CN109312145A - It is used to prepare the carbon monoxide-olefin polymeric, palladium hybrid catalyst system, polyketide preparation method and polyketane polymers using it of polyketide - Google Patents
It is used to prepare the carbon monoxide-olefin polymeric, palladium hybrid catalyst system, polyketide preparation method and polyketane polymers using it of polyketide Download PDFInfo
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- CN109312145A CN109312145A CN201780035036.5A CN201780035036A CN109312145A CN 109312145 A CN109312145 A CN 109312145A CN 201780035036 A CN201780035036 A CN 201780035036A CN 109312145 A CN109312145 A CN 109312145A
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- polyketide
- carbon monoxide
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 92
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 61
- 229930001119 polyketide Natural products 0.000 title claims abstract description 47
- 150000003881 polyketide derivatives Chemical class 0.000 title claims abstract description 47
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 229920001470 polyketone Polymers 0.000 claims abstract description 122
- -1 salt compound Chemical class 0.000 claims abstract description 58
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 42
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims description 100
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 41
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 22
- 150000001721 carbon Chemical group 0.000 claims description 22
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000005864 Sulphur Substances 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000013047 polymeric layer Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910018540 Si C Inorganic materials 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000013310 covalent-organic framework Substances 0.000 claims description 6
- 239000012621 metal-organic framework Substances 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- TZSYLWAXZMNUJB-UHFFFAOYSA-N 1-methylpyridin-1-ium-3-carboxylic acid;chloride Chemical compound [Cl-].C[N+]1=CC=CC(C(O)=O)=C1 TZSYLWAXZMNUJB-UHFFFAOYSA-N 0.000 claims description 5
- 229910006069 SO3H Inorganic materials 0.000 claims description 5
- 229920001222 biopolymer Polymers 0.000 claims description 5
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 claims description 4
- HIBQYYHFLWXBDX-UHFFFAOYSA-N 2-(3-methyl-2H-benzimidazol-1-yl)acetic acid Chemical class CN1CN(CC(O)=O)c2ccccc12 HIBQYYHFLWXBDX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- DXNAVBJNFLKWIK-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O.CC(O)=O DXNAVBJNFLKWIK-UHFFFAOYSA-N 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 89
- 238000006243 chemical reaction Methods 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000000654 additive Substances 0.000 description 27
- 230000000996 additive effect Effects 0.000 description 26
- 238000006277 sulfonation reaction Methods 0.000 description 26
- 230000004048 modification Effects 0.000 description 22
- 238000012986 modification Methods 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 16
- 230000009257 reactivity Effects 0.000 description 16
- 229920001187 thermosetting polymer Polymers 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- WNKVXCWLTXVJKT-UHFFFAOYSA-N 1-(2-methoxyphenyl)propylphosphane Chemical compound COC1=C(C=CC=C1)C(CC)P WNKVXCWLTXVJKT-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- URQYITSPKWWNQV-UHFFFAOYSA-N 2-[3-(2,4,6-trimethylphenyl)imidazol-1-ium-1-yl]acetic acid chloride Chemical compound [Cl-].C(=O)(O)C[N+]1=CN(C=C1)C1=C(C=C(C=C1C)C)C URQYITSPKWWNQV-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- XGRUGEJMSKBMPC-UHFFFAOYSA-N 1-methylpyridin-1-ium-4-carboxylic acid;chloride Chemical compound [Cl-].C[N+]1=CC=C(C(O)=O)C=C1 XGRUGEJMSKBMPC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- JBIBXDFXFBUZTB-UHFFFAOYSA-N 2-(2h-pyridin-1-yl)acetic acid Chemical compound OC(=O)CN1CC=CC=C1 JBIBXDFXFBUZTB-UHFFFAOYSA-N 0.000 description 2
- NBBUVPJYZSUKOR-UHFFFAOYSA-N 2-(3-methylbenzimidazol-3-ium-1-yl)acetic acid bromide Chemical compound [Br-].C(=O)(O)C[N+]1=CN(C2=C1C=CC=C2)C NBBUVPJYZSUKOR-UHFFFAOYSA-N 0.000 description 2
- RNVJFFPLHAPOKP-UHFFFAOYSA-N 2-(3-methylimidazol-3-ium-1-yl)acetic acid;bromide Chemical compound [Br-].CN1C=C[N+](CC(O)=O)=C1 RNVJFFPLHAPOKP-UHFFFAOYSA-N 0.000 description 2
- IIBIQXGYXVVFPI-UHFFFAOYSA-N 2-[3-[2,6-di(propan-2-yl)phenyl]imidazol-1-ium-1-yl]acetic acid bromide Chemical compound [Br-].C(=O)(O)C[N+]1=CN(C=C1)C1=C(C=CC=C1C(C)C)C(C)C IIBIQXGYXVVFPI-UHFFFAOYSA-N 0.000 description 2
- KXHGPWFUKUMTCW-UHFFFAOYSA-N 2-carboxyethyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCC(O)=O KXHGPWFUKUMTCW-UHFFFAOYSA-N 0.000 description 2
- TZWFIGLQGUDMSA-UHFFFAOYSA-N 2-pyridin-1-ium-1-ylacetic acid;bromide Chemical compound [Br-].OC(=O)C[N+]1=CC=CC=C1 TZWFIGLQGUDMSA-UHFFFAOYSA-N 0.000 description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
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- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
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- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- WICWEYHSADNZSA-UHFFFAOYSA-N 2-(3-methyl-2h-imidazol-1-yl)acetic acid Chemical class CN1CN(CC(O)=O)C=C1 WICWEYHSADNZSA-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NKVJKVMGJABKHV-UHFFFAOYSA-N 3-carboxypropyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC(=O)O)C1=CC=CC=C1 NKVJKVMGJABKHV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZYUOGUSHNKQDFS-UHFFFAOYSA-N [Br-].C(=O)(O)C[N+]1=CN(C=C1)C1=C(C=C(C=C1C)C)C Chemical compound [Br-].C(=O)(O)C[N+]1=CN(C=C1)C1=C(C=C(C=C1C)C)C ZYUOGUSHNKQDFS-UHFFFAOYSA-N 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960003403 betaine hydrochloride Drugs 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- SISAYUDTHCIGLM-UHFFFAOYSA-N bromine dioxide Inorganic materials O=Br=O SISAYUDTHCIGLM-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 125000002084 dioxo-lambda(5)-bromanyloxy group Chemical group *OBr(=O)=O 0.000 description 1
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 description 1
- STCDDNDGEFVYKE-UHFFFAOYSA-N diphenylphosphane;propane Chemical compound CCC.C=1C=CC=CC=1PC1=CC=CC=C1.C=1C=CC=CC=1PC1=CC=CC=C1 STCDDNDGEFVYKE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000619 oxo-lambda(3)-bromanyloxy group Chemical group *OBr=O 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 150000003063 pnictogens Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000002077 trioxo-lambda(7)-bromanyloxy group Chemical group *O[Br](=O)(=O)=O 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/32—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings containing at least two non-condensed six-membered aromatic rings in the carbon skeleton
-
- 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
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of carbon monoxide-olefin polymerics for being used to prepare polyketide characterized by comprising salt compound has 5 to 40 carbon atoms, including carrying out the modified carrier in surface or carboxylic acid group with sulfonic group；And palladium-based catalyst.Thus, the present invention can be provided in the preparation of polyketone the palladium hybrid catalyst system for showing high activity and preventing fouling, and by can also be provided using above-mentioned palladium hybrid catalyst system it can prevent from fouling and omit that seed is added, the good polyketide preparation method of stability and activity in polymerization reaction and the high polyketane polymers of the apparent density thus prepared.
Description
Technical field
The present invention relates to can show high activity in the preparation of polyketone and prevent the palladium hybrid catalyst system of fouling, benefit
With the polyketide preparation method of above-mentioned hybrid catalyst system and thus the polyketane polymers prepared.
Background technique
Polyketone is a kind of referred to as carbon monoxide/olefin copolymer polymer.Recently, polyketone is actively used as high intensity
The raw material of fiber and engineering plastics etc., therefore its demand is also increasing.The synthesis of this polyketone is converting carbon monoxide to
There is good industrial applicibility with the aspect of substance and in terms of the polymer compound for being capable of providing excellent physical properties.
In existing polyketone preparation method, in methyl alcohol by catalyst dissolution, then it is added in reactor, under stress
By carbon monoxide and vinyl polymerization synthesizing polyketone.In this existing polyketone preparation method, in the homogeneous state of dissolution in methyl alcohol
Lower carry out polymerization reaction, as a result, formed in a solvent not solubility amorphous slurry formula polyketone (carbon monoxide and ethylene
Copolymer).
However, the existing polyketone of amorphous slurry form, which is made, can not adjust its grain shape, therefore there are apparent densities
The low problem of low, reactor per unit volume productivity.This amorphous slurry formula polyketone particle be adhered to reactor surface,
In blender, delivery pipe etc., to cause scale problems in batch production process.
Also, in existing polyketone preparation method, it is difficult to not directly using additives such as sulfonic acid (sulfonic acid)
In the case where activity is increased to industrially applicable level, but when using highly acid additive, exist and be easy to happen
The problem of fouling, therefore, it is difficult to be suitable for batch production process.
Therefore, it has increasing need for developing a kind of adjustable grain shape, prevents the knot occurred in polymerization process
Reactivity is increased to the preparation method of industrial useful horizontal polyketone by dirty phenomenon.
Summary of the invention
Problems to be solved by the invention
It is an advantage of the invention to provide by the shape and size that can equably control the polyketone finally prepared come
Improve apparent density, prevents the scale formation occurred in process, improve the stability of polymerization reaction and the catalyst group of activity
Close object.
Another object of the present invention is to provide by using can as additive by the salt compound of carboxylic acid-substituted
High activity is shown in the preparation of polyketone and prevents the palladium hybrid catalyst system of fouling.
Another object of the present invention is, by being provided using above-mentioned carbon monoxide-olefin polymeric and palladium hybrid catalyst system
It can prevent fouling and omit that seed, the good polyketide preparation method of stability and activity in polymerization reaction is added
Thus the high polyketane polymers of the apparent density prepared.
Above-mentioned purpose and other purposes of the invention can be realized by invention described below.
The solution to the problem
One embodiment of the present invention is related to a kind of carbon monoxide-olefin polymeric for being used to prepare polyketide, and feature exists
In, comprising: salt (onium salt) compound has 5 to 40 carbon atoms, including carrying out the modified load in surface with sulfonic group
Body or carboxylic acid group；And palladium-based catalyst.
Another embodiment of the present invention is related to a kind of palladium hybrid catalyst system for being used to prepare polyketide, special
Sign is, including the above-mentioned carbon monoxide-olefin polymeric for being used to prepare polyketide, uses alkene and carbon monoxide as reaction
Object.
A further embodiment of the invention is related to a kind of polyketone preparation method characterized by comprising poly- by being used to prepare
The carbon monoxide-olefin polymeric of ketone compound is scattered in the step in solvent；And to the above-mentioned carbon monoxide-olefin polymeric of dispersion be added alkene and
The step of carbon monoxide is to be polymerize.
