CA2286695A1 - Catalyst and use of catalysts in polymerisation - Google Patents
Catalyst and use of catalysts in polymerisation Download PDFInfo
- Publication number
- CA2286695A1 CA2286695A1 CA002286695A CA2286695A CA2286695A1 CA 2286695 A1 CA2286695 A1 CA 2286695A1 CA 002286695 A CA002286695 A CA 002286695A CA 2286695 A CA2286695 A CA 2286695A CA 2286695 A1 CA2286695 A1 CA 2286695A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- compound
- mmol
- endo
- polymerization
- 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.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 polycyclic hydrocarbon Chemical group 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
- 229920001519 homopolymer Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000001925 cycloalkenes Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 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
- 101100295738 Gallus gallus COR3 gene Proteins 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
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 125000001153 fluoro group Chemical group F* 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
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen 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
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims 2
- 125000001814 trioxo-lambda(7)-chloranyloxy group Chemical group *OCl(=O)(=O)=O 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
- 229920000642 polymer Polymers 0.000 description 37
- 238000006116 polymerization reaction Methods 0.000 description 37
- 238000005227 gel permeation chromatography Methods 0.000 description 29
- 239000000203 mixture Substances 0.000 description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 20
- 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 17
- 239000000706 filtrate Substances 0.000 description 14
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 150000004702 methyl esters Chemical class 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- 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 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 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
- 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
- 238000004458 analytical method Methods 0.000 description 3
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical class C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 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
- 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 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- 101100219382 Caenorhabditis elegans cah-2 gene Proteins 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910004064 NOBF4 Inorganic materials 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 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
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920002521 macromolecule Polymers 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
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite group Chemical group N(=O)[O-] IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- XFTXGTMZGBLHQG-UHFFFAOYSA-N sbb039732 Chemical compound C1=CC(C)=CC=C1N1C(=O)C2C(C=C3)CC3C2C1=O XFTXGTMZGBLHQG-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000002348 vinylic group Chemical group 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
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
The invention relates to a catalyst and the use thereof in polymerisation. The catalyst contains a compound of general formula (I), wherein R1 stands for a mono or polycylic hydrocarbon, M1+ means an VIIIb group transition metal and X is at least one non-coordinating or low-coordinating anion.
Description
Catalyst and use of the catalyst for polymerization The present invention relates to a novel catalyst and the use of the catalyst for the polymerization of functionalized and nonfunctionalized cycloolefins.
The vinylic polymerization of norbornene gives a polymer which has a high glass transition temperature, a high density and a high index of refraction, cf. Macromol. Chem. Phys 1886, 197, 3435-3453. The introduction of functional groups on the norbornene skeleton should make it possible to vary the properties of the polymer.
A polynorbornene which is substituted by an ester group in the 2 position, for example vinylically polymerized methyl 5-norbornene-2-carboxylate, displays better solubility properties than unsubstituted polynorbornene n c oocH3 where n is a number > 1. In contrast to pol~norbornene, 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 above 250°C and has a higher density than polynorbornene.
Polymer-analogous reactions such as saponification and the preparation of blends are possible.
The ester can, like many other functionalized norbornene derivatives, be easily prepared by means of the Diets-Alder reaction. However, it can be polymerized only very slowly using the palladium(II)-nitrite catalysts used for the polymerization of norbornene. US-A-3,330,815 describes the polymerization of various norbornene derivatives using Pd(II) chloro complexes.
Macromolecules 1996, 29, 2755-2763 discloses ~3-allylpalladium(II) and palladium(II)-nitrite catalysts for the addition polymerization of norbornene compounds containing functional groups. Such catalysts produce polymers having a molecular weight which is not high enough for industrial applications.
It is an object of the invention to provide a novel catalyst for the polymerization, which has a higher reactivity and produces polymers having a higher molecular weight, and also a process for preparing homopolymers and/or copolymers, The object of the present invention is achieved by a catalyst comprising the compound of the formula (I):
(I).
M~~ XO
where R~ is a monocyclic or polycyclic hydrocarbon, M~+ is a transition metal of group Vlllb, X is at least one noncoordinating or weakly coordinating anion.
