EP0971971A1 - LINEARE ALTERNIERENDE FUNKTIONALISIERTE $g(a)-OLEFIN/CO-COPOLYMERE UND DEREN VERWENDUNG FÜR DIE HERSTELLUNG VON IONENSELEKTIVEN MEMBRANEN - Google Patents
LINEARE ALTERNIERENDE FUNKTIONALISIERTE $g(a)-OLEFIN/CO-COPOLYMERE UND DEREN VERWENDUNG FÜR DIE HERSTELLUNG VON IONENSELEKTIVEN MEMBRANENInfo
- Publication number
- EP0971971A1 EP0971971A1 EP98916986A EP98916986A EP0971971A1 EP 0971971 A1 EP0971971 A1 EP 0971971A1 EP 98916986 A EP98916986 A EP 98916986A EP 98916986 A EP98916986 A EP 98916986A EP 0971971 A1 EP0971971 A1 EP 0971971A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- elements
- group
- olefin
- carbon monoxide
- periodic table
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 55
- 239000012528 membrane Substances 0.000 title claims description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000004711 α-olefin Substances 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical group C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 239000011669 selenium Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 43
- 230000000737 periodic effect Effects 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000012190 activator Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000013522 chelant Substances 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 150000007527 lewis bases Chemical class 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000002841 Lewis acid Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000007517 lewis acids Chemical class 0.000 claims description 7
- 239000002879 Lewis base Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 230000005669 field effect Effects 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- -1 1-heptenyl Chemical group 0.000 description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 14
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 13
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 9
- 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 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229920001897 terpolymer Polymers 0.000 description 8
- 239000002739 cryptand Substances 0.000 description 7
- 229920001169 thermoplastic Polymers 0.000 description 7
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- GZZPOFFXKUVNSW-UHFFFAOYSA-N dodec-11-enoic acid Chemical compound OC(=O)CCCCCCCCCC=C GZZPOFFXKUVNSW-UHFFFAOYSA-N 0.000 description 6
- 229940069096 dodecene Drugs 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920001198 elastomeric copolymer Polymers 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IPPXDEQFPZLVEJ-UHFFFAOYSA-N undec-10-enyl hydrogen carbonate Chemical compound C(CCCCCCCCC=C)OC(O)=O IPPXDEQFPZLVEJ-UHFFFAOYSA-N 0.000 description 2
- 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 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- WKSZPUHKGNXXQX-UHFFFAOYSA-N P.CC#N Chemical compound P.CC#N WKSZPUHKGNXXQX-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- TTZGACSBMSVUOJ-UHFFFAOYSA-N benzene-1,2-diol;boric acid Chemical compound OB(O)O.OC1=CC=CC=C1O TTZGACSBMSVUOJ-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GRERYAZQWYKFMG-UHFFFAOYSA-N but-3-en-1-ol Chemical compound [CH2]C=CCO GRERYAZQWYKFMG-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- USAHNNPOSAWOSH-UHFFFAOYSA-N dec-8-en-1-ol Chemical compound CC=CCCCCCCCO USAHNNPOSAWOSH-UHFFFAOYSA-N 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 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
- 238000004821 distillation Methods 0.000 description 1
- QNXYZQSFDTZEBK-UHFFFAOYSA-N dodec-11-en-1-ol Chemical compound OCCCCCCCCCCC=C QNXYZQSFDTZEBK-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CJMQFVIRHLBLJQ-UHFFFAOYSA-N hept-1-ene;hex-1-ene Chemical compound CCCCC=C.CCCCCC=C CJMQFVIRHLBLJQ-UHFFFAOYSA-N 0.000 description 1
- UFULDTPDHIRNGS-UHFFFAOYSA-N hept-6-en-1-ol Chemical compound OCCCCCC=C UFULDTPDHIRNGS-UHFFFAOYSA-N 0.000 description 1
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- IVJLSPVMJRCRPF-UHFFFAOYSA-N hexadec-15-en-1-ol Chemical compound OCCCCCCCCCCCCCCC=C IVJLSPVMJRCRPF-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- WXPWPYISTQCNDP-UHFFFAOYSA-N oct-7-en-1-ol Chemical compound OCCCCCCC=C WXPWPYISTQCNDP-UHFFFAOYSA-N 0.000 description 1
- KJCIMIKIPFJKAT-UHFFFAOYSA-N octadec-17-en-1-ol Chemical compound OCCCCCCCCCCCCCCCCC=C KJCIMIKIPFJKAT-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 1
- 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 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- FSUXYWPILZJGCC-UHFFFAOYSA-N pent-4-en-1-ol Natural products CC=CCCO FSUXYWPILZJGCC-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 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
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Definitions
- the present invention relates to linear alternating ⁇ -olefin / CO copolymers, obtainable by polymerizing a monomer mixture containing
- the invention relates to a process for the preparation of the functionalized ⁇ -olefin / CO copolymers and their use for the production of moldings, films, fibers and coatings.