A further embodiment of the invention is related to a kind of polyketane polymers, which is characterized in that by according to above-mentioned polyketone system
Preparation Method is formed, with 0.1 to 0.5g/ml apparent density.
The effect of invention
The present invention, which can provide, can show high activity in the preparation of polyketone and prevent the carbon monoxide-olefin polymeric of fouling
With the palladium hybrid catalyst system including it, and can prevent from tying by can also be provided using above-mentioned hybrid catalyst system
Dirt adjusts the shape and size of polyketone, omits and seed, the good polyketide of stability and activity in polymerization reaction is added
Object preparation method and the high polyketane polymers of the apparent density thus prepared.
Detailed description of the invention
Fig. 1 be preparation example 1 in prepare with sulfonic group carries out surface modification carrier SEM photograph.
Fig. 2 be execute embodiment 1 polymerization reaction after recycle preparation example 1 with sulfonic group carries out surface modification
The SEM photograph of carrier.
Fig. 3 be preparation example 2 in prepare with sulfonic group carries out surface modification carrier electron micrograph.
Fig. 4 is to compare carrying out the modified carrier in surface applied to embodiment 3 with sulfonic group for what is prepared in preparation example 2
The SEM photograph of (a) and (b) later before polyketone preparation.
Fig. 5 is the photo of the polyketone prepared in embodiment 1.
Fig. 6 is the photo of the polyketone prepared in embodiment 3.
Fig. 7 is the photo of the polyketone prepared in embodiment 4.
Fig. 8 is the photo of the polyketone prepared in comparative example 2.
Fig. 9 is the photo of the polyketone prepared in comparative example 4.
Figure 10 shows the carrier 100 that surface modification is carried out with sulfonic group of the first specific embodiment of the invention.
Figure 11 shows the carrier 200 that surface modification is carried out with sulfonic group of the second specific embodiment of the invention.
Specific embodiment
Carbon monoxide-olefin polymeric
One embodiment of the present invention is related to a kind of carbon monoxide-olefin polymeric for being used to prepare polyketide, and feature exists
In, comprising: salt compound has 5 to 40 carbon atoms, including carrying out the modified carrier in surface or carboxylic acid group with sulfonic group；
And palladium-based catalyst.
The present invention can be provided in the preparation of polyketone the carbon monoxide-olefin polymeric for showing high activity and preventing fouling as a result,
With the palladium hybrid catalyst system including it, and fouling can be prevented by can also be provided using above-mentioned hybrid catalyst system
And omit seed is added, it the good polyketide preparation method of stability and activity in polymerization reaction and thus prepares
The high polyketane polymers of apparent density.
In particular, the carbon monoxide-olefin polymeric for being used to prepare polyketide and the palladium mixed catalyst body for utilizing it of the invention
System can prevent the fouling occurred in the existing catalyst system for being used to prepare polyketone and be increased to reactivity well
Level, seedage method is not added using be added without individual seed, therefore the excellent polyketone of apparent density can be prepared
Polymer.
(carrying out the modified carrier in surface with sulfonic group)
Above-mentioned heterogeneous (hetero) material for using sulfonic group to carry out modified carrier as the palladium-based catalyst in surface is included in
It is interior.As used herein, term " dissimilar materials " refers to the ingredient contained in carbon monoxide-olefin polymeric, that is, with palladium-based catalyst
Substance existing for mixed state.
In the case, for example, of the invention carries out the modified carrier in surface and palladium base catalysis with sulfonic group with mixing
The carbon monoxide-olefin polymeric of the form of agent, which is in, is supported on the shape carried out on the modified carrier in surface with sulfonic group with palladium-based catalyst
The distinguishing state of the catalyst of formula can equably control the polyketone finally prepared when being suitable for polyketone polymerization process etc.
Shape and size prevent the scale formation occurred in process thus, it is possible to improve the apparent density of polyketone, improve polymerization
The stability and activity of reaction.
In above-mentioned carbon monoxide-olefin polymeric, the equivalent of surface modified carrier and above-mentioned palladium-based catalyst is carried out with sulfonic group
It can be 1:0.1 to 1:2 specifically than that can be 1:0.1 to 1:10.More specifically, equivalent proportion can be 1:0.1 to 1:
1.2.When carrying out polymerizeing using the polyketone of carbon monoxide-olefin polymeric within the above range, fouling can be prevented and obtained higher
The high apparent density of catalytic activity and polyketane polymers.
Carrying out the modified carrier in surface and above-mentioned palladium-based catalyst with sulfonic group can form packet to be scattered in solvent
It includes in above-mentioned carbon monoxide-olefin polymeric.Specifically, above-mentioned solvent can be alcohols solvent, more specifically, can be with 1-
The alcoholic compound of 20 carbon atoms, such as methanol.It, can be further when this carbon monoxide-olefin polymeric is suitable for polyketone polymerization
Improve reactivity, and because low boiling point can be advantageous for last handling process.
The above-mentioned carrier for carrying out surface modification with sulfonic group can equably control the shape and size of polyketone to be polymerized,
The fouling occurred in the polymerization is prevented, and is used to the apparent density that further improvement is formed by polyketone particle.
In particular, the above-mentioned sulfonic group for carrying out the modified carrier in surface with sulfonic group is catalyzed in polymerization process with palladium base
Agent interaction forms the polyketone with the powder type of high apparent density to more efficiently prevent from fouling, will not be to palladium base
The activity of catalyst has an adverse effect, and keeps the excellent effect of high catalytic activity.
Specifically, it is above-mentioned with sulfonic group carry out the modified carrier in surface may include by following chemical formula 1-1 into 1-3
The functional group of expression a kind of be bonded to the structure of carrier surface.
[chemical formula 1-1]
*-SO3H
In above-mentioned chemical formula 1-1, * refers to the part being bonded with carrier surface.
[chemical formula 1-2]
In above-mentioned chemical formula 1-2, R21To R26It is each independently hydrogen or C1~C20 alkyl；* refer to and carrier surface
The part of bonding.
[chemical formula 1-3]
In above-mentioned chemical formula 1-3, R31To R34It is each independently hydrogen or C1~C20 alkyl；* refer to and carrier surface
The part of bonding.
Specifically, *, which can be with carrier surface connection, forms C-C key or Si- in above-mentioned chemical formula 1-1 into 1-3
The binding site of C key.In the case, carrier and the functional group by one of above-mentioned chemical formula 1-1 to 1-3 of formula expression pass through
The high C-C key of bond strength or Si-C key are connected, and therefore, stability is high, and the fixed force of carrier can be improved.
Above-mentioned carrier is the porous particle comprising stomata, and can control the surface of polyketone in polymerization process
Product, pore radius, stomata, volume etc..
Above-mentioned carrier may include silica, zeolite, graphite, carbon black, graphene, carbon nanotube, active carbon, polyphenyl second
Alkene, micropore organic network polymer (microporous organic network), metal organic framework (Metal-Organic
Framework；MOF), zeolite imidazole ester skeleton (Zeolite-Imidazolate Framework；ZIF), covalent organic framework
(Covalent Organic Framework；One of COF) and wrap cellulose-containing biopolymer (biopolymer)
More than.In the case, while the shape and size of polyketone are equably controlled in polymerization process, can further change
The kind effect for preventing fouling, and the process performance of carbon monoxide-olefin polymeric and polyketone prepared therefrom is good, can have for
The more favorable characteristic of postprocessing working procedures.
Specifically, above-mentioned carrier may include silica, zeolite imidazole ester skeleton, polystyrene, micropore organic network
One or more of polymer (microporous organic network).In the case, the shape of polyketone is not only controlled
And size, it can also further improve the effect for preventing fouling, and can be further improved commercial utility.
When using micropore organic network polymer (microporous organic network) as above-mentioned carrier,
Its type is not particularly limited.For example, above-mentioned micropore organic network polymer can for by using end contain there are two or
The compound of more three keys and/or compound Yuan couplings for containing leaving group (leaving group) in end are anti-
It answers, the organic network polymer that Suzuki coupling reaction or known cross-coupling reaction in addition to this are formed.
Yuan coupling reactions of Yong Yu, Suzuki coupling reaction or known friendship in addition to this can be used in above-mentioned leaving group
Pitch the leaving group of coupling reaction, however, the present invention is not limited thereto.Specifically, it includes halogenation that above-mentioned leaving group (X), which can be,
Object (halide), toluene fulfonate (tosylate), fluoroform sulphonate (triflate), mesylate (mesylate), boron
Acid (boronic acid), borate ,-N2+X-Deng the leaving group that can be used for coupling reaction.E.g., including above-mentioned leaving group
The compound of group can be nitride chelate compound (R-N2+), dialkyl ether compounds (R-OR2 +), it is triflated
Close object (R-OSO2RF), toluenesulfonic acid salt compound (R-OTf), halide (R-Cl, R-Br, R-I, R-F), mesylate chemical combination
Object (R-OMs), nitrate compound (R-ONO2), phosphate compounds (R-OPO (OH)2), sulfide compound (R-SR2 +), carboxylic
Acid compound (R-OCOR), alternatively, the compound for including two or more leaving groups can be R-N2X、R-OSO2R、R-
OSO2F、SO2-R、SOR、R-SR、IPhX、IROTf、I(OH)OTs、RCOCl、R-SO2-Cl、R-N2+X-、R-OSO2CF3、R-
OSO2-Rf、R-OSO2CH3、Ar-Ar-I+、R-OPO(OR)2、PF6-、R-B(OR)2、R2N-H、R-X、RCO(SEt)、RCO(SEt)
Ar-SMe、RC≡CH、Ar-N2X, R (C=O) R2, R-HC=O, R-HC=O etc..
Above-mentioned Rf is perfluoroalkyl (perfluoroalkyl), and Tf is triflate (triflate), and Ms is methylsulphur
Acid esters (mesylate), X are halogens, and R is the substituted or unsubstituted hydrocarbon with 1-20 carbon atom, and Ar is with 6-20 carbon
The aromatic hydrocarbons of atom.
In one embodiment, the compound including leaving group (leaving group) can be for by following chemistry
The compound that formula A is indicated.
[chemical formula A]
(X-R10)p(Z)
In above-mentioned chemical formula A, R10For the alkylidene with 1~20 carbon atom or the Asia with 1~20 carbon atom
Aryl, X are separately acetylene (ethyne), halogen radical, boronate, boric acid ester group or trifluoromethanesulfonic acid ester group, and Z is that carbon is former
Son, nitrogen-atoms or the hydrocarbon with 3 to 10 carbon atoms, and p is 2 to 6.
For example, can be the compound with the form by following chemical formula A1 to the A4 skeleton structure indicated respectively.
[chemical formula A1]
[chemical formula A2]
[chemical formula A3]
[chemical formula A4]
In above-mentioned chemical formula A1 into A4, X is separately acetylene (ethyne), halogen radical, boronate, boric acid ester group
Or trifluoromethanesulfonic acid ester group, Z are carbon atom, nitrogen-atoms or the hydrocarbon with 3 to 10 carbon atoms.At this point, having 3 to 10 carbon originals
The hydrocarbon of son can be cyclic hydrocarbon or stereochemical structure hydrocarbon.For example, Z can be the adamantane structure of tetravalence connection in embodiment A4.
