruthenium metal olefin metathesis catalyst provided by the invention, namely also have a characteristic that, the concrete technology step of above-mentioned ring opening metathesis polymerization as follows:
Add dicyclopentadiene or derivatives thereof, ruthenium metal olefin metathesis catalyst in the reactor, after stirring, reactor is heated to 60-80 DEG C, when in reactor, temperature stops heating when steeply rising, allow polyreaction naturally-occurring, after system Temperature fall, obtain solid polymer product.
Further, the application process of ruthenium metal olefin metathesis catalyst provided by the invention, namely also have a characteristic that, the mass ratio of above-mentioned dicyclopentadiene and ruthenium metal olefin metathesis catalyst is 10000:0.1-0.3.
Further, the application process of ruthenium metal olefin metathesis catalyst provided by the invention, also have a characteristic that namely, when carrying out above-mentioned ring opening metathesis polymerization, the raw material adopted is optional to be dissolved in solvent to carry out, this solvent is selected from alkane, dichloromethane, chloroform, esters (such as methyl acetate, ethyl acetate etc.), and the concentration of material solution is 0.1-1g/L.
The effect of the present invention and effect:
The present invention selects the business-like substituted salicylic aldehydes of commercially easily preparation relate to as raw material and be prepared for the alkene part ruthenium catalyst of a series of different substituents, the activity of catalyst is determined by different substituent groups, provides multiple choices for its application carrying out ring opening metathesis polymerization at catalysis dicyclopentadiene.
A series of metal ruthenium catalysts are used in the ring opening metathesis polymerization of dicyclopentadiene by the present invention, activity is high, extent of polymerization is high, catalyst amount is few, polymerizing condition is safely controllable, the mass ratio of monomer and catalyst can up to 100,000, it is more suitable for the high-quality dicyclopentadiene material product of mass industrialized production relative to other olefin metathesis catalysts.
Detailed description of the invention
Embodiment one: ruthenium metal olefin metathesis catalyst 1#
(1) structural formula of ruthenium metal olefin metathesis catalyst 1#:
(2) preparation method:
A. the salicylide of replacement is selectedThrough hydroxyl protection exposed in salicylide molecule gets up to obtain for alkane reaction the salicylide of isopropyl protection with isopropyl halide, structure is
3-methoxyl group-5 nitrosalicylaldehyde 200g and 1LN, dinethylformamide, stirring and dissolving is added in the reaction bulb of 2L.In this reaction bulb, it is slowly added to 200g2-N-Propyl Bromide and 100g potassium carbonate again, heats after 60 DEG C and continue stirring reaction.By TLC monitoring to raw material reaction complete after, reactant liquor is poured in 4L ethyl acetate, then blunge washing three times, add water 4L every time.Adding anhydrous sodium sulfate to be dried, filtration decompression obtain product crude product 250g, productivity 75% after dividing exactly solvent.
B. Wittig is occurred to be obtained by reacting alkene part in strong basicity the salicylide of the isopropyl prepared in step A protection and triphenylphosphine Celfume.
The salicylide that isopropyl is protected250g joins in 10L reaction bulb together with triphenylphosphine Celfume 400g, adds solvents tetrahydrofurane 5L.Cooling down is slowly dividedly in some parts potassium tert-butoxide 100g again after 0 DEG C.Reaction terminates rear removal of solvent under reduced pressure, adds 5L water dissolution.After 10L dichloromethane extraction, anhydrous sodium sulfate dries, filters, and obtains alkene part crude product after solvent evaporated, obtains alkene part then through after decompression distilationYellow oily liquid 200g, productivity 86%.
The concrete preparation process of step C is as follows:
By catalyst precarsor 680g and alkene part340g adds to 10L reactor, adds methylene chloride 5L, adds Cu-lyt. 150g, and when nitrogen protection, 30 DEG C of reacting by heating disappear to raw material, are cooled to room temperature, filter out impurity.After filtrate decompression boils off toluene, add dichloromethane 100mL and methanol 5L and precipitate out product catalyst solid, after filtering drying, obtain final catalyst350g, productivity 69%.
(3) spectral data:
1HNMR(300.18MHz,22℃,CDCl3,Me4: δ=11.17 (s, 1H), Si) 7.70 (s, 1H), 7.44 (s, 1H), 6.76 (s, 4H), 5.34 (m, 1H), 3.83 (s, 1H), 3.22 (s, 4H), 2.34 (s, 3H), 2.66 (s, 6H), 2.22 (s, 12H), 1.35 (d, J=7.8Hz, 6H) ppm.