- the invention relates to ion-selective membranes that can be produced from the functionalized ⁇ -olefin / CO copolymers and their use as a component of ion-selective electrodes or chemically modified field-effect transistors.
- the present invention was therefore based on the object of finding new carbon monoxide copolymers which, owing to the selection of the monomer components in the product, are distinguished by a combination of properties which are coordinated with one another and are therefore suitable for complex applications, and in particular the object of the invention was based on the object to provide ion-selective membranes which essentially consist of the carbon monoxide copolymers according to the invention or contain these as an essential component and which do not have the disadvantages described of such membranes or membrane systems.
- the carbon monoxide copolymers described at the outset have been found. Furthermore, a process for the production of the carbon monoxide copolymers according to the invention and their use for the production of fibers, moldings, coatings, films and ion-selective membranes were found. In addition, ion-selective membranes based on the carbon monoxide copolymers according to the invention and their use as a component of ion-selective electrodes or chemically modified field-effect transistors have been found.
- ⁇ -olefin / CO copolymers which can be prepared by copolymerizing the components
- ⁇ -Olefin / CO copolymers which are obtainable by copolymerization of carbon monoxide (a)), a functionalized 1-alkene (b)) of the general formula (I), are particularly preferred
- k independently of one another 2, 3 or 4,
- q an integer in the range from 4 to 24, in particular in the range from 6 to 16
- the copolymers according to the invention are composed of units which are based on the monomers carbon monoxide and one or more ⁇ -olefinically unsaturated compounds.
- the different monomer units are generally in strict alternation.
- the sequence of carbon monoxide and olefin component is usually also strict alternating, the crown ether-functionalized alkene monomers being incorporated into the linear copolymer chain essentially in a statistical distribution with respect to the olefin incorporation positions in question.
- Suitable ⁇ -olefinically unsaturated components are propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 1 -Dodecenyl, 1-hexadecenyl, 1-octadecenyl or the 1-eicosaenyl radical.
- Compounds b) are preferably used, the ⁇ -olefinically unsaturated portion of which goes back to C 5 - to Ci 8 ⁇ l-alkenyl residues, C - to -C 4 -1-alkenyl residues are particularly preferred.
- crown ethers include, in addition to crown ethers, cryptands, podands and coronands, as described, for example, in F. Vogtle, Supramolecular Chemistry, BG Teubner, Stuttgart, 1989).
- Crown ether units A having 5 to 10 oxygen atoms and cryptand units A containing 3 to 6 oxygen atoms are preferred, and benzene and / or cyclohexane rings can also be integrated into the macrocycles framework, mostly via linkages on adjacent ring carbon atoms.
- the units A are covalent, usually linked to the olefinically unsaturated monomer via a single bond.
- ether, ester, amide or carbamate groups or a carbon / carbon atom can be used as bridging structural elements. be used fertilizer.
- a common connecting unit is the ester group, the carboxylic acid residue forming this group preferably originating from component A and the hydroxyl group from the ⁇ -olefinically unsaturated monomer unit.
- suitable compounds b) can be formally obtained from alcohols, such as allyl alcohol, but-3-en-1-ol, pent-4-en-1-ol, hex-5-en-1-ol, hept-6-en-1 -ol, oct-7-en-l-ol, non-8-en-l-ol, dec-8-en-l-ol, dodec-11-en-l-ol, hexadec-15-en-l -ol, octadec-17-en-l-ol or Eicos-19-en-l-ol, and crown ethers or cryptands provided with carboxylic acid groups can be derived.
