WO1998046614A1 - Catalyseur et son utilisation pour la polymerisation - Google Patents
Catalyseur et son utilisation pour la polymerisation Download PDFInfo
- Publication number
- WO1998046614A1 WO1998046614A1 PCT/EP1998/002003 EP9802003W WO9846614A1 WO 1998046614 A1 WO1998046614 A1 WO 1998046614A1 EP 9802003 W EP9802003 W EP 9802003W WO 9846614 A1 WO9846614 A1 WO 9846614A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- general formula
- mmol
- endo
- group
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- -1 polycyclic hydrocarbon Chemical class 0.000 claims description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000001925 cycloalkenes Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000002848 norbornenes Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 4
- 229910017008 AsF 6 Inorganic materials 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- 241000251730 Chondrichthyes Species 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 2
- 239000004913 cyclooctene Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002577 pseudohalo group Chemical group 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000008648 triflates Chemical class 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- 238000006116 polymerization reaction Methods 0.000 description 39
- 229920000642 polymer Polymers 0.000 description 38
- 238000005227 gel permeation chromatography Methods 0.000 description 29
- 239000000203 mixture Substances 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- 239000000706 filtrate Substances 0.000 description 14
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 150000004702 methyl esters Chemical class 0.000 description 9
- FCCGTJAGEHZPBF-UHFFFAOYSA-N ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OCC)CC1C=C2 FCCGTJAGEHZPBF-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 4
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JFUOAGBSDGCVES-UHFFFAOYSA-N 3-but-2-enyl-4-methylpyrrolidine-2,5-dione Chemical compound CC=CCC1C(C)C(=O)NC1=O JFUOAGBSDGCVES-UHFFFAOYSA-N 0.000 description 1
- MZCFNSAAYVFCKY-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2CC(C(O)=O)C1(C)C=C2 MZCFNSAAYVFCKY-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical class C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- UXRMRBNLTQHPEU-UHFFFAOYSA-N diethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound C1C2C=CC1C(C(=O)OCC)C2C(=O)OCC UXRMRBNLTQHPEU-UHFFFAOYSA-N 0.000 description 1
- VGQLNJWOULYVFV-UHFFFAOYSA-N dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound C1C2C=CC1C(C(=O)OC)C2C(=O)OC VGQLNJWOULYVFV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- NYJLMKJASYHZSM-UHFFFAOYSA-N methyl 2-methylhept-5-enoate Chemical compound COC(=O)C(C)CCC=CC NYJLMKJASYHZSM-UHFFFAOYSA-N 0.000 description 1
- AEBDJCUTXUYLDC-UHFFFAOYSA-N methyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)(C)CC1C=C2 AEBDJCUTXUYLDC-UHFFFAOYSA-N 0.000 description 1
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-FTXFMUIASA-N palladium-101 Chemical compound [101Pd] KDLHZDBZIXYQEI-FTXFMUIASA-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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
Definitions
- the present invention relates to a new catalyst and the use of the catalyst for the polymerization of functionalized and non-functionalized cycloolefins.
- the vinyl polymerization of norbornene gives a polymer which is distinguished by a high glass transition temperature, a high density and a high refractive index, cf. Macromol. Chem. Phys 1886, 197, 3435-3453.
- a polynorbornene substituted at the 2-position with an ester group such as the vinyl-polymerized 5-norbomene-2-carboxylic acid methyl ester, exhibits better solubility properties than the unsubstituted polynorbornene
- n is a number> 1.
- polynorbornene it is readily soluble in tetrahydrofuran, methyl acetate, acetone and other solvents.
- the polymer of the methyl ester is amorphous, has a glass transition temperature that is above 250 ° C and has a higher density than polynorbornene.
- Polymer-analogous implementations such as saponification and the production of blends are possible.
- the ester can easily be prepared using the Diels-Alder reaction.
- the polymerization is only possible with the palladium (II) nitrile catalysts used for the polymerization of norbornene possible very slowly.
- the polymerization of various norbornene derivatives with Pd (II) chloro complexes has been described in US Pat. No. 3,330,815.