In a preferred embodiment of the invention, the catalyst comprises a compound of the formula (I) in which R~ is a monocyclic or polycyclic hydrocarbon having at least one unsaturated bond within or outside the ring, M~+ is Rh, Ru, Pd, Co or Ni, X is BF4_, PFg_, SbFg_, AsFg_, CI04_, BPh4_, where the phenyl groups may be substituted by fluorine or trifluoromethyl, closo-boranes and also carboranes and their halogenated derivatives or triflates.
In a particularly preferred embodiment of the invention, the catalyst comprises a compound of the formula (I) in which R~ is substituted or unsubstituted norbornene, cyclooctene, tricyclodecene or exo-methylenecyclohexene, M~+ is Pd, X is BF4_, PFg_, SbFg_, AsFg_ or a carborane.
The vinylic polymerization of norbornene gives a polymer which has a high glass transition temperature, a high density and a high index of refraction, cf. Macromol. Chem. Phys 1886, 197, 3435-3453. The introduction of functional groups on the norbornene skeleton should make it possible to vary the properties of the polymer.
A polynorbornene which is substituted by an ester group in the 2 position, for example vinylically polymerized methyl 5-norbornene-2-carboxylate, displays better solubility properties than unsubstituted polynorbornene n c oocH3 where n is a number > 1. In contrast to pol~norbornene, 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 above 250°C and has a higher density than polynorbornene.
Polymer-analogous reactions such as saponification and the preparation of blends are possible.
The ester can, like many other functionalized norbornene derivatives, be easily prepared by means of the Diets-Alder reaction. However, it can be polymerized only very slowly using the palladium(II)-nitrite catalysts used for the polymerization of norbornene. US-A-3,330,815 describes the polymerization of various norbornene derivatives using Pd(II) chloro complexes.
Macromolecules 1996, 29, 2755-2763 discloses ~3-allylpalladium(II) and palladium(II)-nitrite catalysts for the addition polymerization of norbornene compounds containing functional groups. Such catalysts produce polymers having a molecular weight which is not high enough for industrial applications.
It is an object of the invention to provide a novel catalyst for the polymerization, which has a higher reactivity and produces polymers having a higher molecular weight, and also a process for preparing homopolymers and/or copolymers, The object of the present invention is achieved by a catalyst comprising the compound of the formula (I):
(I).
M~~ XO
where R~ is a monocyclic or polycyclic hydrocarbon, M~+ is a transition metal of group Vlllb, X is at least one noncoordinating or weakly coordinating anion.
In a preferred embodiment of the invention, the catalyst comprises a compound of the formula (I) in which R~ is a monocyclic or polycyclic hydrocarbon having at least one unsaturated bond within or outside the ring, M~+ is Rh, Ru, Pd, Co or Ni, X is BF4_, PFg_, SbFg_, AsFg_, CI04_, BPh4_, where the phenyl groups may be substituted by fluorine or trifluoromethyl, closo-boranes and also carboranes and their halogenated derivatives or triflates.
In a particularly preferred embodiment of the invention, the catalyst comprises a compound of the formula (I) in which R~ is substituted or unsubstituted norbornene, cyclooctene, tricyclodecene or exo-methylenecyclohexene, M~+ is Pd, X is BF4_, PFg_, SbFg_, AsFg_ or a carborane.
In a very particularly preferred embodiment of the invention, the catalyst comprises a compound of the formula (1) in which R~ is a compound of the formula (II) RZ (~~).
where R2 is a hydrogen atom, a C~-C2p-alkyl group, a Cg-C2p-aryl group, ORS, SRS, OCOR3, R300CCHCOOR3 or R30CCHCOR3, where R3 is a hydrogen atom, a C~-C2p-alkyl group or a Cg-C2p-aryl group, -CN, -SCN, -NR32, N3 or a halogen atom.
According to the invention, the compound of the formula (I) is dissolved in at least one halogenated hydrocarbon, aliphatic hydrocarbon or aromatic hydrocarbon which may, if desired, contain a heteroatom such as halogen, oxycten or nitrogen.
The compound of the formula (I) is preferably dissolved in methylene chloride, chloroform, nitromethane, dimethylformamide, N-methyl-pyrrolidone, dimethylethyleneurea, nitrobenzene or chlorobenzene.
The invention provides a compound of the formula (I) and a cycloolefin which has at least one radical R4, where the ratio of the compound of the formula (I) to the cycloolefin is from 1:1 to 1:10 and R4 is a COORS, -NC or COR3 group.