- alcohols such as allyl alcohol, but-3-en-1-ol, pent-4-en-1-ol, hex-5-en-1-ol, hept-6-en-1 -ol, oct-7-en-l-ol, non-8-en-l-ol, dec-8
- a crown ether with a covalently bonded carboxylic acid group can be obtained, for example, by acylation of benzo-15-crown-5 (for nomenclature and synthesis, see V. Percec, R. Rodenhouse, Macromolecules 1989, 22, 4408) and subsequent oxidation using sodium hypobromite (see M. Bourgoin, KH Wong, JY Hui, J. Smid, J. Am. Chem. Soc. 1975, 97, 3462).
- Preferred ester-bonded olefinically unsaturated compounds b) fall, for example, under the general formula (I)
- k independently of one another 2, 3 or 4,
- q an integer in the range from 4 to 24, in particular 6 to 16
- crown ether functionality meets the following conditions:
- a suitable monomer compound b) for the preparation of the copolymers according to the invention is accordingly, for example, 4 '- (dec-10-enylcarboxylate) benzo-15-crown-5.
- ternary and higher copolymer systems containing functionalized 1-alkenes b) are also accessible.
- Suitable as monomers c) for non-binary copolymers are in particular C 2 - to C 24 -1-alkenes.
- Examples include ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene or 1 -Icos.
- Propene, 1-butene, 1-pentene, 1-hexene-1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene and a 1-octadecene, in particular propene are preferred 1-hexene, 1-dodecene and 1-octadecene are used.
- Particularly preferred among the latter compounds are C ß - to C ⁇ 2 -1 alkenes.
- conjugated or isolated C ⁇ - to C 2 o-dienes for example 1,4-hexadiene and 1,5-hexadiene, are also suitable as olefinically unsaturated compounds c).
- Preferred terpolymers are based on carbon monoxide (a)), a compound (b)) which falls under the general formula (I)
- k independently of one another 2, 3 or 4,
- q an integer in the range from 4 to 24, in particular from 6 to 16
- terpolymers which can be prepared from carbon monoxide, a compound of the general formula (I)
- ternary carbon monoxide copolymers are in particular the systems based on carbon monoxide / propene / 4 '- (undec-10-enylcarbonate), benzo-15-crown-5, carbon monoxide / l-hexene / 4' - (undec-10-enylcarboxylate) benzo-15-crown-5, carbon monoxide / 1-dodecene / 4 '- (undec-10-enylcarboxylate) benzo-15-crown-5 and carbon monoxide / 1-dodecadecen / 4' - (undec-10- enyl carboxylate) benzo-15-crown-5 and ins special carbon monoxide / 1-hexene / 4 '- (undec-10-enyl carboxylate) benzo-15-crown-5 and carbon monoxide / 1-dodecene / 4' - (undec-10-enyl carboxylate
- the average molecular weights M w (measured by the method of gel permeation chromatography (GPC) at 25 ° C. with Microstyragel (Waters) as column material and chloroform as solvent against the polystyrene standard) of the carbon monoxide copolymers according to the invention are usually in the range from 5000 to 200000 g / mol, but copolymers with average molecular weights of up to 300000 g / mol and even 400000 g / mol can also be obtained.
- short-chain monomer components c such as propene
- M w average molecular weights
- long-chain alkenes such as l-octadecene
- the terpolymers according to the invention are distinguished, inter alia, by their thermoplastic elastomeric properties and accordingly have Tg values in the range from 20 to -90 ° C.
- Examples of carbon monoxide copolymers with a particularly suitable thermoplastic elastomeric property profile are those terpolymers whose component b) is based on an ⁇ -olefin functionalized with benzo-15-crown-5 and whose component c) is based on a C 1 -C 12 -alkene.
- Terpolymers according to the present invention are also to be understood as meaning compounds in which the molar proportion of component b) in the total copolymer is 0.01 mol%. As a rule, however, molar proportions of 5 or 10% or above are readily accessible.
- the proportion of head-to-tail linked units in the terpolymers according to the invention is generally in the range from 1 to 80% and is for carbon monoxide copolymers containing, for example, a benzo-15-crown-5 functionality and C 3 - to C 2 - 1-alkenes, usually in the range of 40 to 70%.
- the molecular weight distribution M w / M n (weight average / number average) of the copolymers according to the invention, measured using the gel permeation chromatography (GPC) method analogous to the preceding description, is generally from 1.2 to 4, but preferably assumes a value less than 2.5.