13CNMR(300.18MHz,22℃,CDCl3,Me4Si): δ=156.2,153.1,143.3,141.2,140.8,132.2,132.0,131.5,129.9,11 5.5,113.2,75.6,56.8,44.3,22.8,19.2ppm.
(4) application process:
This ruthenium catalyst catalysis dicyclopentadiene carry out ring opening metathesis polymerization to be embodied as step as follows: in 50mL reactor, add dicyclopentadiene liquid 10g.The toluene solution of preparation catalyst, 1mg catalyst solid is dissolved in 10mL toluene, takes 1mL and adds reactant liquor, stop stirring after stirring.Reactor is heated to 60oC, when temperature stops heating when steeply rising in reactor, allows polyreaction naturally-occurring, after last system Temperature fall, obtain solid polymer product.
The contrast experiment of<table 1>catalysis dicyclopentadiene ring opening metathesis polymerization
From the data of upper table, the catalysis activity of this catalyst is significantly high, just can quickly be polymerized when consumption reaches 0.1/10000.
Embodiment two: ruthenium metal olefin metathesis catalyst 2#
(1) structural formula of ruthenium metal olefin metathesis catalyst 2#:
(2) preparation method:
A. the salicylide of replacement is selectedThrough hydroxyl protection exposed in salicylide molecule gets up to obtain for alkane reaction the salicylide of isopropyl protection with isopropyl halide, structure is
3-trifluoroacetyl group-5 cresotinic acid aldehyde 250g and 1L oxolane, stirring and dissolving is added in the reaction bulb of 2L.In this reaction bulb, it is slowly added to 250g2-N-Propyl Bromide and 80g triethylamine again, heats after 80 DEG C and continue stirring reaction.By TLC monitoring to raw material reaction complete after, reactant liquor is poured in the mixed solution of 4L ethyl acetate and chloroform (1:1), then blunge washing three times, add water 4L every time.Adding anhydrous sodium sulfate to be dried, filtration decompression obtain product crude product 278g after dividing exactly solvent.
B. Wittig is occurred to be obtained by reacting alkene part in strong basicity the salicylide of the isopropyl prepared in step A protection and triphenylphosphine Celfume.
The salicylide that isopropyl is protected250g joins in 10L reaction bulb together with triphenylphosphine Celfume 450g, adds solvents tetrahydrofurane 5L.Cooling down is slowly dividedly in some parts sodium hydride 65g again after 0 DEG C.Reaction terminates rear removal of solvent under reduced pressure, adds 5L water dissolution.After extracting with 10L chloroform, anhydrous sodium sulfate dries, filters, and obtains alkene part crude product after solvent evaporated, obtains alkene part then through after decompression distilationYellow oily liquid 233g.
The concrete preparation process of step C is as follows:
By catalyst precarsor 350g and alkene part200g adds to 10L reactor, adds solvent chloroform 5L, adds Hydro-Giene (Water Science). 90g, and when nitrogen protection, 30 DEG C of reacting by heating disappear to raw material, are cooled to room temperature, filter out impurity.After filtrate decompression boils off toluene, add chloroform 100mL and ethanol 5L and precipitate out product catalyst solid, after filtering drying, obtain final catalyst316g。
(3) spectral data:
Elementary analysis: C, 55.39；H,5.32；F,7.71；O,4.39；
m/z:736.1。
Embodiment three: ruthenium metal olefin metathesis catalyst 3#
(1) structural formula of ruthenium metal olefin metathesis catalyst 3#:
(2) preparation method:
A. the salicylide of replacement is selectedThrough hydroxyl protection exposed in salicylide molecule gets up to obtain for alkane reaction the salicylide of isopropyl protection with isopropyl halide, structure is
Salicylide 200g and the 1LDMF of replacement, stirring and dissolving is added in the reaction bulb of 2L.In this reaction bulb, it is slowly added to 250g2-N-Propyl Bromide and 100g sodium carbonate again, heats after 70 DEG C and continue stirring reaction.By TLC monitoring to raw material reaction complete after, reactant liquor is poured in 4L ethyl acetate, then blunge washing three times, add water 4L every time.Adding anhydrous sodium sulfate to be dried, filtration decompression obtain product crude product 228g after dividing exactly solvent.
B. Wittig is occurred to be obtained by reacting alkene part in strong basicity the salicylide of the isopropyl prepared in step A protection and triphenylphosphine Celfume.