The invention provides a process for preparing the compound of the formula (I), which comprises reacting M~+R~HaI with M2+X
in at least one solvent, where Hal is F , CI , Br , I or a pseudohalogen such as CN or SCN and M2+ is an alkali metal, an alkaline earth metal, Ag, TI or Cu.
The invention provides a process for preparing the compound of the formula (I) and a cycloolefin, which comprises initially charging an amount of from 1:1 to 1:10, based on the compound of the formula (I) and reacting M~+R~HaI with M2+X in at least one solvent.
The invention provides a process for preparing homopolymers and/or copolymers using at least one compound of the formula (I) as catalyst system.
Here, the invention provides a process for preparing a homopolymer and/or copolymer by polymerization of from 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
C ' CH
R'Z.-C R8 (,III) CH
H/ ~R6 C'CH' NCH
( CH
Rte' C R$ CH
HC CH
CH ~ \CH
HC' C~ /CH2 I H
R~ C R$ CH2 (IV') hiC CH
CH ~ \CH
where R2 is a hydrogen atom, a C~-C2p-alkyl group, a Cg-C2p-aryl group, ORS, SRS, OCOR3, R300CCHCOOR3 or R30CCHCOR3, where R3 is a hydrogen atom, a C~-C2p-alkyl group or a Cg-C2p-aryl group, -CN, -SCN, -NR32, N3 or a halogen atom.
According to the invention, the compound of the formula (I) is dissolved in at least one halogenated hydrocarbon, aliphatic hydrocarbon or aromatic hydrocarbon which may, if desired, contain a heteroatom such as halogen, oxycten or nitrogen.
The compound of the formula (I) is preferably dissolved in methylene chloride, chloroform, nitromethane, dimethylformamide, N-methyl-pyrrolidone, dimethylethyleneurea, nitrobenzene or chlorobenzene.
The invention provides a compound of the formula (I) and a cycloolefin which has at least one radical R4, where the ratio of the compound of the formula (I) to the cycloolefin is from 1:1 to 1:10 and R4 is a COORS, -NC or COR3 group.
The invention provides a process for preparing the compound of the formula (I), which comprises reacting M~+R~HaI with M2+X
in at least one solvent, where Hal is F , CI , Br , I or a pseudohalogen such as CN or SCN and M2+ is an alkali metal, an alkaline earth metal, Ag, TI or Cu.
The invention provides a process for preparing the compound of the formula (I) and a cycloolefin, which comprises initially charging an amount of from 1:1 to 1:10, based on the compound of the formula (I) and reacting M~+R~HaI with M2+X in at least one solvent.
The invention provides a process for preparing homopolymers and/or copolymers using at least one compound of the formula (I) as catalyst system.
Here, the invention provides a process for preparing a homopolymer and/or copolymer by polymerization of from 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
C ' CH
R'Z.-C R8 (,III) CH
H/ ~R6 C'CH' NCH
( CH
Rte' C R$ CH
HC CH
CH ~ \CH
HC' C~ /CH2 I H
R~ C R$ CH2 (IV') hiC CH
CH ~ \CH
./~ C~ ,,~ CH .~, ~ RS
HC C~ CH
RZ~C Rg Rg C R1~ ~ M
H C~ CH
C~ ~ CH~ ~ R6 H 'CH~C~CH-._ CH- CH~CH~RS
8' '~ ( ~1~0.. 1t__ ~ _ R1'2 (~ R C-R ~ R C ~ R C ~ M) CH ~ CH ~ CH
CH~ ~ C~ ~ Chli ~ R6 CH ~ ~ CH -~.' ~ R5 aC~ CH CH
R7 C RS ~ (Vil) H CH CH' CH~ ~.. R6 CH
Rto 'CH ~ ~Chl ~ RS
IH ~CH~
. CH CH
R~- C--Rg ~. ~ R11._ C-R12 ~ (VIII) CH
CH CH
\ \ ~ R6 C 'CH ~ ~C~
where R9, R1~, R11, R12, R13, R14, R15 and R16 are identical or different and are each a hydrogen atom or a hydrocarbon radical, where identical radicals in the various formulae may have different meanings and the polycyclic olefins are preferably at least monosubstituted carboxylic acid and/or dicarboxylic acid derivatives, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one monocyclic olefin of the formula IX
CH CH
\ ~ (~X) (CN2)q where q is a number from 2 to 10, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula X
\ /
C (X) t8 where R~3, R14. R15 and R16 are identical or different and are each a hydrogen atom or a hydrocarbon radical, preferably a Cg-Cep-aryl radical or a C1-Cg-alkyl radical.