Also, for example, being easy to supply and receive when the compound by above-mentioned chemical formula A1 and A2 expression is used as reactant
Raw material, it is at low cost, therefore, when being suitable for sweeping large-scale production process, economy can be improved.
Specifically, the average grain diameter of carrier can be 0.01 μm to 5 μm, it can be 0.05 μm to 2 μm more specifically
Or 0.45 μm to 1.8 μm.Within the above range, the shape and size of polyketone can be more uniformly controlled, and table can be improved
See density.For example, the average grain diameter of carrier can be adjusted according to the shape and size of required polyketone particle.
Specifically, the surface area of carrier can be 5m2/ g to 2000m2More specifically/g can be 20m2/ g is extremely
1800m2/ g, 30m2/ g to 1700m2/ g or 30m2/ g to 900m2/g.Within the above range, polyketone can more uniformly be controlled
Shape and size, and apparent density can be improved.For example, load can be adjusted according to the shape and size of required polyketone particle
The surface area of body.
Specifically, the average pore radius of carrier can be 0.1nm to 25nm, it more specifically, can be for 0.5nm extremely
10nm, or 1nm to 6nm.Within the above range, the shape and size of polyketone can be more uniformly controlled, and table can be improved
See density.For example, the average pore radius of carrier can be adjusted according to the shape and size of required polyketone particle.
Specifically, the pore volume of carrier can be 0.01mL/g to 1.0mL/g, more specifically, Ke Yiwei
0.02mL/g to 0.7mL/g or 0.04mL/g to 0.5mL/g.Within the above range, the shape of polyketone can more uniformly be controlled
And size, and apparent density can be improved.For example, carrier can be adjusted according to the shape and size of required polyketone particle
Average pore volume.
Specifically, carrier can contain aromatic ring in the structure.In the case, carrier has good stability, and works as
When carrying out surface modification with sulfonic group, excellent surface modification efficiency may be implemented.
In the first specific embodiment, carry out the modified carrier in surface can be including having by following chemistry with sulfonic group
The hollow knot of the micropore organic network polymer (microporous organic network) for the unit repeatedly that formula 1-4 is indicated
Structure body.
[chemical formula 1-4]
In above-mentioned chemical formula 1-4, A is the connection site of atom.
Figure 10 is exemplarily illustrated the carrier 100 that surface modification is carried out with sulfonic group of above-mentioned first specific embodiment.Ginseng
According to Figure 10, the carrier 100 for carrying out surface modification with sulfonic group of the first specific embodiment is by having empty inner space 102
The hollow structure 101 that hollow (hollow) structure is constituted, above-mentioned hollow structure 101 can be by having by above-mentioned chemical formula 1-
Micropore organic network polymer (the microporous organic network) formation of 4 units repeatedly indicated.For example,
In above-mentioned hollow structure 101, the A of unit with by chemical formula 1-4 indicates another to one indicated by above-mentioned chemical formula 1-4 repeatedly
The A of one unit repeatedly is connected by singly-bound to form organic network, and wherein includes micropore (microporous).
Also, zeolite imidazole ester skeleton etc. can be used as making to have by above-mentioned in the hollow structure 101 of Figure 10
The micropore organic network polymer for the unit repeatedly that chemical formula 1-4 is indicated has the template (template) of hollow structure.Herein
In the case of, carrying out the modified carrier 100 in surface with sulfonic group may include micropore organic network polymer and zeolite imidazole ester bone
Frame is as carrier.Also, the zeolite imidazole ester skeleton for being used as above-mentioned template can be by the state quilt of the removings such as etch process
It uses.
Although in Figure 10 for the ease of expression and the structure of hollow structure 101 is indicated with ball shape, but as long as in having
Hollow structure, shape is unrestricted, for example, hollow structure 101 can have polyhedral shape of inner space sky.
In the second specific embodiment, the above-mentioned carrier for carrying out surface modification with sulfonic group may include that silica carries
Body and be formed in above-mentioned surface of silica support and have had by the micropore of the following chemical formula 1-5 unit repeatedly indicated
Machine network polymer (microporous organic network) layer.
[chemical formula 1-5]
In above-mentioned chemical formula 1-5, A' separately indicates the connection site or repeatedly single for the atom being bonded with carrier
Connection site between position, at least one is the connection site for the atom being bonded with carrier in above-mentioned A', and in above-mentioned A'
At least one is repeatedly the connection site between unit.
Figure 11 shows the carrier 200 that surface modification is carried out with sulfonic group of above-mentioned second specific embodiment.Referring to Fig.1 1,
The carrier 200 for carrying out surface modification with sulfonic group of two specific embodiments includes silica supports 202 and is formed in above-mentioned two
Micropore organic network polymeric layer 201 on silica support surface.Above-mentioned micropore organic network polymeric layer 201 by have by
Micropore organic network (the microporous organic network) polymer for the unit repeatedly that above-mentioned chemical formula 1-5 is indicated
It is formed, the carrier 200 for carrying out surface modification with sulfonic group of above-mentioned second specific embodiment can have micropore organic network
The form that the inside of (microporous organic network) polymeric layer 201 is filled by silica supports 202.Example
Such as, above-mentioned micropore organic network polymeric layer 201 include with by the chemical formula 1-5 unit repeatedly indicated polymer, one
At least one A' is connect with the A' of adjacent unit repeatedly by singly-bound to form organic network in unit repeatedly, at least one A'
Si-C key is formed with silica supports 202.
Also, the micropore organic network polymeric layer 201 in Figure 11 can be by using silica as template
(template) it is formed to make to have by the micropore organic network polymeric layer 201 of the above-mentioned chemical formula 1-5 unit repeatedly indicated
On the surface of silica supports 202.In the case, it may include micro- for carrying out the modified carrier 200 in surface with sulfonic group
Hole organic network polymer and silica are as carrier.
In Figure 11, although the structure of silica supports 202 is indicated by spherical structure for the ease of expression, its shape
Shape is not particularly limited, for example, may include polyhedron-shaped.
In third specific embodiment, the above-mentioned carrier for carrying out surface modification with sulfonic group may include having by followingization
The polystyrene compounds for the unit repeatedly that formula 1-6 is indicated.
[chemical formula 1-6]
In above-mentioned chemical formula 1-6, R6For sulfonic group, p-methyl benzenesulfonic acid base or benzene sulfonic acid base, n is 10 to 20,000.
In the case, carbon monoxide-olefin polymeric can be such that the polyketone particle of final production more miniaturize and further improvement table
See density and uniformity.
Also, above-mentioned polystyrene compounds can be to include by the copolymerization of the above-mentioned chemical formula 1-6 unit repeatedly indicated
Object.For example, polystyrene compounds can be for by the copolymerization of the above-mentioned chemical formula 1-6 unit repeatedly indicated and divinylbenzene
Object.
In the 4th specific embodiment, the above-mentioned carrier for carrying out surface modification with sulfonic group can have silica supports
With the structure of the functional group Si-C bonding indicated by one of above-mentioned chemical formula 1-2 to chemical formula 1-3.In the case, it urges
The stability of agent composition is more improved, and can be further improved the effect for preventing fouling.
For example, sulfuric acid or chlorosulfonic acid can be added to carrier to prepare in the above-mentioned carrier for carrying out surface modification with sulfonic group.
Preparation may include the step of preparing carrier and making carrier table with the method that sulfonic group carries out the modified carrier in surface
Face sulfonation (sulfonation) is to carry out the modified step in surface with sulfonic group.
As described above, above-mentioned carrier may include silica, zeolite, graphite, carbon black, graphene, carbon nanotube, activity
Charcoal, polystyrene, micropore organic network polymer (microporous organic network), metal organic framework
(MOF), zeolite imidazole ester skeleton (ZIF), covalent organic framework (COF) and the cellulose-containing biopolymer of packet
One or more of (biopolymer).Above-mentioned carrier can be commercial product or directly prepare.In the case, poly-
While equably controlling the shape and size of polyketone in conjunction reaction process, it can further improve the effect for preventing fouling, and
And it can be further improved the process performance of carbon monoxide-olefin polymeric and polyketone prepared therefrom.
Specifically, above-mentioned carrier may include silica, zeolite imidazole ester skeleton, polystyrene, micropore organic network
One or more of polymer (microporous organic network).In the case, the shape of polyketone is not only controlled
And size, it can also further improve the effect for preventing fouling, and business efficiency is also more preferable.
Specifically, the step of preparing carrier may include after preparing carrier, make prepared carrier with by following
The aitiogenic step of compound that chemical formula 5 or chemical formula 6 indicate.Thus, it is possible to be formed on the surface of the carrier comprising aromatic ring
Structure, the modified efficiency in surface is carried out to carrier with sulfonic group to further increase, and further increase sulfonic group and carrier
Between bonding force.
[chemical formula 5]
Ar-X2
[chemical formula 6]
Ar-Mg-X
In above-mentioned chemical formula 5 into chemical formula 6, Ar is benzyl or phenyl, and Mg is magnesium, and X is halogen.
Specifically, in above-mentioned chemical formula 5 into chemical formula 6, for example, halogen can be Cl, Br, F or I, it is more specific and
Speech, can be I, Cl or Br.In the case, economical and practical because can easily supply and receive raw material, and can be into one
Step improves reactivity.
It in one embodiment, can be by using zeolite imidazole ester skeleton as mould in the step of preparing carrier
Plate is to make four-(4- ethynyl phenyl)-methane (tetra- (4-ethynylphenyl)-methane) and by above-mentioned chemical formula 1-
6 compounds indicated are in Pd (PPh3)2Cl2Carrier is prepared with method aitiogenic under CuI catalyst.In the case, made
Standby carrier is by the step of making sulfonating surface (sulfonation), so as to provide as including having by above-mentioned chemistry
The hollow structure of the micropore organic network polymer for the unit repeatedly that formula 1-4 is indicated carries out the modified load in surface with sulfonic group
Body.
In another embodiment, in the step of preparing carrier, can be come by using silica as template
Make four-(4- ethynyl phenyl)-methane (tetra- (4-ethynylphenyl)-methane) and by above-mentioned chemical formula 1-6 table
The compound shown is in Pd (PPh3)2Cl2Carrier is prepared with method aitiogenic under CuI catalyst.In the case, prepared
Carrier by the step of making sulfonating surface (sulfonation), so as to provide including silica supports and being formed in
In above-mentioned surface of silica support and with the micropore organic network polymer by the above-mentioned chemical formula 1-5 unit repeatedly indicated
(microporous organic network) layer carries out the modified carrier in surface with sulfonic group.
In still another embodiment, the step of preparing carrier may include by the support dispersion Jing Guo dehydration molten
In agent, the compound that being then added is indicated by above-mentioned chemical formula 5 reacts to generate, and aromatic functional group is made to be bonded to carrier surface
On step.In this case, it is possible to further increase the surface modification efficiency and carrier in sulfonation (sulfonation) step
Stability.
Specifically, the dehydration of carrier can by using heating furnace at 600 DEG C to 900 DEG C the supply of nitrogen or argon
Gas carries out.