The salicylide that isopropyl is protected200g joins in 10L reaction bulb together with triphenylphosphine Celfume 350g, adds solvent anhydrous tetrahydro furan 4L.Cooling down is slowly dividedly in some parts sodium tert-butoxide 95g again after 0 DEG C.Reaction terminates rear removal of solvent under reduced pressure, adds 4L water dissolution.After extracting with 7L chloroform, anhydrous sodium sulfate dries, filters, and obtains alkene part crude product after solvent evaporated, obtains alkene part then through after decompression distilationWhite solid 226g.
The concrete preparation process of step C is as follows:
By catalyst precarsor 400g and alkene part200g adds to 10L reactor, adds solvent petroleum ether 5L, adds Cu-lyt. 90g, and when nitrogen protection, 30 DEG C of reacting by heating disappear to raw material, are cooled to room temperature, filter out impurity.After filtrate decompression steaming petroleum ether, add ether 100mL, chlorobenzene 100ml and ethanol 5L precipitates out product catalyst solid, after filtering drying, obtain final catalyst355g。
(3) spectral data:
Elementary analysis: C, 58.47；H,6.30；O,4.55；N,6.00；
m/z:697.2。
Embodiment four: ruthenium metal olefin metathesis catalyst 4#
(1) structural formula of ruthenium metal olefin metathesis catalyst 4#:
(2) preparation method:
A. the salicylide of replacement is selectedPassing through and cylite reacts and gets up to obtain the salicylide of benzyl protection by hydroxyl protection exposed in salicylide molecule, structure is
Salicylide 150g and 1L toluene, the stirring and dissolving of replacement is added in the reaction bulb of 2L.In this reaction bulb, it is slowly added to 200g cylite and 55g potassium tert-butoxide again, heats after 60 DEG C and continue stirring reaction.By TLC monitoring to raw material reaction complete after, reactant liquor is poured 4L ethyl acetate into: in ether (1:0.5), then blunge washing three times, add water 4L every time.Adding anhydrous sodium sulfate to be dried, filtration decompression obtain product crude product 232g after dividing exactly solvent.
B. Wittig is occurred to be obtained by reacting alkene part in strong basicity the salicylide of the benzyl protection prepared in step A and triphenylphosphine Celfume.
By the salicylide of benzyl protection250g joins in 10L reaction bulb together with triphenylphosphine Celfume 500g, adds solvent anhydrous tetrahydro furan 4L.Cooling down is slowly dividedly in some parts sodium hydride 155g again after 0 DEG C.Reaction terminates rear removal of solvent under reduced pressure, adds 4L water dissolution.After extracting with 7L chloroform, anhydrous sodium sulfate dries, filters, and obtains alkene part crude product after solvent evaporated, obtains alkene part then through after decompression distilationYellow solid 231g.
The concrete preparation process of step C is as follows:
By catalyst precarsor 400g and alkene part250g adds to 10L reactor, adds solvent petroleum ether 5L, adds Cu-lyt. 150g, and when nitrogen protection, 30 DEG C of reacting by heating disappear to raw material, are cooled to room temperature, filter out impurity.After filtrate decompression steaming petroleum ether, add chlorobenzene 100ml and ethanol 5L and precipitate out product catalyst solid, after filtering drying, obtain final catalyst366g。
(3) spectral data:
Elementary analysis: C, 58.91；H,5.40；O,6.51；N,5.73；
m/z:735.1。
Claims (10)
1. a ruthenium metal olefin metathesis catalyst, it is characterised in that for the compound shown in following structure:
Wherein, R1For alkyl, aryl；
R2For hydrogen；
R3For CONMe2、SO2CF3、COCF3。
Or, R1For alkyl, aryl；
R2For alkyl, alkoxyl, aryl；
R3For CONMe2、SO2CF3、COCF3、NO2。
2. ruthenium metal olefin metathesis catalyst as claimed in claim 1 a kind of, it is characterised in that for the compound shown in following structure:
Wherein, R2For hydrogen；
R3For CONMe2、SO2CF3、COCF3。
Or, R2For alkyl, alkoxyl, aryl；
R3For CONMe2、SO2CF3、COCF3、NO2。
3. a kind of ruthenium metal olefin metathesis catalyst as claimed in claim 2, it is characterised in that:
Described R2Selected from H, Me, Et, i-Pr, t-Bu, OMe, OEt.