According to the invention, homopolymers and/or copolymers of norbornenecarboxylic acid derivatives and norbornenedicarboxylic acid derivatives are obtained. Here, homopolymers and/or copolymers of the norbornene substituted by at least one carboxyl, ester, amide or nitrite group or the norbornenecarboxylic anhydride or -imide are obtained.
Preferred examples of norbornenecarboxylic acid and norbornenedicarboxylic acid derivatives are:
methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate, ethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate, bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, bicyclo[2.2.1]hept-5-ene, methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate, dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, diethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, N-p-tolylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide and also further aliphatic and aromatic N-substituted norbornene-2,3-dicarboximides.
The derivatives can also be substituted in the 7 position.
HC C~ CH
RZ~C Rg Rg C R1~ ~ M
H C~ CH
C~ ~ CH~ ~ R6 H 'CH~C~CH-._ CH- CH~CH~RS
8' '~ ( ~1~0.. 1t__ ~ _ R1'2 (~ R C-R ~ R C ~ R C ~ M) CH ~ CH ~ CH
CH~ ~ C~ ~ Chli ~ R6 CH ~ ~ CH -~.' ~ R5 aC~ CH CH
R7 C RS ~ (Vil) H CH CH' CH~ ~.. R6 CH
Rto 'CH ~ ~Chl ~ RS
IH ~CH~
. CH CH
R~- C--Rg ~. ~ R11._ C-R12 ~ (VIII) CH
CH CH
\ \ ~ R6 C 'CH ~ ~C~
where R9, R1~, R11, R12, R13, R14, R15 and R16 are identical or different and are each a hydrogen atom or a hydrocarbon radical, where identical radicals in the various formulae may have different meanings and the polycyclic olefins are preferably at least monosubstituted carboxylic acid and/or dicarboxylic acid derivatives, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one monocyclic olefin of the formula IX
CH CH
\ ~ (~X) (CN2)q where q is a number from 2 to 10, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula X
\ /
C (X) t8 where R~3, R14. R15 and R16 are identical or different and are each a hydrogen atom or a hydrocarbon radical, preferably a Cg-Cep-aryl radical or a C1-Cg-alkyl radical.
According to the invention, homopolymers and/or copolymers of norbornenecarboxylic acid derivatives and norbornenedicarboxylic acid derivatives are obtained. Here, homopolymers and/or copolymers of the norbornene substituted by at least one carboxyl, ester, amide or nitrite group or the norbornenecarboxylic anhydride or -imide are obtained.
Preferred examples of norbornenecarboxylic acid and norbornenedicarboxylic acid derivatives are:
methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate, ethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate, bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, bicyclo[2.2.1]hept-5-ene, methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate, dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, diethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, N-p-tolylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide and also further aliphatic and aromatic N-substituted norbornene-2,3-dicarboximides.
The derivatives can also be substituted in the 7 position.
The invention provides for the use of a compound of the formula (I) as catalyst system for preparing homopolymers and/or copolymers.
The invention is illustrated by the following examples.
Examples General procedures The analyses were carried out by the methods described below. The NMR
spectra were recorded on a Bruker AC 300 spectrometer at a frequency of -300 MHz for ~H-NMR and 75 MHz for ~3C-NMR. The IR spectra were recorded on a Perkin Elmer FT-IR spectrometer 1600. Solids were measured as pressed KBr disks, liquids were measured between two sodium chloride plates. The GPC (gel permeation chromatography) analyses were carried out using a solution of 0.2 g of polymer in 10 ml of tetrahydrofuran on two 10 mm polymer-mixed-gel columns (600 x 8 mm) of PSS. A differential refractometer and differential viscornetsr from Knauer served as detector. A Knauer pump was employed. The inherent viscosities were determined at a temperature of 25°C on 0.5 percent strength by weight polymer solutions in dichloromethane. The GC analyses were carried out on a gas chromatograph model 5890 from Hewlett Packard. Injector and detector had a temperature of 300°C. The temperature program employed was: isothermal at 70°C for 4 minutes, then heating to 280°C at a heating rate of 15°C/min. The capillary column HP-5 (crosslinked with 5% of PhMe silicone) from Hewlett Packard having a film thickness of 25 mm, a length of 30 m and an internal diameter of 0.32 mm was used.