- the molar ratio of carbon monoxide to the sum of the structural units attributable to the olefinically unsaturated monomers in the binary and higher carbon monoxide copolymers according to the invention is generally 1: 1.
- the polymer materials according to the invention Due to their impact modifying properties and their biocompatible behavior, the polymer materials according to the invention have a variety of possible uses, e.g. in the field of polymer blend technology or medical technology.
- carbon monoxide can be copolymerized with olefinically unsaturated compounds in a virtually alcohol-free or water-free polymerization medium in the presence of a catalyst whose active composition is formed from
- M is a metal from Group VIIIB of the Periodic Table of the Elements
- E 1 , E 2 an element from group VA of the periodic table of the elements
- a bridging structural unit consisting of one, two, three or four substructural units from elements of group IVA, VA, VIA of the periodic table of the elements,
- R 1 to R 4 substituents selected from the group consisting of C ⁇ ⁇ to C 2 o _ carbonaceous organic and C 3 - to C 3 o -organosilicon radicals, where the radicals one element or more elements of Group IVA, VA, VIA and VIIA of the Periodic Table of the Elements can contain
- a further method for producing the linear, thermoplastic, elastomeric copolymers according to the invention is the copolymerization of carbon monoxide with olefinically unsaturated compounds in a virtually alcohol-free or water-free polymerization medium in the presence of a catalyst, the active mass of which is formed
- E 1 , E 2 an element from group VA of the periodic table of the elements
- Z is a bridging structural unit from one, two, three or four substructure units from
- R 1 to R 4 substituents selected from the group of Ci to C 20 carbon organic and C 3 to
- C3o-organosilicon radicals the radicals being one or more elements of the group IVA, VA, VIA and VIIA of the Periodic Table of the Elements can contain
- the polymerizations for the preparation of the carbon monoxide copolymers according to the invention can be carried out either batchwise or continuously in the presence of a polymerization catalyst from A '), or i), ii), iii) and optionally B') or iv).
- Possible polymerization catalysts are metal compounds of the eighth subgroup of the Periodic Table of the Elements (VIIIB), which exist as defined metal complexes (II) or in situ from a metal salt i) of the metals of Group VIIIB of the Periodic Table of the Elements, proton and / or Lewis acids ii ) and a chelate compound iii) of the formula (III) can be formed.
- activators B ') or iv) can be added to the metal compounds.
- Suitable metals M are the metals from group VIIIB of the periodic table of the elements, that is, in addition to iron, cobalt and nickel, primarily the platinum metals such as ruthenium, rhodium, osmium, iridium and platinum and very particularly palladium.
- the metals nickel, palladium and platinum are generally formally charged twice positively, the metals cobalt, rhodium and iridium are generally formally singly charged and the metals iron, ruthenium and osmium are generally formally uncharged in the complexes.
- the elements E 1 and E 2 of the chelate ligand are the elements of the 5th main group of the Periodic Table of the Elements (group VA), that is to say nitrogen, phosphorus, arsenic, antimony or bismuth. Nitrogen or phosphorus, in particular phosphorus, are particularly suitable.
- the chelate ligand or the chelate compound (III) can contain different elements E 1 and E 2 , for example nitrogen and phosphorus, but preferably it contains the same elements E 1 and E 2 and in particular E 1 and E 2 are phosphorus.
- the bridging structural unit Z is an atomic grouping that connects the two elements E 1 and E 2 to one another.
- Substructure units consisting of one atom or a plurality of interconnected atoms from group IVA, VA or VIA of the periodic table of the Elements usually form the bridge between E 1 and E 2 .
- Possible free valences of these bridge atoms can be saturated in a variety of ways, for example by substitution with hydrogen or with elements from group IVA, VA, VIA or VIIA of the periodic table of the elements. These substituents can form ring structures with one another or with the bridge atom.
- elements from group IVA of the periodic table of the elements such as methylene (-CH 2 -), 1,2-ethylene (-CH 2 -CH 2 -), 1, 3-propylene (-CH2-CH 2 -CH 2 -),
- 1,2-Ethylene, 1,3-propylene and 1,4-butylene may be mentioned as particularly suitable bridging structural units.