- the object of the invention is to provide a new catalyst for the polymerization which has a higher reactivity and produces polymers with a higher molecular weight, and a process for the preparation of homopolymers and / or copolymers.
- R 1 represents a mono- or polycyclic hydrocarbon
- M 1 + is a transition metal from group VIIIb
- X means at least one non- or weakly coordinating anion.
- a preferred embodiment of the invention lies in the compound having the general formula (I),
- R 1 is a mono- or polycyclic hydrocarbon with at least one unsaturated bond inside or outside the ring, M 1 + Rh, Ru, Pd, Co or Ni, X " BF 4 -, PF 6 -, SbF 6 -, AsF 6 -, CIO 4 -, BPh 4 -, whereby the phenyl groups by Fluorine or trifluoromethyl can be substituted, closo-boranes and carboranes and their halogenated derivatives or triflates means.
- a particularly preferred embodiment of the invention lies in the compound having the general formula (I), where
- R 1 is substituted or unsubstituted norbornene, cyclooctene, tricyclodecene or exo-methylenecyclohexene, M 1+ is Pd, X "is BF 4 -, PF 6 -, SbF 6 -, AsF 6 - or carboranes.
- a very particularly preferred embodiment of the invention lies in the compound having the general formula (I), where R 1 is a compound having the general formula (II)
- R 2 is a hydrogen atom, a C 1 -C 20 alkyl group, C 6 -C 20 aryl group, OR 3 -,
- R 3 represents a hydrogen atom, a C 1 -C 20 alkyl group or C 6 -C 20 aryl group, a -CN , -SCN, -NR 3 2 , N 3 group or a halogen atom.
- the compound having the general formula (I) is dissolved in at least one halogenated hydrocarbon, aliphatic or aromatic hydrocarbon, which may optionally contain a heteroatom such as halogen, oxygen or nitrogen.
- the compound having the general formula (I) is preferably dissolved in methylene chloride, chloroform, nitromethane, dimethylformamide, N-methylpyrolidone, dimethylethylene urea, nitrobenzene, or chlorobenzene.
- a compound having the general formula (I) and a cycloolefin which has at least one radical R 4 , the ratio of the compound having the general formula (I) to the cycloolefin being from 1: 1 to 1:10 and R 4 represents a COOR 3 , or -NC, COR 3 - group.
- M 2+ is an alkali, alkaline earth metal, Ag, Tl or Cu.
- a process for the preparation of the compound having the general formula (I) and a cycloolefin is provided, an amount from 1: 1 to 1:10, based on the compound having the general formula (I), and M 1+ R 1 Hal " with M 2+ X " is reacted in at least one solvent.
- a process for the preparation of homopolymers and / or copolymers with at least one compound of the general formula (I) is provided as the catalyst system.
- a method for producing a homo- and / or copolymer is provided by polymerization of 0.1 to 100% by weight, based on the total amount of monomers, of at least one polycyclic olefin of the formula III, IV, IV, V, VI , VII or VIII
- the polycyclic olefins are preferably at least monosubstituted carboxylic acid and / or dicarboxylic acid derivatives and 0 to 99.9% by weight, based on the total amount of monomers, of at least one monocyclic olefin of the formula IX
- R 13 , R 14 , R 15 and R 16 are the same or different and represent a hydrogen atom or a hydrocarbon radical, preferably a C 6 -C 10 aryl radical or a C -C ⁇ alkyl radical.
- homo- and / or copolymers of norbomene carboxylic acid derivatives and norbomene dicarboxylic acid derivatives are obtained.
- Homo- and / or copolymers of norbornene which is at least monosubstituted by carboxyl, ester, amide and nitrile groups or of norbornene carboxylic acid anhydride and imide are obtained.
- Preferred examples of norbomene carboxylic acid and norbornene dicarboxylic acid derivatives are: bicyclo [2.2.1] hept-5-en-2-carboxylic acid methyl ester,
- the derivatives can also be substituted in the 7-position.
- the use of a compound with the general formula (i) is provided as a catalyst system for the production of homopolymers and / or copolymers.
- the analysis would be carried out using the methods listed below.