Specifically, the solvent for the support dispersion Jing Guo dehydration can be that ether solvent more specifically can be with
It is alkyl ether solvent, for example, it may be diethylether solvent.In this case, it is possible to further increase dispersibility.
For example, prepared carrier is by making table when above-mentioned carrier is silica and Ar is benzyl in chemical formula 5
The step of face sulfonation (sulfonation), so as to provide with silica supports and by above-mentioned chemical formula 1-2 expression
The structure of functional group Si-C bonding carries out the modified carrier in surface with sulfonic group.
For example, prepared carrier is by making table when above-mentioned carrier is silica and Ar is phenyl in chemical formula 5
The step of face sulfonation (sulfonation), so as to provide with silica supports and by above-mentioned chemical formula 1-3 expression
The structure of functional group Si-C bonding carries out the modified carrier in surface with sulfonic group.
Carrier surface sulfonation (sulfonation) is set to carry out the modified step in surface with sulfonic group to may include quasi- to institute
The step of standby above-mentioned carrier addition sulfuric acid or chlorosulfonic acid carry out sulfonation (sulfonation).
Specifically, can be handled with sulfuric acid (95%) or chlorosulfonic acid in carrying out the modified step in surface with sulfonic group
The above-mentioned carrier that is prepared causes sulfonating reaction on the phenyl ring in the structure that carrier is included.Each above-mentioned carrier as a result,
It is modified as with the functional group on terminal phenyl rings including sulfonic structure.
When prepare by this method carry out the modified carrier in surface with sulfonic group when, pass through the conversion ratio of the carrier of sulfonation
(surface degree of modification) is very excellent.Also, C- even is formed by under the extreme reaction condition of the processing concentrated sulfuric acid or chlorosulfonic acid
C key or Si-C key will not be destroyed, therefore the form that most of functional groups are fixed on the surface of carrier may be implemented.
In one embodiment, the sulfonation (sulfonation) of carrier can by the reactions of following reaction equations 1 into
Row.
[reaction equation 1]
In another embodiment, the aromatics sulfonation of carrier can by the reaction of following reaction equations 2 or reaction equation 3 into
Row.
[reaction equation 2]
[reaction equation 3]
For example, with make organic substance and silica surface hydroxyl (≡ Si-OH) generate react with pass through Si-O key and
The method immobilized is compared, as shown in above-mentioned reaction equation 2 to 3, when aromatic ring is connect with carrier, then make its sulfonation come into
When row surface is modified, the bonding force between surface-modifying groups and carrier surface is more excellent.In the case, it is modified that there are surfaces
Group is not easy the advantages of desorbing (leaching).Therefore, surface modification is carried out with sulfonic group by prepared by this preparation method
Carrier have excellent stability and can help to realize high activity in polymerization reaction.
Specifically, carrying out the modified carrier in surface with sulfonic group may include 0.1mmol-H+/ g to 3mmol-H+/ g's
Sulfonic group.In this case, it is possible to further increase the efficiency by sulfonic polyketone synthesis procedure.
(salt compound comprising carboxylic acid group)
When being suitable for polyketone preparation method, the above-mentioned salt compound comprising carboxylic acid group can be by reducing entire polymerization
Reaction speed in reaction more efficiently prevents from fouling.The above-mentioned salt compound comprising carboxylic acid group is used to make use of the invention
It realizes and occurs in the existing catalyst system for being used to prepare polyketone first in the palladium hybrid catalyst system for preparing polyketone
The different reaction pattern of the increase of the sharply reaction speed of beginning polymerization reaction.
As a result, using the of the invention of the above-mentioned carbon monoxide-olefin polymeric for being used to prepare polyketone and palladium hybrid catalyst system
Polyketone preparation method can be omitted controls reaction pressure, temperature, solvent, reaction time and reaction rate in polymerization process
Process, fouling can be prevented, and can be realized excellent activity.These characteristics, which are provided with, to be conducive in large-scale production process
Applicable advantage.
Also, the palladium catalyst that the salt (salt) of the above-mentioned salt compound comprising carboxylic acid group can polymerize with for polyketone
Interaction forms the heterogeneous seed (heterogeneous seed) for itself having very small size, and can control and urging
The shape of the polyketane polymers synthesized around agent.
Specifically, the above-mentioned salt compound comprising carboxylic acid group is the compound for replacing salt compound with carboxylic acid group,
And salt compound may include nitrogen race (pnictogen) element, sulfur family (chalcogen) element and halogen (halogen)
One or more of element, for example, can be ammonium, oxygen, Phosphonium, sulfonium compound etc..
More specifically, the above-mentioned salt compound comprising carboxylic acid group can be indicated by following formula 2-1.
[chemical formula 2]
[Z-COOH]+[X]-
In above-mentioned chemical formula 2, Z is the alkyl with 1 to 20 carbon atom containing nitrogen, phosphorus or sulphur；[X]-be comprising
The anion (anion) of halogen, oxygen, boron, phosphorus, sulphur or combinations thereof.
It, can be into one when being used as the salt compound comprising carboxylic acid group using the compound indicated by above-mentioned chemical formula 2
Step improves the effect that reactivity is improved while preventing fouling and while not adding individual seed prepared by raising
Polyketide apparent density effect.
The above-mentioned alkyl with 1 to 20 carbon atom is not particularly limited, for example, may include having 1 to 20 carbon original
The alkyl of son, the miscellaneous alkyl with 1 to 20 carbon atom, has 6 to 20 carbon originals at the naphthenic base with 1 to 20 carbon atom
Sub aryl and the heteroaryl etc. with 3 to 20 carbon atoms.In the case, it not only easily can supply and receive original
Material, and can further improve the effect for improving reactivity while preventing fouling and not add the same of individual seed
The effect of the apparent density of polyketide prepared by Shi Tigao.
In a particular embodiment, in above-mentioned chemical formula 2, Z can be the aromatic heterocyclic radical containing nitrogen, phosphorus or sulphur or contain
The branched heteroalkyl groups of nitrogen, phosphorus or sulphur.
Also, the above-mentioned alkyl with 1 to 20 carbon atom can independently be substituted or unsubstituted, at this point, for example,
Substituent group can be alkyl with 1 to 10 carbon atom, the aryl with 6 to 20 carbon atoms and halogen radical etc..
In above-mentioned chemical formula 2, [X]-be can be bonded the ion replaced by carboxylic acid group comprising halogen, oxygen, boron,
The anion (anion) of phosphorus, sulphur or combinations thereof.
Specifically, for example, [X]-It can be the halide anion for including anion such as chlorine, bromine or iodine etc.；Including boric acid
Salt, sulfonate, carbonate, nitrate, sulfate, nitrite, phosphate, phosphite, sulphite, toluene fulfonate etc.
Oxygen anion；Anion including boron atom；Anion including phosphorus atoms；Including tetrafluoro boric acid salt anionic, four aryl
(aryl is pentafluorophenyl group (Ar=C to borate anion6F5)), sulfonic acid anion, p-methyl benzenesulfonic acid anion, trifluoroacetic acid yin
Ion, trifluoromethanesulfonic acid anion, hexafluorophosphoric acid anion, ClO4 -、ClO3 -、ClO2 -、ClO-、BrO4 -、BrO3 -、BrO2 -、
BrO-、IO4 -、IO3 -、IO2 -、IO-、CO3 2-Equal anion contain the two or more anion in halogen, oxygen, boron, p and s
Deng.
Also, the above-mentioned anion (anion) comprising halogen, oxygen, boron, phosphorus, sulphur or combinations thereof can be independently substituted
Or it is unsubstituted, at this point, for example, the example of substituent group can for 1 to 10 carbon atom alkyl, have 6 to 20 carbon
Aryl, halogen radical of atom etc..
For example, may include glycinebetaine hydrochloride (glycine by the compound that above-mentioned chemical formula 2 indicates
Betaine hydrochloride), trigonelline hydrochloride (trigonelline hydrochloride), 3- (carboxymethyl)-
1- mesitylene base -1H- imidazoles -3- bromide (3- (carboxymethyl) -1-mesityl-1H-imidazol-3-ium
Bromide), 3- (carboxymethyl) -1- (2,6- diisopropyl phenyl) -1H- imidazoles -3- bromide (3- (carboxymethyl) -
1- (2,6-diisopropylphenyl) -1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1- methyl-1 H- miaow
Azoles -3- bromide (3- (carboxymethyl) -1-methyl-1H-imidazol-3-ium bromide), 3- (carboxymethyl) -
1- methyl-1 H- benzo [d] imidazoles -3- bromide (3- (carboxymethyl) -1-methyl-1H-benzo [d]
Imidazol-3-ium bromide), 1- (carboxymethyl) pyridine -1- bromide (1- (carboxymethyl)pyridin-1-
Ium bromide), 4- carboxyl -1- picoline -1- chloride (4-carboxy-1-methylpyridin-1-ium
Chloride), 3- (carboxymethyl) -1- mesitylene base -1H- imidazoles -3- chloride (3- (carboxymethyl) -1-
Mesityl-1H-imidazol-3-ium chloride), 2- carboxy-N, N, N- trimethyl second -1- ammonium bromide (2-carboxy-
N, N, N-trimethylethan-1-aminium bromide) and (3- carboxylic propyl) triphenylphosphinebromide ((3-
One or more of carboxypropyl) triphenylphosphonium bromide).When the chemical combination using above-mentioned example
When object is used as the salt compound comprising carboxylic acid group, the effect that reactivity is improved while preventing fouling can be further improved
Fruit and improved while not adding individual seed prepared polyketide apparent density effect.
It can be with 0.1 × 10-3M to 1.0 × 10-3The molar concentration of M includes the above-mentioned salt compound comprising carboxylic acid group.
In the case, in polyketone preparation method, polymerization stability and activation grade are further enhanced, and can be with excellent
Yield prepares polyketide.
(palladium-based catalyst)
As palladium-based catalyst used in the present invention, as long as can be used for the conventional palladium-based catalyst of polyketone polymerization,
Just it is not particularly limited.
Above-mentioned palladium-based catalyst uses the catalyst for the form not being supported on carrier etc..Also, do not existed with previous load
Above-mentioned carries out the form on the modified carrier in surface using above-mentioned palladium-based catalyst with sulfonic group, but in polymerization with independent
Isolated state adds above-mentioned palladium-based catalyst.In this case, it is possible to reduce the loss of activity of palladium-based catalyst and more effective
Reduce fouling in ground.
Above-mentioned palladium-based catalyst can be the Pd catalyst for polyketone polymerization reaction.
Above-mentioned palladium-based catalyst can be the catalyst indicated by one of following chemical formula 3 to chemical formula 5.
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
In above-mentioned chemical formula 3 to 5, R1To R4It is each independently hydrogen, the alkyl with 1 to 10 carbon atom, has 1
To the alkoxy of 10 carbon atoms or the aromatic hydrocarbyl with 6 to 20 carbon atoms, Y1And Y2It is each independently halide anion
Or fluoroacetic acid root anion, Y3To Y5It is each independently hydrogen, the alkyl with 1 to 10 carbon atom, there is 1 to 10 carbon original
Organic silicon substrate of son, the naphthenic base with 3 to 10 carbon atoms or aromatic hydrocarbyl, Y with 6 to 20 carbon atoms6For with 1
Alkylidene to 10 carbon atoms, the cycloalkylidene with 3 to 10 carbon atoms or the divalent aromatic with 6 to 20 carbon atoms
Alkyl.
