KR101746030B1 - Solid catalyst for polyketone polymerization and its manufacturing method - Google Patents
Solid catalyst for polyketone polymerization and its manufacturing method Download PDFInfo
- Publication number
- KR101746030B1 KR101746030B1 KR1020160014194A KR20160014194A KR101746030B1 KR 101746030 B1 KR101746030 B1 KR 101746030B1 KR 1020160014194 A KR1020160014194 A KR 1020160014194A KR 20160014194 A KR20160014194 A KR 20160014194A KR 101746030 B1 KR101746030 B1 KR 101746030B1
- Authority
- KR
- South Korea
- Prior art keywords
- bis
- acid
- group
- methoxyphenyl
- phosphine
- Prior art date
Links
- 229920001470 polyketone Polymers 0.000 title claims abstract description 25
- 239000011949 solid catalyst Substances 0.000 title claims description 10
- 238000006116 polymerization reaction Methods 0.000 title abstract description 15
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000003446 ligand Substances 0.000 claims abstract description 28
- -1 Bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diyl bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) Chemical compound 0.000 claims abstract description 17
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 17
- 150000001450 anions Chemical class 0.000 claims abstract description 14
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 14
- 229910052696 pnictogen Inorganic materials 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 5
- HFEAMIKDDWKNAG-UHFFFAOYSA-N bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1PC1=CC=CC=C1OC HFEAMIKDDWKNAG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000002685 polymerization catalyst Substances 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 2
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 description 2
- 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
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- NVVMHYYKCATJAN-UHFFFAOYSA-K 3-oxobutanoate;ruthenium(3+) Chemical compound [Ru+3].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O NVVMHYYKCATJAN-UHFFFAOYSA-K 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- YLDJNDYRGPTCKV-UHFFFAOYSA-N (2-diphenylphosphanylcyclohexyl)-diphenylphosphane Chemical compound C1CCCC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YLDJNDYRGPTCKV-UHFFFAOYSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- SXXPTCXIFIOPQF-UHFFFAOYSA-N 3-bis(2-methoxyphenyl)phosphanylpropyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CCCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC SXXPTCXIFIOPQF-UHFFFAOYSA-N 0.000 description 1
- HEALSPFCFYXUNT-UHFFFAOYSA-N 4,4-dimethyl-2-pyridin-2-yl-3h-pyridine Chemical group C1=CC(C)(C)CC(C=2N=CC=CC=2)=N1 HEALSPFCFYXUNT-UHFFFAOYSA-N 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VNSCZCOQSKBQEA-UHFFFAOYSA-N C(=O)=P(CCCP(=C=O)=C=O)=C=O Chemical compound C(=O)=P(CCCP(=C=O)=C=O)=C=O VNSCZCOQSKBQEA-UHFFFAOYSA-N 0.000 description 1
- BEICNOXVGVRCAL-UHFFFAOYSA-N COC1=C(C=CC=C1)P(C1=C(C=CC=C1)OC)C(C)(C)P(C1=C(C=CC=C1)OC)C1=C(C=CC=C1)OC Chemical compound COC1=C(C=CC=C1)P(C1=C(C=CC=C1)OC)C(C)(C)P(C1=C(C=CC=C1)OC)C1=C(C=CC=C1)OC BEICNOXVGVRCAL-UHFFFAOYSA-N 0.000 description 1
- IZYVVBNBOZCGQY-UHFFFAOYSA-N COC1=CC=CC=C1P(CC1(CP(C2=C(OC)C=CC=C2)C2=C(OC)C=CC=C2)COC(C)(C)OC1)C1=CC=CC=C1OC Chemical compound COC1=CC=CC=C1P(CC1(CP(C2=C(OC)C=CC=C2)C2=C(OC)C=CC=C2)COC(C)(C)OC1)C1=CC=CC=C1OC IZYVVBNBOZCGQY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- ZAADBUUITKVBKF-UHFFFAOYSA-N [3-bis(2-methoxyphenyl)phosphanyl-2,2-dimethylpropyl]-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CC(C)(C)CP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC ZAADBUUITKVBKF-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- SWLVQIMVWOZJHL-UHFFFAOYSA-N acetyl acetate;nickel Chemical compound [Ni].CC(=O)OC(C)=O SWLVQIMVWOZJHL-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- HHZAIOOQYMFSFC-UHFFFAOYSA-L cobalt(2+);3-oxobutanoate Chemical compound [Co+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O HHZAIOOQYMFSFC-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
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Abstract
The present invention relates to a Group 8 transition metal compound; (Bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diyl bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) ligand having a Group 15 element and an anion of an acid having a pKa of 4 or less Wherein the Group 8 transition metal compound is palladium acetate and the anion of the acid with a pKa of 4 or less is selected from the group consisting of trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and sulfuric acid One kind thereof.