- the NMR spectra were recorded on a Bruker AC 300 spectrometer with a frequency of 300 MHz at 1 H-NMR and 75 MHz at 13 C-NMR.
- the IR spectra were recorded on an FT-IR spectrometer 1600 from Perkin Elmer. Solids were measured as KBr compacts, liquids between two sodium chloride plates.
- the GPC analyzes by means of gel permeation chromatography were carried out with a solution of 0.2 g polymer in 10 ml tetrahydrofuran on two 10 mm polymer mixed gel columns (600 * 8 mm) from PSS.
- a differential refractometer and differential viscometer from Knauer served as the detector.
- a Knauer pump was used. The inherent viscosities were determined at a temperature of 25 ° C for polymer solutions with 0.5 percent by weight in dichloromethane.
- the GC analyzes were carried out on a Hewlett Packard 5890 gas chromatograph. The injector and detector were at a temperature of 300 ° C. The temperature program used was: Isotherm from 70 ° C for 4 minutes, then heat to 280 ° C at a rate of 15 ° C / min.
- the capillary column HP-5 cross-linked with 5% Ph Me silicone) from Hewlett Packard with a film thickness of 25 mm, a length of 30 m and an inner diameter of 0.32 mm was used.
- VZ viscosity number in cm 3 / g
- the polymer was precipitated from methanol, filtered off, washed with methanol and dried at 100 ° C. for 8 hours. 1.82 g (71% of theory) of a white solid were obtained.
- the filtrate was added to 0.80 ml (0.88 g, 5.8 mmol) of 5-norbornene-2-carboxylic acid methyl ester.
- the polymerization solution was stirred for 5 days at room temperature.
- the polymer was precipitated in methanol, filtered off, washed and dried at 100 ° C. for 8 hours. 0.84 g (96% of theory) of a white solid were obtained.
- the polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 1.21 g (24% of the Theory) of a white solid.
- the polymerization solution was stirred for half an hour at room temperature.
- the polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 0.70 g (54% of theory) of a white solid were obtained.
- the polymerization solution was stirred at a temperature of 40X for three hours.
- the polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 194.8 mg (8.9% of theory) of a white solid were obtained.
- the yellow polymerization solution was stirred at a temperature of 60% for half an hour.
- the polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 251.6 mg (11.4% of theory) of a white solid were obtained.
- the yellow polymerization solution was stirred for 5 days at room temperature. The solution turned green after 10 minutes. The polymer was precipitated in methanol filtered off, washed and dried at 100 ⁇ for 8 hours. 0.43 g (18.8% of theory) of a white solid were obtained.
- the polymer was precipitated from methanol, filtered off and washed with methanol. The product was dried at 100X for 8 hours. 1.49 g (47% of theory) of the polymer were obtained.
- the yellow catalyst solution was filtered through a Millipor filter and the filtrate was added to 3.34 g (22.0 mmol) of 5-norbornene-2-carboxylic acid ethyl ester in 3.6 ml of dichloromethane.
- the yellow polymerization mixture was stirred at room temperature for 20 hours.
- the Polymer was precipitated from methanol, filtered off, washed with methanol.