Specifically, above-mentioned Y3To Y5And Y6It can be substituted or unsubstituted respectively, and may include or do not include
One or more hetero atoms can be monocycle or multiring structure in the case where cyclic structure.
Palladium-based catalyst, which can be scattered in polymer solvent (for example, alcohols solvent), to be used.For example, can will be dispersed in
Palladium-based catalyst in polymer solvent is added in reactor, is then stirred at room temperature and adds olefin gas and carbon monoxide gas
Body is to be saturated, by rising the temperature of reactor to carry out the copolyreaction of alkene and carbon monoxide.
In the polymerization reaction of above-mentioned alkene and carbon monoxide, urged by the palladium base that one of above-mentioned chemical formula 3 to 5 indicates
The copolymerization activity of alkene and carbon monoxide can be improved in agent, and can prepare polyketide.
Above-mentioned palladium-based catalyst is not particularly limited, for example, can be for selected from by 1,3- bis- (2- o-methoxyphenyl phosphines)
Propane] Pd (OAc)2(1,3-Bis(di-o-methoxyphenylphosphino)propane]Pd(OAc)2) catalyst, Pd
(2- o-methoxyphenyl phosphine) (pairs of 2-phenyl-phosphine oxide) (OAc)2(Pd(di-o-methoxyphenylphosphino)
(diphenylphosphino)propane)(OAc)2) catalyst and Pd (1,3- pairs of 2-phenyl-phosphine oxide) (OAc)2(Pd(1,3-
bis(diphenylphosphino)propane)(OAc)2) catalyst composition one or more of group.In the case, alkene
The copolymerization and activity of hydrocarbon and carbon monoxide are better, moreover, by with the above-mentioned salt compound comprising carboxylic acid group
Interaction is to allow the effect for preventing scale formation to be further enhanced.Also, in the case, not only activity is excellent
It is different, but also scale formation can be further prevented and the polyketone of equably alternating polymerization can be formed.
In particular, can further improve when using the catalyst of above-mentioned example through salt (salt) and palladium catalyst
Self aggregation (self aggregation) adjusts the forms (morphology) of the polyketane polymers synthesized around catalyst
Effect.
Specifically, the solvent of above-mentioned catalyst system can be alcoholic solvent, more specifically, can be with 1-20
The alcoholic compound of carbon atom, it is, for example, possible to use methanol.In the case, polyketone preparation method have it is higher reactivity and
Activity, low boiling point therefore can be advantageous for postprocessing working procedures.
It is used to prepare the carbon monoxide-olefin polymeric of polyketide
A further embodiment of the invention is related to being used to prepare the palladium hybrid catalyst system of polyketide, and feature exists
In using alkene and carbon monoxide as reactant including the above-mentioned carbon monoxide-olefin polymeric for being used to prepare polyketide.This
When, the particular content about carbon monoxide-olefin polymeric is identical as above-mentioned content.
The preparation method of polyketone
A further embodiment of the invention is related to a kind of polyketone preparation method characterized by comprising poly- by being used to prepare
The carbon monoxide-olefin polymeric of ketone compound is scattered in the step in solvent；And to the above-mentioned carbon monoxide-olefin polymeric of dispersion be added alkene and
The step of carbon monoxide is to be polymerize.
According to the polyketone preparation method of a specific embodiment have it is above-mentioned use sulfonic group carry out the modified carrier in surface as
The form that dissimilar material is mixed with palladium-based catalyst carries out table with sulfonic group for example, having to be different from palladium-based catalyst and be supported on
The state of the catalyst of form on the modified carrier in face equably controls most as a result, when being suitable for polyketone polymerization process etc.
The shape and size of the polyketone prepared eventually, so as to improve polyketone apparent density and prevent the scale formation occurred in process,
And realize the effect of the stability and activity that improve polymerization reaction.
According to the polyketone preparation method of another specific embodiment, the salt and palladium of the above-mentioned salt compound comprising carboxylic acid group are urged
Agent interaction, to generate the heterogeneous seed of microsize in reaction solution, is formed by this time with agglomerated together
Condensate it is small-sized, be about 100nm, therefore can control the particle size and form for being formed by polyketane polymers, and
It can be improved apparent density.Above-mentioned polyketone preparation method of the invention is realized just difficult by the existing method that heterogeneous seed is added
High apparent density with obtained degree not only omits and seed is added, also only brings raising activity by additive, prevent fouling
Effect.
As described above, fouling can be prevented when using carbon monoxide-olefin polymeric of the invention to polymerize polyketone, it is prepared
The grain shape of polyketone can be conditioned according to the form of modified carrier.In this case, it is possible to which generating has height apparent close
The polymer beads of degree, therefore can be improved productivity.
It include carrying out the modified carrier or carboxylic acid in surface with sulfonic group used in the specific preparation method in polyketone
The particular content of base and salt compound and palladium-based catalyst with 5 to 40 carbon atoms is identical as above-mentioned content.
Solvent in polymerization reaction can be the alcoholic compound with 1 to 20 carbon atom.
It, can be with 0.1 × 10 in polymerization reaction-3M to 1.0 × 10-3The molar concentration of M includes above-mentioned palladium-based catalyst.
In the case, the polymerization stability of polyketone preparation method and activation grade can further be improved, and can be with good
Yield prepares polyketide.
It, can be with 0.1 × 10 in polymerization reaction-3M to 1.0 × 10-3The molar concentration of M include it is above-mentioned with sulfonic group into
The modified carrier in row surface or the salt compound of carboxylic acid group.In the case, the polymerization stability of polyketone preparation method and work
Change degree can further be improved, and can prepare polyketide with good yield.
In one embodiment, the above-mentioned carbon monoxide-olefin polymeric for being used to prepare polyketide include with sulfonic group into
When the carrier that row surface is modified, polyketide preparation method be may further include by adding sulfuric acid or chlorosulfonic acid to carrier
To prepare the step of carrying out the modified carrier in surface with sulfonic group.At this point, carrying out the modified carrier in surface about with sulfonic group
The particular content of preparation method is identical as above-mentioned content.
For example, above-mentioned alkene can be ethylene, propylene, 1- butylene, 2- butylene, 1- amylene, 1- hexene, 1- octene, the 1- last of the ten Heavenly stems
Alkene, 1- dodecylene, cyclopentene, norbornene, bicyclopentadiene, cyclo-octene, cyclododecene, styrene, Alpha-Methyl benzene second
Alkene, (methyl) acrylic acid and Arrcostab of (methyl) acrylic acid etc..Above-mentioned alkene can be used alone or be applied in combination two kinds with
On.
More specifically, ethylene, propylene, hexene, decene can be used alone or be used in mixed way.In the case, because
With the interaction yield that is excellent and can be further improved activity and polyketane polymers of catalyst.
In one embodiment, relative to 100 parts by weight ethylene mix 1 to 4 parts by weight propylene come in use,
The melting temperature of prepared polyketone can be reduced, and can be realized good thermal denaturation temperature.
Specifically, the molar ratio of above-mentioned alkene and above-mentioned carbon monoxide can be 95:5~5:95, more specifically, can be with
For 5:1~1:5.In the case, the reactivity of polyketone preparation method can further be improved.
Specifically, the content ratio of above-mentioned alkene and above-mentioned carbon monoxide can be 10~20 bars: 30~40 bars.Herein
In the case of, the reactivity of polyketone preparation method can further be improved.
Specifically, include it is above-mentioned with sulfonic group carries out the salt compound of the modified carrier in surface or above-mentioned carboxylic acid group with
The equivalent proportion of above-mentioned palladium-based catalyst can be 1:0.1 to 1:10.In the case, the reactivity and production of polyketone preparation method
Rate can further be improved.
In one embodiment, above-mentioned palladium-based catalyst and the modified carrier in surface and above-mentioned palladium base are carried out with sulfonic group
The equivalent proportion of catalyst can be 1:0.1 to 1.2, and more specifically, equivalent proportion can be 1:0.1 to 1:1.2.In above range
When inside carrying out polymerizeing using the polyketone of carbon monoxide-olefin polymeric, fouling can be prevented and obtain higher catalytic activity and polyketone
The high apparent density of polymer.
In another embodiment, above-mentioned palladium-based catalyst and working as including the above-mentioned salt compound comprising carboxylic acid group
Measuring ratio can be 1:0.1 to 1:10.In the case, the reactivity of polyketone preparation method and yield can further be changed
It is kind.
Specifically, reaction temperature may remain in 50 DEG C~150 DEG C, more specifically, may remain in 70 DEG C~130 DEG C
In the range of.In the case, the reactivity of polyketone preparation method can further be improved.
Specifically, polymerization reaction can press since carbon monoxide and some alkene are gas at the temperature disclosed above
It is carried out in power reactor.In the case, the reactivity of polyketone preparation method and activation grade can further be improved.
Specifically, reactor internal pressure can be 200atm or smaller, more specifically 100atm or smaller.In this feelings
Under condition, the reactivity and activation grade of polyketone preparation method can further be improved.
Specifically, in above-mentioned polyketone preparation method, the above-mentioned palladium hybrid catalyst system for being used to prepare polyketone can be with
Exist with the state being scattered in solvent, with catalytic polymerization.
Specifically, solvent can be alcoholic solvent, more specifically, the alcohol compound with 1-20 carbon atom can be
Object, it is, for example, possible to use methanol.In the case, polyketone preparation method has higher reactivity and active, low boiling point, because
This, can be advantageous for postprocessing working procedures.
In one embodiment, the above-mentioned carrier for carrying out surface modification with sulfonic group is not dissolved in organic solvent,
Therefore can exist in a form of slurry.
It in another embodiment, can be with using the polyketone preparation method of the above-mentioned salt compound comprising carboxylic acid group
For seedage method is not added.
Polyketane polymers
A further embodiment of the invention is related to the polyketane polymers by being formed according to above-mentioned polyketone preparation method.
In one embodiment, can be by the polyketane polymers that above-mentioned polyketone preparation method is formed makes above-mentioned to use sulphur
Acidic group carries out the modified carrier in surface and interacts to prepare as dissimilar materials and palladium-based catalyst, and can have improvement
Apparent density.
In another embodiment, the form of the polyketane polymers formed by above-mentioned polyketone preparation method can pass through
The tiny size that salt and the palladium catalyst interaction of the above-mentioned salt compound comprising carboxylic acid group simultaneously agglomerate to be formed simultaneously
Heterogeneous seed is controlled.It is about 100nm at this point, being formed by the small-sized of condensate, therefore, it is poly- is formed by polyketone
The apparent density for closing object can be very big, can be about 0.1g/ml to 0.5g/ml, for example, it may be about 0.27g/ml to 0.47g/
ml。
Embodiment
In the following, embodiment the composition and effect that the present invention will be described in more detail through the invention.It is understood, however, that
It is that this is merely to illustrate that and illustrates, without the limitation present invention should be construed as.