Abbreviations:
VN - viscosity number in cm3/g GC - gas chromatograph MW - weight average molar mass in g/mol MW/M~ - molar mass distribution, determined by gel permeation chromatography Starting compounds Example 1 Ethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (exo/endo=25/75) In a 1 I three-necked flask, 342.53 g (3.42 mol) of ethyl acrylate were added to 268 g (4.05 mol) of freshly distilled cyclopentadiene while cooling in ice. The ice bath was removed and the mixture was stirred for 8 hours on a water bath at 20°C and then heated at 40°C for 1 hour.
After distillation (boiling point: 73°C/6 mbar), 454.4 g (80% of theory) of the ethyl ester were obtained. GC analysis indicated an exo-endo ratio of 20:80.
Elemental analysis found C 72.27, H 8.59 (calculated for C~pH1402, C
72.26, H 8.49).
~H-NMR (CDCI3): b = 1.2 (4H, m, exo/endo-Ct-13, 1/2 endo-CH2), 1.3 (2H, m, exo/endo-CH2), 1.4 (1 H, m, 1/2 exo-CHZ), 1.8 (1 H, m, 1/2 exo/endo-CH2), 2.1 (1 H, m, exo-CHCCO), 2.8 (2H,- m, exo/endo-CH, endo-CHCOO), 2.9 (1 H, m, exo-CH), 3.1 (1 H, m, endo-CH), 4.0 (2H, m, exo/endo-COOCH2), 5.8 (1 H, dd, endo = CH), 6.0 (2H, dd, exo =-CH), 6.1 (1 H, dd, endo = CH) ppm 13C-NMR (CDCI3): exo: 8 = 14.1 (1 C, s, CH3), 30.1 (1 C, s, CH2), 41.5 (1C, s, (1C, 1s, =CH), 137.8 (1C, 1s, =CH), 175.9 (1C, 1 s, CO) ppm endo: 8 = 14.1 (1 C, s, CH3), 29.0 (1 C, 1 s, CH2), 2.4 (1 C, 1 s, CH), 43.4 (1 C, 1 s, CHCOO), 45.5 (1 C, 1 s, CH), 49.4 (1 C, 1 s, CH2) 59.8 (1 C, 1 s, OCHl), 132.2 (1C, 1s, =CH), 137.4 (1C, 1s, =CH), 174.4 (1C, 1s, CO) ppm IR (KBr): v = 3061 (m), 2978 (s), 2956 (s), 2903 (m), 2874 (m), 1733 (s), 1447 (m), 1370 (s), 1335 (s), 2171 (s), 1186 (s), 1110 (s), 1039 (s), 862 (m), 838 (m), 712 (s) cm ~
The invention is illustrated by the following examples.
Examples General procedures The analyses were carried out by the methods described below. The NMR
spectra were recorded on a Bruker AC 300 spectrometer at a frequency of -300 MHz for ~H-NMR and 75 MHz for ~3C-NMR. The IR spectra were recorded on a Perkin Elmer FT-IR spectrometer 1600. Solids were measured as pressed KBr disks, liquids were measured between two sodium chloride plates. The GPC (gel permeation chromatography) analyses were carried out using a solution of 0.2 g of polymer in 10 ml of tetrahydrofuran on two 10 mm polymer-mixed-gel columns (600 x 8 mm) of PSS. A differential refractometer and differential viscornetsr from Knauer served as detector. A Knauer pump was employed. The inherent viscosities were determined at a temperature of 25°C on 0.5 percent strength by weight polymer solutions in dichloromethane. The GC analyses were carried out on a gas chromatograph model 5890 from Hewlett Packard. Injector and detector had a temperature of 300°C. The temperature program employed was: isothermal at 70°C for 4 minutes, then heating to 280°C at a heating rate of 15°C/min. The capillary column HP-5 (crosslinked with 5% of PhMe silicone) from Hewlett Packard having a film thickness of 25 mm, a length of 30 m and an internal diameter of 0.32 mm was used.