- the product was dried at 100X for 8 hours. 0.47 g (14% of theory) of the polymer were obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002286695A CA2286695A1 (fr) | 1997-04-11 | 1998-04-07 | Catalyseur et son utilisation pour la polymerisation |
EP98921435A EP0973786A1 (fr) | 1997-04-11 | 1998-04-07 | Catalyseur et son utilisation pour la polymerisation |
JP54343798A JP2001519821A (ja) | 1997-04-11 | 1998-04-07 | 触媒および重合のためのその触媒の使用 |
AU74294/98A AU7429498A (en) | 1997-04-11 | 1998-04-07 | Catalyst and use of catalysts in polymerisation |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19715104.3 | 1997-04-11 | ||
DE19715104 | 1997-04-11 | ||
DE19716312.2 | 1997-04-18 | ||
DE19716312A DE19716312A1 (de) | 1997-04-11 | 1997-04-18 | Katalysator und Verwendung des Katalysators für die Polymerisation |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998046614A1 true WO1998046614A1 (fr) | 1998-10-22 |
Family
ID=26035688
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/002003 WO1998046614A1 (fr) | 1997-04-11 | 1998-04-07 | Catalyseur et son utilisation pour la polymerisation |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0973786A1 (fr) |
JP (1) | JP2001519821A (fr) |
AU (1) | AU7429498A (fr) |
CA (1) | CA2286695A1 (fr) |
WO (1) | WO1998046614A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2177598A1 (fr) * | 2008-10-14 | 2010-04-21 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Isomères de l'acide bicyclo[2.2.1]hept-5-ène-2-carboxylique, ester éthylique et leur utilisation dans des compositions de parfums |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7989571B2 (en) | 2002-07-10 | 2011-08-02 | Lg Chem, Ltd. | Method for producing norbornene monomer composition, norbornene polymer prepared therefrom, optical film comprising the norbornene polymer, and method for producing the norbornene polymer |
DE60311103T2 (de) * | 2002-07-10 | 2007-10-25 | Lg Chem, Ltd. | Auf norbornenester basierendes polymerisat und verfahren zu seiner herstellung |
US7312285B2 (en) | 2002-07-10 | 2007-12-25 | Lg Chem, Ltd. | Method for preparing norbornene based addition polymer containing ester or acetyl functional group |
KR100561068B1 (ko) | 2002-07-10 | 2006-03-15 | 주식회사 엘지화학 | 노보넨-에스테르계 부가중합체 및 이의 제조방법 |
KR101046430B1 (ko) * | 2008-09-11 | 2011-07-05 | 삼성전기주식회사 | 저유전율 및 저손실 특성을 가진 노르보넨계 중합체, 이를이용한 절연재, 인쇄회로기판 및 기능성 소자 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4447066A1 (de) * | 1994-12-29 | 1996-07-04 | Hoechst Ag | Heterocyclische Carbene enthaltende Metallkomplexverbindungen |
US5569730A (en) * | 1993-11-16 | 1996-10-29 | The B. F. Goodrich Company | Addition polymers derived from norbornene-functional monomers and process therefor |
-
1998
- 1998-04-07 AU AU74294/98A patent/AU7429498A/en not_active Abandoned
- 1998-04-07 CA CA002286695A patent/CA2286695A1/fr not_active Abandoned
- 1998-04-07 EP EP98921435A patent/EP0973786A1/fr not_active Withdrawn
- 1998-04-07 JP JP54343798A patent/JP2001519821A/ja active Pending
- 1998-04-07 WO PCT/EP1998/002003 patent/WO1998046614A1/fr not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5569730A (en) * | 1993-11-16 | 1996-10-29 | The B. F. Goodrich Company | Addition polymers derived from norbornene-functional monomers and process therefor |
DE4447066A1 (de) * | 1994-12-29 | 1996-07-04 | Hoechst Ag | Heterocyclische Carbene enthaltende Metallkomplexverbindungen |
Non-Patent Citations (4)
Title |
---|
ACTA POLYM. (1997), 48(9), 385-391 CODEN: ACPODY;ISSN: 0323-7648, 1997 * |
CHEMICAL ABSTRACTS, vol. 127, no. 22, 1 December 1997, Columbus, Ohio, US; abstract no. 307733, HEINZ, B. S. ET AL: "Poly(norbornene carboxylic acid ester). Synthesis and properties" XP002075149 * |
CHEMICAL ABSTRACTS, vol. 129, Columbus, Ohio, US; abstract no. 68084, HEINZ, BEATE S. ET AL: "Pd(II)-catalyzed vinylic polymerization of norbornene and copolymerization with norbornene carboxylic acid esters" XP002075150 * |