- Suitable carbon-organic radicals R 1 to R 4 are, independently of one another, aliphatic, cycloaliphatic and aromatic with 1 to 20 C atoms, for example the methyl, ethyl, 1-propyl, 1-butyl, 1- Pentyl, 1-hexyl and 1-octyl groups and their structural analogues.
- Linear arylalkyl groups with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical are also suitable, such as benzyl.
- Aryl radicals may be mentioned as further radicals R 1 to R 4 , for example tolyl, anisyl, preferably ortho-anisyl, xylyl and other substituted phenyl groups, in particular phenyl.
- Suitable cycloaliphatic radicals are C 3 - to Cio-monocyclic systems such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclohexyl is particularly preferred.
- Suitable branched aliphatic radicals are C 3 to C 20, preferably C 3 to C 2 alkyl radicals, such as the i-propyl, i-butyl, s-butyl, neopentyl and t-butyl group.
- Particularly suitable branched aliphatic radicals are the t-butyl group, the i-propyl group and the s-butyl group.
- Alkyl groups with branching located further outside are also suitable as substituents R 1 to R 4 , such as the i-butyl, the 3-methyl-but-2-yl and 4-methylpentyl group.
- the substituents R 1 to R 4 can also, independently of one another, contain atoms from the group IVA, VA, VIA or VIIA of the Periodic Table of the Elements, for example halogen, oxygen, Sulfur, nitrogen, silicon, here for example the bis (trimethylsilylmethyl group.
- Functional groups which are inert under the polymerization conditions can also be considered in this context.
- Preferred hetero substituents R 1 to R 4 are C 3 - to C 3 o-organosilicon radicals, that is to say tetravalent silicon atoms which are bonded to E 1 or E 2 on the one hand and their other valences with three carbon-organic radicals such as alkyl and / or Aryl radicals are saturated, the sum of the carbon atoms of these three silicon-bonded radicals being in the range from three to thirty. Examples include the trimethylsilyl, t-butyldimethylsilyl or triphenylsilyl group, especially the trimethylsilyl group.
- chelate ligands or chelate compound (III) Preferably used as chelate ligands or chelate compound (III), 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane or 1,4-bis (diphenylphosphino) butane.
- Chelate compounds (III) are 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) utane.
- Lewis bases ie compounds, preferably organic compounds with at least one lone pair of electrons or water, are generally suitable as formally uncharged ligands L 1 , L 2 .
- Lewis bases whose free electron pair or whose free electron pairs are located on a nitrogen or oxygen atom, ie nitriles, R-CN, ketones, ethers or preferably water, are particularly suitable.
- Suitable Lewis bases are ci- to ci-nitriles such as acetonitrile, propionitrile, benzonitrile or C 3 - to cio-ketones such as acetone, acetylacetone or C 2 - to cio-ethers such as dimethyl ether, diethyl ether or tetrahydrofuran.
- ligands L 1 , L 2 in (II) are those of the formula (IV)
- T means hydrogen or a Ci to Ci 5 carbon organic provided with a Lewis basic group
- C 1 to C 5 organic carbon radicals T are, for example, linear or also cyclic CH 2 -) - n units, in which n is 1 to 10, that is methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene , 1,9-nonylene or 1, 10-decylene.
- Suitable Lewis base groups are ethers, esters, ketones, amines, phosphines and in particular nitrile (-C ⁇ N) or tertiary amines.
- R ' is Ci to Cio-alkyl or C 3 - to C ⁇ represents 0 cycloalkyl, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclopentyl , Cyclohexyl.
- R 'can also mean C 8 to C 10 aryl, such as phenyl or naphthyl.
- the ligands T-OH, apart from water, are bound to the metal M in (II) via the already defined Lewis base group.
- Suitable anions X in (II) are, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as, for example, acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, for example methylsulfonate, trifluoromethylsulfonate and p -Toluenesulfonate, also tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate, hexa luoroarsenate or hexafluoroantimonate.
- Perchlorate, trifluoroacetate, sulfonates such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate, tetrafluoroborate or hexafluorophosphate and in particular trifluoroacetate, perchlorate or p-toluenesulfonate are preferably used as the anion X.
- the metal complexes of the general formula (II) are generally prepared by processes known from the literature, such as in Makromol. Chem. 1993, 194, p. 2579. Tetrakis-ligand-metal complexes, such as tetrakis-acetonitrile-palladium-bistrafluoroborate, can usually be reacted with the chelate compounds (III) and the ligands L 1 , L 2 or TOH to give the metal complexes (II).