Preparation example 1: preparation carries out the modified carrier in surface with sulfonic group
(preparing carrier)
By the methanol (Methanol) of 500mL, the H of 90mL2O, the Ammonia (Ammonium of 32mL
Hydroxide solution) and 1.2g cetyl trimethylammonium bromide (Hexadecyltrimethyl ammonium
Bromide, CTAB) it is added sequentially in 1L beaker and with 300RPM stirring 30 minutes.While being stirred with 300RPM, it is added former
Tetraethyl orthosilicate (Tetraethyl orthosilicate, TEOS).While stirring with 300RPM, 24 are reacted at room temperature
Hour.With the synthesized silica (Si lica) of centrifuge separation, is cleaned with methanol and dried in an oven.Then it will do
Dry silica is calcined 5 hours at 550 DEG C.Silica by preparation by calcining in mortar fine gtinding and
It is heated 12 hours at 850 DEG C in Ar furnace, to prepare carrier.
Benzylmagnesium chloride (benzyl magnesium chloride) is added to silica supports prepared above
In, in nitrogen atmosphere, it is stirred at room temperature to generate reaction, to be surface-treated, benzyl is connected to silica
On the surface of carrier.
(sulfonation)
Sulfuric acid is added in the silica supports for being connected with benzyl prepared as described above, is stirred at room temperature overnight,
Modified carrier (the 1.8 μm of SiO in surface are carried out with sulfonic group with preparation2-SO3H).The use so prepared is confirmed by SEM photograph
Sulfonic group carries out the modified carrier in surface, and the results are shown in Fig. 1.
Preparation example 2: preparation carries out the modified carrier in surface with sulfonic group
(preparing carrier)
By zinc nitrate hexahydrate (Zinc nitrate hexahydrate, 1eq, 0.1mol, 297.49g/mol,
It 29.75g) is dissolved in the methanol of 500mL to prepare zinc nitrate solution (Zinc nitrate solution), by cetyl
Trimethylammonium bromide (Hexadecyltrimethyl ammonium bromide；CTAB, 99+%, 0.25eq, 0.025mol,
364.45g/mol, 9.1g) it is dissolved in the methanol of 125mL to prepare solution (CTAB solution).Also, by 2-methylimidazole
(4eq, 0.4mol, 82.10g/mol, 32.84g) is dissolved in the methanol of 500mL to prepare solution (2-methylimidazole solution).
100mL zinc nitrate solution prepared above is added in the RB (5) of 250mL, while being stirred with 1100rpm
The CTAB solution of 20mL and the 2-methylimidazole solution of 100mL are sequentially added, is also stirred 5 minutes.Hereafter, stop stirring, and
Mixture (room temperature) is stood 18 hours in the case where not vibrating, then discards supernatant liquid, prepared by centrifuge separation
ZIF-8.Isolated ZIF-8 carrier is cleaned twice with methanol, it is dry with vacuum pump (Vacuum pump), it is then used as template.
After flame dry 100mL Schlenk bottle (Schlenk flask), argon gas is added.Then, it is added sequentially into bottle
Pd(PPh3)2Cl2(10mol%, 0.024mmol, 701.90g/mol, 0.0168g), CuI (10mol%, 0.024mmol,
190.45g/mol, 0.0046g) and 0.4g the ZIF-8 as carrier prepared above.Later, it is further added thereto
Triethylamine (the Triethylamine of 60mL；TEA disperse 1.5 hours) and in ultrasonoscope to prepare dispersion liquid.To above-mentioned point
In dispersion liquid be added four-(4- ethynyl phenyl)-methane (tetra- (4-ethynylphenyl)-methane, 1eq,
0.24mmol, 416.51g/mol, 0.1g) and Isosorbide-5-Nitrae-diiodo-benzene (Isosorbide-5-Nitrae-Diiodobenzene, 2eq, 0.48mmol,
329.90g/mol, 0.1584g), disperse 5 minutes in ultrasonoscope again.Hereafter, mixture is made to react 24 at 100 DEG C small
When, it is cooled to room temperature, and being separated by centrifuge includes the upper surface of synthesized carrier, that is, ZIF-8 prepared as the hollow of template
The carrier (ZIF-8@MON) of structural body form.By acetone (Acetone), methylene chloride (Dichloromethane), methanol
(Methanol) and the sequence of acetone (Acetone) is using synthesized carrier is cleaned twice, then dry with vacuum pump.
Further, carrier (ZIF-8@MON, 0.16g) prepared above and 15mL methanol are added in Falcon pipe simultaneously
Then the acetic acid (Acetic acid) of 20mL is added thereto, is etched while stirring the mixture for 1 hour for dispersion
(Etching), further to promote to be formed micropore organic network polymer (microporous organic in the carrier
network).Then, it is separated with centrifuge through overetched carrier (HMON), is cleaned 10 times with methanol (MeOH), it is clear with acetone
It washes twice, it is dry with vacuum pump, to be used for sulfonation.
(sulfonation)
Flame dries 100mL Schlenk bottle, and argon gas is then added.It is added into above-mentioned bottle as including micropore organic network
The dichloro of carrier (the HMON 0.04g) and 20mL of the hollow structure of polymer (microporous organic network)
Methane is simultaneously fully dispersed.After distribution, 0 DEG C is cooled the temperature to, the ClSO of 0.6mL is very slowly added3H rises to temperature
Room temperature, and reacted 1.5 hours at Ar.After temperature is down to 0 DEG C again, remaining ClSO is quenched with methanol3H.Pass through centrifugation
Machine separation carries out the modified carrier in surface with sulfonic group, with by methanol and H2The solution that O is mixed with the ratio of 2:1 is in pH7
Under cleaned.It is dry with vacuum pump after being cleaned twice again with methanol.
By using sulphur prepared by SEM ((a) of Fig. 3 partially and the part (b)) and the confirmation of TEM (part (c) of Fig. 3) photo
Acidic group carries out the modified carrier in surface, and the results are shown in Fig. 3.
Preparation example 3: preparation carries out the modified carrier in surface with sulfonic group
(preparing carrier)
200mL ethyl alcohol (Ethanol) is added into 250mL round-bottomed flask, the H of the distillation of 23mL is then added2O and 7mL
Ammonia (28-30%), and with 300RPM stirring 30 minutes.Later, the tetraethyl orthosilicate of 18mL is added
(Tetraethyl orthosilicate；TEOS, 1eq, 0.081mol, 208.33g/mol 0.933g/mL) and at room temperature
It quickly stirs 18 hours and is reacted.After acetic acid is dripped in addition 5,100mL hexane and 150mL methylene chloride is added and shakes,
Then with the silica of centrifuge separation agglutination, the ratio to 1:1 mixes mixed solution made of hexane and methylene chloride
Cleaning three times, will be heated overnight and dry at 80 DEG C in an oven, to prepare silica supports as template.
After the dry 100mL Schlenk bottle of flame, argon gas is added.Then, Pd (PPh is added in sequence3)2Cl2(10mol%,
0.024mmol, 701.90g/mol, 0.0168g), CuI (10mol%, 0.024mmol, 190.45g/mol, 0.0046g) and
The silica supports of the upper surface of 0.6g preparation.Then, triethylamine (Triethylamine is further added；TEA, 60mL),
Fully dispersed 1.5 hours in ultrasonoscope, to prepare dispersion liquid.Four-(4- ethynyl phenyl)-methane are added to above-mentioned dispersion
(1eq, 0.24mmol, 416.51g/mol, 0.1g) and Isosorbide-5-Nitrae-diiodo-benzene (2eq, 0.48mmol, 329.90g/mol,
0.1584g), disperse 5 minutes in ultrasonoscope again.Later, after being reacted 24 hours at 100 DEG C, reaction product is cooling
To room temperature, preparation of the upper surface of using centrifuge separation synthesized includes silica supports as template and including the organic net of micropore
Carrier (the SiO of network polymeric layer2@MON).By acetone (Acetone), methylene chloride (Dichloromethane), methanol and third
The sequence of ketone is then dry with vacuum pump using synthesized carrier is cleaned twice.
(sulfonation)
After the dry 100mL Schlenk bottle of flame, argon gas is added.It include silica supports conduct to being added in above-mentioned bottle
Template and carrier (SiO including micropore organic network polymeric layer2@MON, 0.72g) and 60mL methylene chloride, sufficiently point
It dissipates.After distribution, 0 DEG C is cooled the temperature to, the ClSO of 1.8mL is very slowly added3Temperature is warmed to room temperature by H, and at Ar
Carry out reaction 1.5 hours.After temperature is down to 0 DEG C again, methanol is added so that remaining ClSO is quenched3H.It is separated by centrifuge
The modified carrier in surface is carried out with sulfonic group, with by methanol (Methanol) and H2O is existed with the solution that the ratio of 2:1 mixes
It is cleaned under pH7.It is dry with vacuum pump after being cleaned twice again with methanol.
Preparation example 4: preparation carries out the modified carrier in surface with sulfonic group
(reactant that preparation is used to prepare carrier)
Purified styrene: the stabilizer (4- tert-butyl catechol) of styrene is removed
30mL methylene chloride is added in 200mL styrene.The 1M sodium hydroxide of 50mL is added into above-mentioned mixed solution
Solution extracts 3 times.After being dehydrated with magnesium sulfate, methylene chloride is removed with vacuum pump.Stop light, then the freezen protective under argon.
Purifying divinylbenzene: the stabilizer (4- tert-butyl catechol) of divinylbenzene is removed
10mL methylene chloride is added in 80mL styrene.The 1M sodium hydroxide that 50mL is added into above-mentioned mixed solution is molten
Liquid extracts 3 times.After being dehydrated with magnesium sulfate, methylene chloride is removed with vacuum pump.Stop light, then the freezen protective at Ar.
(preparing carrier)
After the dry mono- neck Schlenk bottle of 100mL of flame, argon gas is added.After distilled water is added to this, purifying above is added
Styrene (Styrene) and divinylbenzene (Divinylbenzene), be heated to 65 DEG C.Removing while being blown into argon gas
After gas in solution, stirring at least 15 minutes until form lotion.It is added in above-mentioned mixed solution and is dissolved with potassium peroxydisulfate
Distilled water and reacted 20 hours at 65 DEG C.After the reaction, it puts it into refrigerator 2 hours, is then warmed to room temperature temperature.
After the dilution of about 80mL ethyl alcohol, with the prepared Polystyrene powder (Polystyrene powder) of centrifuge separation, second is used
Alcohol is washed 5 times and is dried with vacuum pump.
(sulfonation)
After the dry mono- neck Schlenk bottle of 50mL of flame, argon gas is added.Polystyrene (Polystyrene is added
Powder) powder and sulfuric acid (sulfuric acid) are then ultrasonically treated 30 minutes.At least 18 hours are stirred at 40 DEG C simultaneously
It is cooled to room temperature.With methanol dilution and it is centrifuged to sink.With by methanol and H2The solution that O is mixed with the ratio of 2:1 is in pH7
Under cleaned.It is dry with vacuum pump after being cleaned twice again with methanol.