On the other hand, the polyketone polymerization ligand of the present invention can be produced by reacting a bis (bis (2, 2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Methoxyphenyl) phosphine), thereby making it possible to apply various ligands to polyketone polymerization.
Description
TECHNICAL FIELD The present invention relates to a polyketone polymerization catalyst having a high activity in a polyketone polymerization catalyst, and a polymerization catalyst ligand which is simple in structure and simple in production process and easy to mass-synthesize in a commercial manner, and a process for producing the same.
The polymerization catalyst used in the production of polyketones generally consists of a system of Pd (II) / Bidentate Phosphine Ligand / Acid. (Pd (OAc) 2-BDOMPP-TFA) system commercialized by Shell in 1999 is a representative example.
1,3-bis [bis (2-methoxyphenyl) phosphino] propane (F.wt: 532.54 g / mol)
The development of highly active polymerization catalysts used in the production of polyketones is centered on the modification of bidentate phosphine ligands among the three components of the catalyst. (2-methoxyphenyl) phosphine] propane, 3,3-bis [bis- (2-methoxyphenyl) Phenylmethyl] -1,5, -dioxa-spiro [5,5] undecane, and the like are known. On the average, they exhibit a polymerization activity of more than 2 times as much as the BDOMPP system. However, since lithium is used in the synthesis, it is a dangerous reaction that can be synthesized only on a laboratory scale, so that commercial mass synthesis is not easy and expensive.
(F.wt .: 560.59 g / mol), 2,2-dimethoxy-1,3-bis [di (2-methoxyphenyl)
[5,5] undecane (International Patent Publication No. WO 01 / 02463A1) (F.wt: 672.73 g) was added to a solution of 3,3-bis [bis- (2- methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [ / mol)
(Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) ligand is easy to mass-produce commercially, and Shell 2 < / RTI > polymerization activity than BDOMPP, a commercially available ligand. It is possible to develop a polyketone highly active catalyst. It is necessary to develop a ligand exhibiting a polymerization activity equal to or higher than that of the ligand.
Bis (bis (2-methoxyphenyl) phosphine (F.wt: 672.73 g / mol)
The present invention aims at providing a novel ligand (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine having a high polymerization activity.
According to a preferred embodiment of the present invention, a Group 8 transition metal compound; (Bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diyl bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) ligand having a Group 15 element and an anion of an acid having a pKa of 4 or less Wherein the Group 8 transition metal compound is palladium acetate and the anion of the acid with a pKa of 4 or less is selected from the group consisting of trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and sulfuric acid One kind thereof.
According to another preferred embodiment of the present invention, a solvent is added to the Group 8 transition metal compound; Bis (bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine) which is a ligand having a Group 15 element and an anion of an acid having a pKa of 4 or less are added, To form a three-component complex, removing the solvent from the three-component complex, freezing at a temperature below -10 ° C to form a single crystal, and grinding the single crystal to form a solid phase catalyst. A method for producing a ketone polymerization catalyst is provided.
The polyketone polymerization ligand of the present invention can be produced by reacting a polyketone polymerization ligand ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis Phenyl) phosphine), which makes it possible to apply various ligands during polyketone polymerization.
Hereinafter, the present invention will be described.
The present invention relates to a Group 8 transition metal compound; A ligand having a Group 15 element; And an anion of an acid having a pKa of 4 or less, and provides a polyketone polymerization catalyst.
Examples of the Group 8 transition metal compounds include complexes of palladium, nickel, cobalt, iron, rhodium, ruthenium, osmium, iridium or platinum. Specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, (Diethylamine) palladium, palladium sulfate, cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium acetylacetate, ruthenium acetylacetate, trifluoromethanesulfonic acid, Ruthenium, and the like, but are not limited thereto.
Among these Group VIII transition metal compounds, a transition metal compound which is inexpensive and economically preferable is a nickel compound, and a preferable transition metal compound from the viewpoint of yield and molecular weight of polyketone is a palladium compound, and from the viewpoint of improving catalytic activity and intrinsic viscosity It is most preferred to use palladium acetate.