4. the preparation method of a kind of ruthenium metal olefin metathesis catalyst as claimed in claim 1; it is characterized in that: after salicylaldehyde derivatives is substituted the reaction acquisition protected salicylaldehyde derivatives of hydroxyl; carrying out Wittig and be obtained by reacting the alkene part of correspondence, described alkene part reacts with catalyst precarsor and finally gives final catalyst.
5. the preparation method of a kind of ruthenium metal olefin metathesis catalyst as claimed in claim 1, it is characterised in that: concrete technology step is as follows:
Step one, salicylaldehyde derivatives, solvent, highly basic and halogenated alkane are put into reactor, be stirred at room temperature uniformly；
Step 2, react at the temperature of 60-70 DEG C to salicylaldehyde derivatives reaction complete；
Step 3, addition organic solvent, extract after repeatedly through water, the concentrated protected salicylaldehyde derivatives of acquisition hydroxyl；
Step 4, the product of step 3 is joined in reactor together with solvent, be stirred at room temperature uniformly；
Step 5, addition triphenylphosphine Celfume, be cooled to less than 0 DEG C；
Step 6, in above-mentioned reactant liquor, it is dividedly in some parts highly basic, is maintained at 0 DEG C and is carried out below Wittig reaction；
Step 7, when the protected salicylaldehyde derivatives of hydroxyl after completion of the reaction, after solvent is evaporated add water；
After product is extracted by step 8, employing organic solvent, concentrated, decompression distillation obtains alkene part；
Step 9, by catalyst precarsor, alkene part and solvent add to stirring and dissolving in reactor,
Step 10, addition metallic catalyst stirring, react complete to catalyst precarsor reaction at the temperature of 30-50 DEG C；
Step 11, cooled, filter, concentration, recrystallization obtain target product.
6. the preparation method of a kind of ruthenium metal olefin metathesis catalyst as claimed in claim 5, it is characterised in that:
The mol ratio of described salicylaldehyde derivatives, alkyl halide and highly basic is 1:1-2:0.1-1；
The mol ratio of the protected salicylaldehyde derivatives of described hydroxyl, triphenylphosphine Celfume and highly basic is 1:1-1.2:1.2-1.5；
The mol ratio of described catalyst precarsor and alkene part is 1:1-2.5.
7. the preparation method of a kind of ruthenium metal olefin metathesis catalyst as claimed in claim 5, it is characterised in that:
One or more in oxolane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, ether, methyl tertiary butyl ether(MTBE), normal hexane, normal heptane, petroleum ether, toluene, chlorobenzene, dichloromethane of described solvent；
One or more in potassium carbonate, cesium carbonate, triethylamine, diisopropyl ethyl amine, potassium tert-butoxide, sodium tert-butoxide, sodium hydride of described highly basic；
One or more in esters solvent, ether solvent, chloroform, dichloromethane, chlorobenzene, benzene, toluene of described organic solvent.
8. the application process of a ruthenium metal olefin metathesis catalyst, it is characterised in that: the ruthenium metal olefin metathesis catalyst as described in claim 1-7 is applied in ring opening metathesis polymerization；
Wherein, the monomer of described ring opening metathesis polymerization is dicyclopentadiene and derivant thereof.
9. the application process of a kind of ruthenium metal olefin metathesis catalyst as claimed in claim 8, it is characterised in that: the concrete technology step of described ring opening metathesis polymerization is as follows:
Add dicyclopentadiene or derivatives thereof, ruthenium metal olefin metathesis catalyst in the reactor, after stirring, reactor is heated to 60-80 DEG C, when in reactor, temperature stops heating when steeply rising, allow polyreaction naturally-occurring, after system Temperature fall, obtain solid polymer product.
10. the application process of a kind of ruthenium metal olefin metathesis catalyst as claimed in claim 9, it is characterised in that:
The mass ratio of described dicyclopentadiene and ruthenium metal olefin metathesis catalyst is 10000:0.1-0.3.
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| CN110105400B (en) * | 2019-05-31 | 2021-11-12 | 上海化工研究院有限公司 | Temperature-sensitive ruthenium carbene complex and preparation method and application thereof |
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| CN113292692B (en) * | 2021-05-26 | 2022-07-22 | 广州优润合成材料有限公司 | Polyurethane reaction type organic metal catalyst, preparation method and application thereof |
| CN114653404A (en) * | 2022-03-28 | 2022-06-24 | 安徽泽升科技有限公司 | Ruthenium compound catalyst and application thereof in olefin metathesis |
| CN114653404B (en) * | 2022-03-28 | 2022-10-11 | 安徽泽升科技有限公司 | Ruthenium compound catalyst and application thereof in olefin metathesis |
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