Preparation example 5: it prepares without carrying out the modified carrier in surface
Other than omitting sulfonation procedure, remaining prepares carrier in method identical with preparation example 2.
The physical property of the carrier prepared in above-mentioned preparation example 1 to 5 is shown in the following table 1.
Table 1
Embodiment 1
Pd (the 1,3- bis- (two (2- methoxyphenyl) phosphino- propane) (OAc) of 1.0mg is added in the methanol of 10mL2With
What is prepared in the upper surface of 2.7mg preparation example 1 carries out modified carrier (the 1.8 μm of SiO in surface2-SO3H it) is at room temperature mixed
It closes, to prepare carbon monoxide-olefin polymeric.
Above-mentioned carbon monoxide-olefin polymeric is fitted into high-pressure reactor (~50mL size), organizes holding reactor, and at room temperature
25 bars of ethylene gas and 35 bars of CO are added while stirring to be saturated.Temperature of reactor is risen to 90 DEG C, is gathered
Close reaction about 15 hours.After the reaction, the polyketone powder (activity: 33.84Kg/g-Pd of 4.8g is obtained；1.29kg/g- catalyst,
Apparent density: 0.297g/mL)
Through the foregoing embodiment 1 method prepare polyketone after, recycling is used in the reaction to be prepared in preparation example 1
Sulfonation carrier it is shown in Figure 2 come the SEM photograph shot.
The photo of prepared polyketone is as shown in figure 5, and with the naked eye confirming fouling not occurring.
Embodiment 2
Pd (1,3- bis- (two (2- methoxyphenyl) phosphino- propane) in addition to 1.5mg is added in the methanol of 10mL
(OAc)2With carrier (the 1.8 μm of SiO for carrying out surface and being modified of 4.0mg prepared in preparation example 12-SO3H) come at room temperature
It is mixed, to prepare except carbon monoxide-olefin polymeric, remaining is carried out in method identical with above-described embodiment 1.After the reaction, it obtains
Obtain the polyketone powder (activity: 23.26kg/g-Pd of 4.95g；0.90kg/g- catalyst, apparent density: 0.309g/mL).
Embodiment 3
Pd (1,3- bis- (two (2- methoxyphenyl) phosphino- propane) in addition to 0.6mg is added in the methanol of 20mL
(OAc)2With 0.8mg prepared in preparation example 2 carry out except the modified carrier in surface, remaining with 1 phase of above-described embodiment
Same method carries out.After the reaction, the polyketone powder (activity: 61.23Kg/g-Pd of 5.6g is obtained；4.08kg/g- catalyst, table
See density: 0.374g/mL).
Through the foregoing embodiment 3 method prepare polyketone before, recycle prepared in preparation example 2 carried out with sulfonic group
The modified carrier in surface is shown in part (a) of Fig. 4 come the SEM photograph shot.
Through the foregoing embodiment 3 method prepare polyketone after, recycling is used in the reaction to be prepared in preparation example 2
Carry out the modified carrier in surface with sulfonic group and be shown in part (b) of Fig. 4 come the SEM photograph shot.
Referring to Fig. 4, preparation example 2 before reactions to carry out the diameter of the carrier of surface modification with sulfonic group be 521nm
And with a thickness of 20nm, after reacting, above-mentioned diameter becomes 625nm and above-mentioned thickness becomes 120nm.
Embodiment 4
Pd (1,3- bis- (two (2- methoxyphenyl) phosphino- propane) in addition to 1.0mg is added in the methanol of 10mL
(OAc)2Carried out except the modified carrier in surface with what is prepared in the upper surface of 1.1mg preparation example 3, remaining with above-described embodiment 1
Identical method carries out.After the reaction, the polyketone powder (activity: 26.53kg/g-Pd of 3.7g is obtained；1.86kg/g- catalyst,
Apparent density: 0.310g/mL).
The photo of prepared polyketone is as shown in fig. 7, and with the naked eye confirming fouling not occurring.
Embodiment 5
Pd (1,3- bis- (two (2- methoxyphenyl) phosphino- propane) in addition to 1.5mg is added in the methanol of 10mL
(OAc)2Modified carrier is mixed at room temperature with the progress surface for preparing in the upper surface of 1.0mg preparation example 4, with preparation
Except carbon monoxide-olefin polymeric, remaining is carried out in method identical with above-described embodiment 1.After the reaction, the polyketone powder of 2.5g is obtained
Last (activity: 11.94kg/g-Pd；1.02kg/g- catalyst, apparent density: 0.318g/mL).
Embodiment 6
In addition to replacing Pd (1,3- bis- (two (2- methoxyphenyl) phosphino- propane) (OAc)2Using the Pd of 0.8mg, (1,3- is bis-
Diphenylphosphine propane) (OAc)2Except palladium catalyst, remaining is carried out in method identical with above-described embodiment 1.It is reacting
Afterwards, the polyketone powder (activity: 1.89Kg/g-Pd of 0.265g is obtained；0.135kg/g- catalyst, apparent density: 0.389g/
mL)。
Comparative example 1
Other than being added without when preparing carbon monoxide-olefin polymeric and carrying out the modified carrier in surface, remaining with above-mentioned implementation
The identical method of example 2 carries out (catalyst activity: 0.478kg/g-Pd).
Comparative example 2
P-methyl benzenesulfonic acid is added come other than generating reaction in addition to replacing carrying out the modified carrier in surface, remaining with above-mentioned reality
Apply the progress of the identical method of example 2.After the reaction, the polyketone powder (activity: 6.27kg/g-Pd of 1.33g is obtained；0.814kg/g-
Catalyst).
The photo of prepared polyketone is as shown in figure 8, and with the naked eye confirmation generation fouling.
Comparative example 3
Pd (dmppp) (OAc) in addition to 1.5mg is added in the methanol of 10mL2With not including for the upper surface of 0.4mg preparation
The carrier of sulfonic preparation example 5, and being mixed at room temperature to prepare except carbon monoxide-olefin polymeric, remaining with above-mentioned reality
It applies the identical method of example 2 and carries out (catalyst activity: 0.771kg/g-Pd).
Comparative example 4
Other than Amberlyst 15 is added when preparing carbon monoxide-olefin polymeric as with sulfonic group modified carrier,
It is remaining to be carried out in method identical with above-mentioned comparative example 2.After the reaction, the polyketone powder (activity: 3.01kg/g- of 0.64g is obtained
Pd；0.388kg/g- catalyst).
The photo of prepared polyketone is as shown in figure 9, and with the naked eye confirmation generation fouling.
Table 2
Embodiment 7
By [bis- (two-o-methoxyphenyl phosphino-s) propane of 1,3-] Pd (OAc) in high-pressure reactor (50ml size)2It urges
Agent (2 μm of ol) is scattered in methanol (MeOH, 10ml), then organizes holding reactor, and 25 bars are added while being stirred at room temperature
Ethylene gas and 35 bars of carbon monoxide (CO) are saturated.Later, as shown in Table 3 below add is added to above-mentioned reactor
Add agent, the temperature of reactor is risen to 90 DEG C, is carried out polymerization reaction about 15 hours under 62 bars.It is completed in above-mentioned polymerization reaction
Afterwards, reaction product is cooled to room temperature, is filtered, and is 1 hour dry in 65 DEG C of baking oven, obtain polyketane polymers powder.
Embodiment 8 to 16 and comparative example 5 to 12
Other than changing the composition for the ingredient being added in reaction as shown in table 3 below, remaining is with side same as Example 7
Method carries out polymerization reaction.
Table 3
The type of the palladium catalyst used in above-described embodiment 7 to 22 and comparative example 5 to 12 is as follows.
[catalyst A]
: bis- (the 2- o-methoxyphenyl phosphine) propane of 1,3-] Pd (OAc)2
[catalyst B]
: Pd (2- o-methoxyphenyl phosphine) (pairs of 2-phenyl-phosphine oxide) (OAc)2
[catalyst C]
: Pd (1,3- pairs of 2-phenyl-phosphine oxide) (OAc)2
[catalyst D]
:1,3-Bi s(di-o-methoxyphenylphosphino)propane]Pd(Cl)2
The type of the additive used in above-described embodiment 7 to 22 and comparative example 5 to 12 is as follows.
[additive 1A]
: glycinebetaine hydrochloride (glycine betaine hydrochloride)
[additive 1B]
: 3- (carboxymethyl) -1- mesitylene base -1H- imidazoles -3- chloride (3- (carboxymethyl) -1-
mesityl-1H-imidazol-3-ium chloride)
[additive 1C]
: trigonelline hydrochloride (trigonell ine hydrochloride)
[additive 1D]
: 3- (carboxymethyl) -1- (2,6- diisopropyl phenyl) -1H- imidazoles -3- bromide (3- (carboxymethyl) -
1-(2,6-diisopropylphenyl)-1H-imidazol-3-ium bromide)
[additive 1E]
: 3- (carboxymethyl) -1- methyl-1 H- imidazoles -3- bromide (3- (carboxymethyl) -1-methyl-1H-
imidazol-3-ium bromide)
[additive 1F]
: 3- (carboxymethyl) -1- methyl-1 H- benzo [d] imidazoles -3- bromide (3- (carboxymethyl) -1-
methyl-1H-benzo[d]imidazol-3-ium bromide)
[additive 1G]
: 1- (carboxymethyl) pyridine -1- bromide (1- (carboxymethyl) pyridin-1-ium bromide)
[additive 1H]
: 4- carboxyl -1- picoline -1- chloride (4-carboxy-1-methylpyridin-1-ium chloride)
[additive 1I]
: 3- (carboxymethyl) -1- mesitylene base -1H- imidazoles -3- chloride (3- (carboxymethyl) -1-
mesityl-1H-imidazol-3-ium chloride)
[additive 1J]
: 2- carboxy-N, N, N- trimethyl second -1- ammonium bromide (2-carboxy-N, N, N-trimethylethan-1-
aminium bromide)
[additive 1K]
: (3- carboxylic propyl) triphenylphosphinebromide ((3-carboxypropyl) triphenylphosphonium
bromide)
[additive 2]
[additive 3]
[additive 4]
[additive 5]
[additive 6]
[additive 7]
The activation grade of the polymerization reaction carried out in above-described embodiment 7 to 22 and comparative example 5 to 12 is shown in the following table 4.
Table 4
By upper table 3 and table 4 it is found that confirming that packet can be used in the embodiment 7 to 22 of polyketone preparation method according to the present invention
Salt compound containing carboxylic acid group prevents fouling as additive, and in polymerization reaction, stability and activity are excellent.
In contrast, confirm and low-down activity is presented in the comparative example 5 for not including additive, pair used as strong acid
As the comparative example 6 and 7 of additive fouling occurs for toluenesulfonic acid (p-toluenesulfonic acid, TsOH).Also, confirm
Because and do not include carboxylic acid group or do not include salt compound due to have the use additive 3 of the structure entirely different with the present invention to
The comparative example 8 to 12 of additive 7 has low-down activity, therefore, it is difficult to be sufficiently formed polyketane polymers, and fouling occurs.
Simple deformation and change of the invention can easily be implemented by those of ordinary skill in the art, also, this change
Shape or change can be considered included in the field of the invention.