In general, examples of ligands having a Group 15 element include 2,2-bipyridyl, 4,4-dimethyl-2,2-bipyridyl, 2,2- (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) bis (bis (2-methoxyphenyl) phosphine), 1,2- (Diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Di (2-methoxyphenyl) phosphine] propane, 1,3-bis [di (2-methoxyphenyl) Bis (diphenylphosphino) benzene, 1,2-bis [(diphenylphosphino) phenyl] phosphine] propane, 1,2-bis (diphenylphosphino) cyclohexane, Bis [[di (2-methoxy-4-sulfonic acid sodium-phenyl) -phosphoric acid methyl] benzene, 1,2- Methyl] benzene, 1,1-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3 And phosphorus ligands such as bis [di (2-methoxyphenyl) phosphino] propane and 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) But is not limited thereto.
Among them, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of the yield of polyketone are ((2,2-dimethyl- Bis (di (2-methoxyphenyl) phosphino] propane, 1, 3-dioxane-5,5-diyl) bis (methylene) bis Bis [di (2-methoxyphenyl) phosphino] methyl] benzene in view of molecular weight of polyketone and 2-hydroxy- Propane and 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane. In view of safety without requiring an organic solvent, Phenyl] phosphino] methyl] benzene, which is easy to synthesize and has a large amount of (meth) And preferred in terms of economy are 1,3-bis (di Carbonyl phosphino) propane, 1,4-bis (diphenylphosphino) butane.
In the present invention, a ligand (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine used in a polymerization catalyst is used. The method is as follows.
The ligand can be synthesized through the following four steps. First, diethyl malonate and 1,5-dibromopentane are boiled under sodium ethoxide and ethanol, and then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexane dimethanol. And reacted with tosyl chloride under pyridine to give the leaving group. The ligand can be obtained by reacting it with 2-methoxyphenylphosphine and sodium hydride under dimethylsulfoxide. Each step is subjected to purification steps such as column chromatography and recrystallization, and the purity of each step can be confirmed by nuclear magnetic resonance analysis.
On the other hand, examples of the anion of the acid having a pKa of 4 or less include an anion of an organic acid having a pKa of 4 or less such as trifluoroacetic acid, trifluoromethanesulfonic acid, or p-toluenesulfonic acid; Anions of inorganic acids having a pKa of 4 or less such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate. It does not.
Particularly, the anion of an acid having a pKa of 4 or less, which is preferred in the present invention, is trifluoroacetic acid, which makes it possible to produce a polyketone having a high catalytic activity and a high intrinsic viscosity.
In the present invention, a polyketone polymer having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography is particularly preferable. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (hexafluoroisopropyl alcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, More preferably, it is 1.0 dl / g to 2.5 dl / g. If the intrinsic viscosity is less than 1.0 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 2.5 dl / g, the workability is deteriorated.
On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. When the ratio is less than 1.5, the polymerization yield decreases. When the ratio is 2.5 or more, the moldability is poor. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.
On the other hand, the present invention provides a process for producing the above polyketone polymerization catalyst.
(Cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine and a pKa of 4 Or less, and then the mixture is stirred to form a three-component complex.
At this time, the solvent is not particularly limited, but acetone is preferably used.
The bis (bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine, which is a ligand having the Group 8 transition metal compound and the Group 15 element, Examples of the anion of an acid are as described above.
Then, the solvent is removed from the three-component complex formed as described above.
In the present invention, a rotary evaporator is used to remove the solvent, but the present invention is not limited thereto.
The solution from which the solvent has been removed is frozen at a temperature of -10 ° C or lower, and then left standing for a predetermined time to form a single crystal.
On the other hand, the solution used for crystallization can be reused by concentrating with a rotary evaporator.
Then, the formed single crystal is washed several times with an inert hydrocarbon solvent such as hexane or heptane, and then pulverized to form a solid catalyst.
At this time, the particle size of the ground solid catalyst is preferably 5 nm to 100 μm, and when the particle size is within the above range, the catalytic activity is excellent.
A method of producing polyketone using the solid catalyst for polyketone polymerization produced through the above-described process will be described.
In the present invention, a polyketone is prepared by copolymerizing carbon monoxide and an ethylenically unsaturated compound in the presence of the solid catalyst for polyketone polymerization.
At this time, it is preferable to use a gas phase polymerization method as the polymerization method, and the reactor used in the polymerization can be used as it is or in a known manner.
The polymerization temperature is not particularly limited and is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. The pressure at the time of polymerization is not particularly limited, and is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa.
On the other hand, examples of the ethylenically unsaturated compound copolymerized with the carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, -Olefins such as tetradecene, 1-hexadecene, and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic acid esters such as ethyl acrylate and methyl acrylate, but are not limited thereto. These ethylenically unsaturated compounds may be used singly or as a mixture of plural kinds.
Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.