MACROMOL. RAPID COMMUN. (1998), 19(5), 251-256 CODEN: MRCOE3;ISSN: 1022-1336, 1998 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2177598A1 (fr) * | 2008-10-14 | 2010-04-21 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Isomères de l'acide bicyclo[2.2.1]hept-5-ène-2-carboxylique, ester éthylique et leur utilisation dans des compositions de parfums |
Also Published As
Publication number | Publication date |
---|---|
JP2001519821A (ja) | 2001-10-23 |
AU7429498A (en) | 1998-11-11 |
CA2286695A1 (fr) | 1998-10-22 |
EP0973786A1 (fr) | 2000-01-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1770491C3 (de) | Verfahren zur Herstellung von trans-Polynentenamer | |
DE2729196A1 (de) | Verfahren zur herstellung von polymeren oder copolymeren von olefinen mit zumindest 3 kohlenstoffatomen | |
DE19654074A1 (de) | Verfahren zur Herstellung hydrierter ringgeöffneter Metathesepolymeren | |
DE2027905B2 (de) | Verfahren zur herstellung von polyalkenameren | |
DE112020002202T5 (de) | Neuartige Diaroylcarbazolverbindung und Verwendung derselben als Sensibilisierungsmittel | |
Heinz et al. | Poly (norbornene carboxylic acid ester) s: Synthesis and properties | |
WO1998046614A1 (fr) | Catalyseur et son utilisation pour la polymerisation | |
DE1945358B2 (de) | Niedermolekulare Polyalkenamere und Verfahren zu deren Herstellung | |
US3081334A (en) | Bicyclo-[2.2.2]oct-2-ene-1, 4-dicarboxylic acid, its preparation and functional derivatives | |
DE60024682T2 (de) | Durch ringöffnende polymerisation hergestellte copolymere, hydrierungsprodukt durch ringöffnende polymerisation hergestellter copolymere und verfahren zur herstellung derselben | |
DE19716312A1 (de) | Katalysator und Verwendung des Katalysators für die Polymerisation | |
Pittman Jr et al. | Organometallic polymers. XXX. Synthesis and copolymerization of η6-(2-phenylethyl methacrylate) tricarbonylchromium with organic monomers | |
DE1770642C2 (de) | Verfahren zur Herstellung von Copolymerisaten von Maleinsäureanhydrid und konjugierten Dienen | |
Pittman JR et al. | Organometallic polymers. XXVII. Radical-initiated polymerization and copolymerization of π-(2, 4-hexadien-1-yl acrylate) tricarbonyliron | |
CH434761A (de) | Verfahren zur Umwandlung von olefinischen Polymeren in hydroxylgruppenhaltige Polymere | |
MXPA06006495A (es) | Copolimeros funcionales, lineales, de etileno con distribuciones precisas minimas de longitud de recorrido y metodos para hacer los mismos. | |
DE1954255C3 (de) | Polymere mit einem System von konjugierten Doppelbindungen in der Hauptkette und Verfahren zu deren Herstellung | |
EP0661310A2 (fr) | Copolymères de cyclooléfines et procédé de leur préparation | |
DE2521152A1 (de) | Polymeren aus cis-5-norbornen- 2,3-dicarboxy-anhydrid | |
EP0973813A1 (fr) | Preparation d'homopolymeres, de copolymeres ou de copolymeres sequences a base d'unites monomeres cyclo-olefiniques | |
DE1520013A1 (de) | Poly(2-butindiol-1,4) sowie Verfahren zu dessen Herstellung | |
Qureshi et al. | Investigations into the free radical polymerizations of allyl carbonates—I. The reaction of t-butoxyl radical | |
DE2334606A1 (de) | Polymerisation von norbornenderivaten | |
DE69704507T2 (de) | Katalytische Komponente auf Basis von Vanadium und ihre Verwendung zur Herstellung von EP (D) M | |
DE2316112A1 (de) | Verfahren zur herstellung von mischpolymerisaten aus maleinsaeure und konjugierten dienen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AU AZ BA BB BG BR BY CA CN CU CZ EE GE GW HU ID IL IS JP KG KP KR KZ LC LK LR LT LV MD MG MK MN MX NO PL RO RU SG SI SK SL TJ TM TR TT UA US UZ VN YU |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1998921435 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2286695 Country of ref document: CA Ref country code: CA Ref document number: 2286695 Kind code of ref document: A Format of ref document f/p: F |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1998 543437 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09402856 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 1998921435 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1998921435 Country of ref document: EP |