- a preferred method for producing aquo complexes (II) is the reaction of the chelate phosphane-acetonitrile metal complexes with water. The reaction is generally carried out in a solvent, for example dichloromethane, acetonitrile, water, at temperatures in the range from -78 to 40.degree.
- the metals M are usually used in the form of their salts and brought into contact with the chelate compound iii) of the general formula (III) and the acids ii). This can be done before the catalytically active composition obtained in this way comes into contact with the monomer and, if appropriate, further activator iv), generally outside the polymerization reactor.
- the reaction of the individual components metal salt i), chelate compound iii) of the general formula (III), acid ii) and optionally activator component iv) can also be carried out in the polymerization reactor in the presence of the monomers.
- Suitable salts of customarily divalent metals M are halides, sulfates, phosphates, nitrates and carboxylates, such as acetates, propionates, oxalates, citrates, benzoates, and sulfonic acid salts such as, for example, methyl sulfonates, trifluoromethyl sulfonate and p-toluenesulfonate. Carboxylates, sulfonic acid derivatives and in particular acetates are preferably used.
- catalyst components i) are palladium dicarboxylates, preferably palladium diacetate, palladium dipropionate, palladium bis (trifluoroacetate) and palladium oxalate, and also palladium sulfonates, preferably palladium bis (trifluoromethanesulfona), palladium bis (methanesulfonate), palladium bis (p-toat), in particular one uses palladium diacetate.
- catalyst components ii) are palladium dicarboxylates, preferably palladium diacetate, palladium dipropionate, palladium bis (trifluoroacetate) and palladium oxalate, and also palladium sulfonates, preferably palladium bis (trifluoromethanesulfona), palladium bis (methanesulfonate), palladium bis (p-toat), in particular one uses palladium diacetate.
- Suitable protonic acids ii) are strong mineral acids, such as sulfuric acid and perchloric acid, and also strong organic acids, for example trichloro and trifluoroacetic acid, and also the sulfonic acids methanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid, that is to say in each case those acids which are preferably less than a pKa value 3 have.
- the acidic salts of strong acids with weak bases such as ammonium salts of the aforementioned acids, are also suitable.
- Suitable Lewis acids are halides of the elements of group IIIA of the periodic table of the elements, for example boron trifluoride, boron trichloride, aluminum trifluoride, aluminum trichloride, halides of the elements of group VA of the periodic table of the elements, such as phosphorus pentafluoride, antimony pentafluoride, and halides of the metals subgroup IVB of the Periodic Table of the Elements, such as titanium tetrachloride or zirconium tetrachloride.
- Other suitable Lewis acids are organically substituted Lewis acids, for example tris (pentafluorophenyDboran.
- the preferred Lewis acids used are boron trifluoride, antimony pentafluoride or tris (pentafluorophenyDborane.
- Particularly preferred components ii) are those which have a weakly coordinating conjugated anion, i.e. an anion which forms only a weak bond to the central metal of the complex, such as tetrafluoroborate, hexafluorophosphate, perchlorate, trifluoroacetate, trifluoromethylsulfonate, p-tosylate and borates, such as pyrocatecholate borate and tetraarylborate, with 2, 5-dimethylphenyl in particular being the aryl group, Bistrifluoromethylphenyl- or Pentafluorphenyl- come into question.
- a weakly coordinating conjugated anion i.e. an anion which forms only a weak bond to the central metal of the complex
- a weakly coordinating conjugated anion i.e. an anion which forms only a weak bond to the central metal of the complex
- a weakly coordinating conjugated anion i.e. an anion which forms
- suitable catalyst components i) and ii) are those as are generally known for systems with bisphosphines from EP-A 501 576 and 516 238.
- the catalyst systems contain a chelate compound R 1 R 2 E 1 -ZE 2 R 3 R 4 (III), which was already described in the discussion of the metal complexes (II).
- the ratio of the catalyst constituents i), ii) and iii) to one another is generally chosen so that the molar ratio of the metal compound i) to the acid ii) is 0.01: 1 to 100: 1, preferably 0.1: 1 to 1: 1 and the molar ratio of the metal compound i) to component iii) is 0.01: 1 to 10: 1, preferably 0.1: 1 to 2: 1.