The charging ratio of the carbon monoxide and the ethylenic unsaturated compound is not particularly limited, but it is preferably adjusted to 1: 1 to 1: 2.
Hereinafter, the present invention will be described concretely with reference to Examples. However, the following Examples are merely illustrative of one embodiment of the present invention, and the scope of the present invention is not limited by the following Examples.
Comparative Example 1
≪ Step 1 > Preparation of ternary complex
8.3035 g (13.12 mmol) of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) bis (bis (2- methoxyphenyl) phosphine) was added to 5 L of acetone solvent (12.50 mmol) of palladium acetate was added to the mixture and stirred for 30 minutes to completely dissolve the mixture. The two components , 14.25 g (124.9 mmol) of trifluoroacetic acid was added, and the mixture was stirred for 30 minutes to form a three-component complex.
≪ Step 2 > Preparation of solid catalyst
The three-component complex solution prepared in Step 1 was evaporated using a rotary evaporator until the total volume became 1 L, and then 1 L of hexane or heptane was added slowly to the remaining solution so that the solution was not mixed with the acetone solution. Thereby forming a solution layer.
Then, store in a frozen state at -10 ° C or lower. After standing for 1 day in the frozen state, a reddish yellow single crystal was obtained. The obtained single crystals were washed with hexane at room temperature and then ground to a size of 1 mu m or less using a micronizer to prepare a solid catalyst.
Example 1
≪ Step 1 > Preparation of ternary complex
8.3035 g (13.12 mmol) of bis (bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diylbis (methylene)) bis (13.12 mmol) was added to 5 L of acetone solvent and the mixture was stirred for 30 minutes in a magnetic stirrer Then, 2.8061 g (12.50 mmol) of palladium acetate was added, and the mixture was completely dissolved by stirring for 30 minutes. After dissolution of the two components was confirmed, trifluoroacetic acid 14.25 g (124.9 mmol) of trifluoroacetic acid was added, and the mixture was stirred for 30 minutes to form a three-component complex.
≪ Step 2 > Preparation of solid catalyst
The three-component complex solution prepared in Step 1 was evaporated using a rotary evaporator until the total volume became 1 L, and then 1 L of hexane or heptane was added slowly to the remaining solution so that the solution was not mixed with the acetone solution. Thereby forming a solution layer.
Then, store in a frozen state at -10 ° C or lower. After standing for 1 day in the frozen state, a reddish yellow single crystal was obtained. The obtained single crystals were washed with hexane at room temperature and then ground to a size of 1 mu m or less using a micronizer to prepare a solid catalyst.
The polymerization activity test results are shown in Table 1.
Example 1 using the novel ligand (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine showed superior amount of acid yield and excellent catalytic activity as compared with Comparative Example 1 .
Claims (3)
Bis (bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diyl bis (methylene)) bis (bis (2-methoxyphenyl) phosphine having the following structural formula and having a Group 15 element
anions of acids with a pKa of 4 or less;
≪ RTI ID = 0.0 > polyketone < / RTI >
Wherein said Group 8 transition metal compound is palladium acetate,
Wherein the anion of the acid having a pKa of 4 or less is one selected from the group consisting of trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and sulfuric acid.
Removing the solvent from the three-component complex, and then freezing at a temperature of -10 ° C or lower to form a single crystal; And
Pulverizing the single crystal to form a solid catalyst;
≪ / RTI >
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| KR102134158B1 (en) * | 2019-03-18 | 2020-07-15 | 효성화학 주식회사 | Manufacturing method of polyketone using solid acids |
| KR20200126502A (en) * | 2019-04-30 | 2020-11-09 | 효성화학 주식회사 | Manufacturing method of polyketone using solid acids |
| CN115819753A (en) * | 2022-11-02 | 2023-03-21 | 黄河三角洲京博化工研究院有限公司 | Polyketone polymerization method |
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| KR102134158B1 (en) * | 2019-03-18 | 2020-07-15 | 효성화학 주식회사 | Manufacturing method of polyketone using solid acids |
| KR20200126502A (en) * | 2019-04-30 | 2020-11-09 | 효성화학 주식회사 | Manufacturing method of polyketone using solid acids |
| KR102179648B1 (en) | 2019-04-30 | 2020-11-18 | 효성화학 주식회사 | Manufacturing method of polyketone using solid acids |
| CN115819753A (en) * | 2022-11-02 | 2023-03-21 | 黄河三角洲京博化工研究院有限公司 | Polyketone polymerization method |
| CN115819753B (en) * | 2022-11-02 | 2024-03-29 | 黄河三角洲京博化工研究院有限公司 | Polymerization method of polyketone |
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