Abbreviations:
VN - viscosity number in cm3/g GC - gas chromatograph MW - weight average molar mass in g/mol MW/M~ - molar mass distribution, determined by gel permeation chromatography Starting compounds Example 1 Ethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (exo/endo=25/75) In a 1 I three-necked flask, 342.53 g (3.42 mol) of ethyl acrylate were added to 268 g (4.05 mol) of freshly distilled cyclopentadiene while cooling in ice. The ice bath was removed and the mixture was stirred for 8 hours on a water bath at 20°C and then heated at 40°C for 1 hour.
After distillation (boiling point: 73°C/6 mbar), 454.4 g (80% of theory) of the ethyl ester were obtained. GC analysis indicated an exo-endo ratio of 20:80.
Elemental analysis found C 72.27, H 8.59 (calculated for C~pH1402, C
72.26, H 8.49).
~H-NMR (CDCI3): b = 1.2 (4H, m, exo/endo-Ct-13, 1/2 endo-CH2), 1.3 (2H, m, exo/endo-CH2), 1.4 (1 H, m, 1/2 exo-CHZ), 1.8 (1 H, m, 1/2 exo/endo-CH2), 2.1 (1 H, m, exo-CHCCO), 2.8 (2H,- m, exo/endo-CH, endo-CHCOO), 2.9 (1 H, m, exo-CH), 3.1 (1 H, m, endo-CH), 4.0 (2H, m, exo/endo-COOCH2), 5.8 (1 H, dd, endo = CH), 6.0 (2H, dd, exo =-CH), 6.1 (1 H, dd, endo = CH) ppm 13C-NMR (CDCI3): exo: 8 = 14.1 (1 C, s, CH3), 30.1 (1 C, s, CH2), 41.5 (1C, s, (1C, 1s, =CH), 137.8 (1C, 1s, =CH), 175.9 (1C, 1 s, CO) ppm endo: 8 = 14.1 (1 C, s, CH3), 29.0 (1 C, 1 s, CH2), 2.4 (1 C, 1 s, CH), 43.4 (1 C, 1 s, CHCOO), 45.5 (1 C, 1 s, CH), 49.4 (1 C, 1 s, CH2) 59.8 (1 C, 1 s, OCHl), 132.2 (1C, 1s, =CH), 137.4 (1C, 1s, =CH), 174.4 (1C, 1s, CO) ppm IR (KBr): v = 3061 (m), 2978 (s), 2956 (s), 2903 (m), 2874 (m), 1733 (s), 1447 (m), 1370 (s), 1335 (s), 2171 (s), 1186 (s), 1110 (s), 1039 (s), 862 (m), 838 (m), 712 (s) cm ~
Example 2 Ethyl bicylco[2.2.1]hept-5-ene-2-carboxylate (exo/endo=60/40) In a 200 ml flask, 1.65g (24.2 mmol) of sodium ethoxide were added to 80.51 g (0.485 mol) of ethyl 5-norbornene-2-carboxylate (exo/endo=25/75) and the mixture was stirred for 20 hours at a temperature of 100°C. The ester was subsequently distilled under reduced pressure in the presence of the sodium ethoxide via a 60 cm Vigreux column at a reflux ratio of 1:20.
After the distillation (boiling point found: 86-88°C/16 mbar), 73.3 g (91 % of theory) of a colorless liquid were obtained. GC analysis indicated an exo/endo ratio =20/80=60/40.
Example 3 Methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (exo/endo=70/30) In a 1 I three-necked flask, 239.43 g (2.78 mol) of methyl acrylate .were added to 218.91 g (3.31 mol) of freshly distilled cyclopentadiene while cooling in ice. The ice bath was removed and the mixture was stirred for 8 hours at 20°C on a water bath and then heated at 40°C for 1 hour. After distillation (boiling point: 73°C/14 mbar), 377.8 g (89% of theory) of the methyl ester were obtained. GC analysis indicated an exo/endo ratio of 20/80.