- the activator component B ') or iv) is generally a chemical compound which contains at least one hydroxyl group in the molecule.
- These include above all ci- to cio alcohols, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, t-butanol, n-hexanol, n-octanol, n- Decanol, cyclohexanol, phenol or water.
- Methanol and / or water is preferably used as activator component B ') or iv).
- the molar ratio of activator component B ') or iv) to metal M is in the range from 0 to 1500, preferably in the range from 0 to 1300. It has proven advantageous not to exceed the maximum ratio in the polymerization reaction, since otherwise the average molecular weights M w of the carbon monoxide copolymers formed may be too low.
- the polymerization reactions can be carried out in the gas phase in a fluidized bed or stirred, in suspension, in liquid and in supercritical monomers and in solvents which are inert under the polymerization conditions.
- the polymerization reactions can be carried out in a virtually alcohol-free or water-free polymerization medium. This means that the reaction mixture of monomers, catalyst and optionally inert solvent or suspending agent, except optionally the activator component B ') or iv), no further amount of alcohol or water has been or will be added.
- Suitable inert solvents and suspending agents are those which contain no hydroxyl group in the molecule, i.e. ethers such as diethyl ether, tetrahydrofuran, aromatic solvents such as benzene, toluene, ethylbenzene, chlorobenzene, aliphatic hydrocarbons such as i-butane or chlorinated aliphatic hydrocarbons such as dichloromethane, 1, 1 , 1-trichloromethane or mixtures of the compounds mentioned.
- ethers such as diethyl ether, tetrahydrofuran
- aromatic solvents such as benzene, toluene, ethylbenzene, chlorobenzene
- aliphatic hydrocarbons such as i-butane or chlorinated aliphatic hydrocarbons such as dichloromethane, 1, 1 , 1-trichloromethane or mixtures of the compounds mentioned.
- a particularly well-suited polymerization process has been the introduction of the catalyst in the inert solvent, optionally subsequent addition of activator component B ') or iv) and the subsequent addition of the monomers and polymerization at a temperature in the range from 20 to 100 ° C. and a pressure in Range from 1000 to 10000 kPa.
- the carbon monoxide copolymers according to the invention can be processed by means of injection molding, blow molding, spinning, rotary molding, extrusion or spin coating.
- the coating of metallic, ceramic and other surfaces e.g. those made of plastic materials.
- the carbon monoxide copolymers according to the invention are suitable for the production of fibers, films, moldings and coatings. Furthermore, the carbon monoxide copolymers according to the invention are suitable for the production of ion-selective membranes.
- films or foils can be produced which are particularly suitable as ion-selective membranes.
- These membranes can be used, among other things, as a component of small-format analysis devices, such as ion-selective electrodes (cf. J. Moody, BB Saad, JDR Thomas, Selective Electrode Rev.
- CHEMFETs chemically modified field-effect transistors
- CHEMFETs chemically modified field-effect transistors
- the membranes according to the invention are characterized in particular by the fact that no plasticizer is required and that the activation energy for the transport of ions is minimized due to the presence of polar CO groups in the polymer.
- the hydrophobic surface character ter obtained whereby the process of fouling in the aqueous phase is significantly suppressed or completely prevented.
- membranes based on the carbon monoxide copolymers of the invention provide easy access to e.g. Sensor components with a long service life that can be easily produced on an industrial scale.
- Molecular weights M w and molecular weight distributions M w / M n were determined by GPC in CHCI 3 using a Waters 590 HPLC pump, Waters Microstyragelsaulen with pore sizes of 10 5 , 10 4 and 10 3 ⁇ , a Waters 410 differential refractometer and a Waters 486 UV detector determined.
- the DSC data were determined using the Perkin Elmer DSC 7 device equipped with a Perkin Elmer TAC 7 / DX thermal controller; Cyclohexane, indium and gallium were used for the calibration.
- IR spectra were recorded on a Bruker IFS 66V spectrometer.
- the test samples were prepared by drawing a thin film on KBr plates from a dichloromethane solution.
- the catalyst used was [Pd [dppp] (NCCH3) 2 ] (BF 4 ) 2 , produced from [Pd [NCCH 3 ) 4 ] (BF 4 ) 2 (from Aldrich) and 1,3-bis (diphenylphosphino) propane ( ⁇ dppp) (from Strem Chemicals) according to FY Xu,
- the polymerizations were carried out in 50 or 100 ml steel autoclaves by stirring at room temperature and a CO pressure of 6.1 ⁇ 10 6 Pa in 25 ml dichloromethane.