Claims (27)
1. a kind of carbon monoxide-olefin polymeric for being used to prepare polyketide characterized by comprising
Salt compound has 5 to 40 carbon atoms, including carrying out the modified carrier in surface or carboxylic acid group with sulfonic group；And
Palladium-based catalyst.
2. the carbon monoxide-olefin polymeric according to claim 1 for being used to prepare polyketide, which is characterized in that above-mentioned to use sulphur
It includes being bonded to carrier by the functional group that one of following chemical formula 1-1 to 1-3 is indicated that acidic group, which carries out the modified carrier in surface,
The structure on surface:
[chemical formula 1-1]
*-SO3H
In above-mentioned chemical formula 1-1, * refers to the part being bonded with carrier surface.
[chemical formula 1-2]
In above-mentioned chemical formula 1-2, R21To R26It is each independently hydrogen or C1~C20 alkyl；* refer to and be bonded with carrier surface
Part.
[chemical formula 1-3]
In above-mentioned chemical formula 1-3, R31To R34It is each independently hydrogen or C1~C20 alkyl；* refer to and be bonded with carrier surface
Part..
3. the carbon monoxide-olefin polymeric according to claim 2 for being used to prepare polyketide, which is characterized in that above-mentioned carrier
Including silica, zeolite, graphite, carbon black, graphene, carbon nanotube, active carbon, polystyrene, the polymerization of micropore organic network
One of object, metal organic framework, zeolite imidazole ester skeleton, covalent organic framework and the cellulose-containing biopolymer of packet with
On.
4. the carbon monoxide-olefin polymeric according to claim 3 for being used to prepare polyketide, which is characterized in that above-mentioned to use sulphur
Acidic group carries out the modified carrier in surface to be including having to be gathered by the micropore organic network of the following chemical formula 1-4 unit repeatedly indicated
Close the hollow structure of object:
[chemical formula 1-4]
In above-mentioned chemical formula 1-4, A is the connection site of atom.
5. the carbon monoxide-olefin polymeric according to claim 3 for being used to prepare polyketide, which is characterized in that above-mentioned to use sulphur
Acidic group carry out the modified carrier in surface include silica supports and be formed in above-mentioned surface of silica support have by
The micropore organic network polymeric layer for the unit repeatedly that following chemical formula 1-5 is indicated:
[chemical formula 1-5]
In above-mentioned chemical formula 1-5, A' each independently represent the atom being bonded with carrier connection site or repeatedly unit it
Between connection site, at least one of above-mentioned A' is at least one in the connection site for the atom being bonded with carrier and above-mentioned A'
A is repeatedly the connection site between unit.
6. the carbon monoxide-olefin polymeric according to claim 3 for being used to prepare polyketide, which is characterized in that above-mentioned to use sulphur
It includes with the polystyrene compounds by the following chemical formula 1-6 unit repeatedly indicated that acidic group, which carries out the modified carrier in surface:
[chemical formula 1-6]
In above-mentioned chemical formula 1-6, R6For sulfonic group, p-methyl benzenesulfonic acid base or benzene sulfonic acid base, n is 10 to 20,000.
7. the carbon monoxide-olefin polymeric according to claim 3 for being used to prepare polyketide, which is characterized in that above-mentioned to use sulphur
Acidic group carries out the modified carrier in surface and passes through by silica supports and by one of above-mentioned chemical formula 1-2 to chemical formula 1-3
The functional group Si-C of expression is bonded.
8. the carbon monoxide-olefin polymeric according to claim 1 for being used to prepare polyketide, which is characterized in that above-mentioned to use sulphur
Acidic group, which carries out the modified carrier in surface and above-mentioned palladium-based catalyst, has the form being scattered in solvent.
9. the carbon monoxide-olefin polymeric according to claim 8 for being used to prepare polyketide, which is characterized in that above-mentioned solvent
It is the alcoholic compound with 1-20 carbon atom.
10. the carbon monoxide-olefin polymeric according to claim 1 for being used to prepare polyketide, which is characterized in that including upper
It states carboxylic acid group and the salt compound with 5 to 40 carbon atoms is indicated by following chemical formula 2:
[chemical formula 2]
[Z-COOH]+[X]-
In above-mentioned chemical formula 2, Z is the alkyl with 1 to 20 carbon atom containing nitrogen, phosphorus or sulphur；[X]-For comprising halogen,
The anion of oxygen, boron, phosphorus, sulphur or combinations thereof.
11. the carbon monoxide-olefin polymeric according to claim 10 for being used to prepare polyketide, which is characterized in that above-mentioned
In chemical formula 2, Z is aromatic heterocycle.
12. the carbon monoxide-olefin polymeric according to claim 10 for being used to prepare polyketide, which is characterized in that above-mentioned
In chemical formula 2, Z is branched heteroalkyl groups.
13. the carbon monoxide-olefin polymeric according to claim 10 for being used to prepare polyketide, which is characterized in that by above-mentioned
The compound that chemical formula 2 indicates includes glycinebetaine hydrochloride, trigonelline hydrochloride, the equal front three of 3- (carboxymethyl) -1-
Phenyl -1H- imidazoles -3- bromide, 3- (carboxymethyl) -1- (2,6- diisopropyl phenyl) -1H- imidazoles -3- bromide, 3- (carboxylic
Methyl) -1- methyl-1 H- imidazoles -3- bromide, 3- (carboxymethyl) -1- methyl-1 H- benzo [d] imidazoles -3- bromide, 1- (carboxylic
Methyl) pyridine -1- bromide, 4- carboxyl -1- picoline -1- chloride, 3- (carboxymethyl) -1- mesitylene base -1H- miaow
Azoles -3- chloride, 2- carboxy-N, N, one of N- trimethyl second -1- ammonium bromide and (3- carboxylic propyl) triphenylphosphinebromide with
On.
14. the carbon monoxide-olefin polymeric according to claim 1 for being used to prepare polyketide, which is characterized in that above-mentioned palladium
Base catalyst is indicated by one of following chemical formula 3 to chemical formula 5:
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
In above-mentioned chemical formula 3 to 5, R1To R4It is each independently hydrogen, the alkyl with 1 to 10 carbon atom, has 1 to 10
The alkoxy of a carbon atom or aromatic hydrocarbyl with 6 to 20 carbon atoms, Y1And Y2It is each independently halide anion or oxygen
Acetic acid anion, Y3To Y5It is each independently hydrogen, the alkyl with 1 to 10 carbon atom, with 1 to 10 carbon atom
Organic silicon substrate, the naphthenic base with 3 to 10 carbon atoms or aromatic hydrocarbyl, Y with 6 to 20 carbon atoms6For with 1 to 10
The alkylidene of a carbon atom, the cycloalkylidene with 3 to 10 carbon atoms or the divalent aromatic hydrocarbon with 6 to 20 carbon atoms
Base.
15. the carbon monoxide-olefin polymeric according to claim 1 for being used to prepare polyketide, which is characterized in that above-mentioned palladium
Base catalyst is selected from by bis- (the 2- o-methoxyphenyl phosphine) propane of 1,3-] Pd (OAc)2Catalyst, Pd (2- o-methoxyphenyl
Phosphine) (pairs of 2-phenyl-phosphine oxide) (OAc)2Catalyst and Pd (1,3- pairs of 2-phenyl-phosphine oxide) (OAc)2In the group of catalyst composition
More than one.
16. the carbon monoxide-olefin polymeric according to claim 1 for being used to prepare polyketide, which is characterized in that including upper
State the equivalent proportion of salt compound and above-mentioned palladium-based catalyst that the modified carrier in surface or above-mentioned carboxylic acid group are carried out with sulfonic group
For 1:0.1 to 1:10.
17. a kind of palladium hybrid catalyst system for being used to prepare polyketide, which is characterized in that including according to claim 1
The carbon monoxide-olefin polymeric for being used to prepare polyketide, uses alkene and carbon monoxide as reactant.
18. a kind of polyketone preparation method characterized by comprising
The step in solvent is dispersed by the carbon monoxide-olefin polymeric according to claim 1 for being used to prepare polyketide；
And
The step of alkene and carbon monoxide are to be polymerize is added to the above-mentioned carbon monoxide-olefin polymeric of dispersion.
19. polyketone preparation method according to claim 18, which is characterized in that above-mentioned solvent is with 1 to 20 carbon original
The alcoholic compound of son.
20. polyketone preparation method according to claim 18, which is characterized in that with 0.1 × 10-3M to 1.0 × 10-3M's rubs
It includes the above-mentioned salt compound that carrier or carboxylic acid group that surface is modified are carried out with sulfonic group that your concentration, which is added,.
21. polyketone preparation method according to claim 18, which is characterized in that
The above-mentioned carbon monoxide-olefin polymeric for being used to prepare polyketide includes carrying out the modified carrier in surface with sulfonic group,
The carrier that surface is modified is carried out with sulfonic group to prepare and sulfuric acid or chlorosulfonic acid is added to carrier.
22. polyketone preparation method according to claim 18, which is characterized in that with 0.1 × 10-3M to 1.0 × 10-3M's rubs
Your concentration includes above-mentioned palladium-based catalyst.
23. polyketone preparation method according to claim 18, which is characterized in that
Above-mentioned alkene is or mixtures thereof ethylene, propylene, hexene, decene.
24. polyketone preparation method according to claim 18, which is characterized in that with 20~30 bars: 30~40 bars of ratio
Above-mentioned alkene and above-mentioned carbon monoxide is added.
25. polyketone preparation method according to claim 18, which is characterized in that
Above-mentioned polymerization reaction executes at 50 DEG C to 150 DEG C.
26. polyketone preparation method according to claim 18, which is characterized in that
Above-mentioned polyketone preparation method is that seedage method is not added.
27. a kind of polyketane polymers, which is characterized in that formed, had by polyketone preparation method according to claim 18
There is 0.1 to 0.5g/ml apparent density.
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| KR10-2017-0061232 | 2017-05-17 | ||
| KR1020170061232A KR101828292B1 (en) | 2017-05-17 | 2017-05-17 | Pd CATALYST SYSTEMS FOR POLYKETONE SYNTHESIS, METHOD OF MANUFACTURING POLYKETONE COMPOUND USING THE SAME, AND POLYKETONE POLYMER |
| PCT/KR2017/009060 WO2018034549A1 (en) | 2016-08-19 | 2017-08-18 | Catalyst composition for preparing polyketone compound, palladium mixed catalyst system, method for preparing polyketone compound using same, and polyketone polymer |
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| CN114044895A (en) * | 2021-12-15 | 2022-02-15 | 黄河三角洲京博化工研究院有限公司 | Polyketone with high elongation at break and synthesis method thereof |
| CN115536836A (en) * | 2022-11-02 | 2022-12-30 | 黄河三角洲京博化工研究院有限公司 | Preparation method of polyketone with high bulk density |
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| CN115536836A (en) * | 2022-11-02 | 2022-12-30 | 黄河三角洲京博化工研究院有限公司 | Preparation method of polyketone with high bulk density |
| CN115536836B (en) * | 2022-11-02 | 2024-07-26 | 黄河三角洲京博化工研究院有限公司 | Preparation method of polyketone with high bulk density |
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