- the amount of the activator (methanol) added in each case, the amount of ⁇ -olefin and catalyst used and the reaction conditions can be found in Table 1.
- the polymerization was terminated by degassing the autoclave and adding an excess of methanol. The solvent was then removed, the residue was taken up in dichloromethane and catalyst residues were removed via a short silica gel column.
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DE19714031A DE19714031A1 (de) | 1997-04-04 | 1997-04-04 | Lineare alternierende funktionalisierte alpha-Olefin/CO-Copolymere und deren Verwendung für die Herstellung von ionenselektiven Membranen |
PCT/EP1998/001553 WO1998045352A1 (de) | 1997-04-04 | 1998-03-18 | LINEARE ALTERNIERENDE FUNKTIONALISIERTE α-OLEFIN/CO-COPOLYMERE UND DEREN VERWENDUNG FÜR DIE HERSTELLUNG VON IONENSELEKTIVEN MEMBRANEN |
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---|---|---|---|---|
JPS59135224A (ja) * | 1983-01-24 | 1984-08-03 | Idemitsu Kosan Co Ltd | ポリケトンの製造方法 |
DE3480845D1 (de) * | 1983-04-06 | 1990-02-01 | Shell Int Research | Verfahren zur herstellung von polyketonen. |
NL8602733A (nl) * | 1986-10-30 | 1988-05-16 | Shell Int Research | Nieuwe polymeren. |
US5077384A (en) * | 1989-08-17 | 1991-12-31 | Shell Oil Company | Carbon monoxide/olefin copolymer having wide molecular weight distribution |
US5216120A (en) * | 1991-02-26 | 1993-06-01 | Shell Oil Company | Polymerization of co/olefin with catalyst comprising palladium compound, lewis acid and bronsted acid |
EP0512647A3 (en) * | 1991-05-08 | 1993-09-15 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of linear alternating polymers of carbon monoxide and one or more olefins |
US5210177A (en) * | 1991-05-31 | 1993-05-11 | Shell Oil Company | Polymerization of co/olefin with tetra ethyl diphosphine |
US5241036A (en) * | 1991-09-04 | 1993-08-31 | National Science Council | Side-chain liquid crystalline polymer containing crown ether based mesogens |
US5352767A (en) * | 1992-01-08 | 1994-10-04 | University Of Massachusetts - Amherst | Alpha-olefin/carbon monoxide attenuating copolymers and improved catalyst and method for copolymerizing the same |
DE19518737A1 (de) * | 1995-05-22 | 1996-11-28 | Basf Ag | Kohlenmonoxid/Olefin-Copolymere |
DE19610358A1 (de) * | 1996-03-15 | 1997-09-18 | Basf Ag | Thermoplastische elastomere Kohlenmonoxid/Olefin-Copolymere |
DE19649072A1 (de) * | 1996-11-28 | 1998-06-04 | Basf Ag | Thermoplastische, elastomere Kohlenmonoxid/Olefin-Copolymere |
DE19714031A1 (de) * | 1997-04-04 | 1998-10-08 | Basf Ag | Lineare alternierende funktionalisierte alpha-Olefin/CO-Copolymere und deren Verwendung für die Herstellung von ionenselektiven Membranen |
-
1997
- 1997-04-04 DE DE19714031A patent/DE19714031A1/de not_active Withdrawn
-
1998
- 1998-03-18 EP EP98916986A patent/EP0971971A1/de not_active Withdrawn
- 1998-03-18 WO PCT/EP1998/001553 patent/WO1998045352A1/de not_active Application Discontinuation
- 1998-03-18 AU AU70364/98A patent/AU7036498A/en not_active Abandoned
- 1998-03-18 JP JP54229598A patent/JP2001518951A/ja active Pending
- 1998-05-18 US US09/402,091 patent/US6133410A/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9845352A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU7036498A (en) | 1998-10-30 |
WO1998045352A1 (de) | 1998-10-15 |
JP2001518951A (ja) | 2001-10-16 |
US6133410A (en) | 2000-10-17 |
DE19714031A1 (de) | 1998-10-08 |
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