8.0 g (0.15 mmol) of sodium methoxide were added to 377.8 g (2.48 mol) of methyl 5-norbornene-2-carboxylate (exo/endo=20/80) and the mixture was stirred for 20 hours at a temperature of 105°C. The ester was subsequently distilled under reduced pressure in the presence of the sodium methoxide via a 100 cm packed column containing rolls of woven wire mesh at a reflux ratio of 1:100. After the distillation (boiling point found: 75°C-77°C/19 mbar), 280.9 g (74% of theory) of a colorless liquid were obtained. GC analysis indicated an exo/endo ratio of 70/30.
Elemental analysis found C 71.02, H 8.04 (calculated for CgH~202, C 71.03, H 7.94).
After the distillation (boiling point found: 86-88°C/16 mbar), 73.3 g (91 % of theory) of a colorless liquid were obtained. GC analysis indicated an exo/endo ratio =20/80=60/40.
Example 3 Methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (exo/endo=70/30) In a 1 I three-necked flask, 239.43 g (2.78 mol) of methyl acrylate .were added to 218.91 g (3.31 mol) of freshly distilled cyclopentadiene while cooling in ice. The ice bath was removed and the mixture was stirred for 8 hours at 20°C on a water bath and then heated at 40°C for 1 hour. After distillation (boiling point: 73°C/14 mbar), 377.8 g (89% of theory) of the methyl ester were obtained. GC analysis indicated an exo/endo ratio of 20/80.
8.0 g (0.15 mmol) of sodium methoxide were added to 377.8 g (2.48 mol) of methyl 5-norbornene-2-carboxylate (exo/endo=20/80) and the mixture was stirred for 20 hours at a temperature of 105°C. The ester was subsequently distilled under reduced pressure in the presence of the sodium methoxide via a 100 cm packed column containing rolls of woven wire mesh at a reflux ratio of 1:100. After the distillation (boiling point found: 75°C-77°C/19 mbar), 280.9 g (74% of theory) of a colorless liquid were obtained. GC analysis indicated an exo/endo ratio of 70/30.
Elemental analysis found C 71.02, H 8.04 (calculated for CgH~202, C 71.03, H 7.94).
Example 4 Bicyclo[2.2.1]heptadienepalladium chloride In a 200 ml flask, 2.00 g (11.3 mmol) of palladium(II) chloride were dissolved in 5 ml of concentrated hydrochloric acid by stirring at 50°C
for 1 hour. The solution was then cooled to room temperature. 150 ml of ethanol were added to the brown solution, the solution was filtered and the residue was washed with 20 ml of ethanol. 2.5 ml (2.27 g, 25 mmol) of norbornadiene were added to the filtrate whilst stirring. A yellow precipitate was formed and this was filtered off after 10 minutes and washed three times with 30 ml each time of diethyl ether. The product was recrystallized from dichloromethane. After drying, 2.28 g (77% of theory) of a yellow crystalline solid were obtained. Elemental analysis found C 31.38, H 2.98 (calculated for C~HgPdCl2, C 31.20, H 2.99).
~ H-NMR (DMSO-d6): b = 1.87 (t, J = 1.6 Hz, 2H, CH2), 3.56 (quip, J =
1.8Hz,2H,CH),6.76(t,J=l.9Hz,4H,CH)ppm ~3C-NMR (DMSO-d6): a = 50.4 (CH), 74.8 (CH2), 143.1 (CH) ppm IR (KBr): v = 3047 (s), 2956 (w), 2924 (w), 1407 (s), 1304 (s), 1226 (m), 1183 (m), 967 (m~, 939 (m), 898 (m), 828 (m), 792 (s), 769 (s) cm Example 5 Di-~-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a.2n)palla-dium(II) In a 100 ml nitrogen flask, 4 ml of methanol were added under nitrogen to 300 mg (1.11 mmol) of bicyclo[2.2.1]heptadienepalladium chloride and 101 mg (0.95 mmol) of sodium carbonate and the mixture was stirred at room temperature. After one hour, a light-yellow, fine precipitate had formed and this was filtered off and dried under an oil pump vacuum.
289 mg (98% of theory) of a light-yellow solid were obtained. Elemental analysis found C 35.88, H 4.27 (calculated for C~gH22Pd2C12, C 36.25, H
4.18).
~ H-NMR (CDCI3): 8 = 6.09 (t, J = 3.87 Hz, =CH), 5.88 (t, J = 3.87 Hz, 1 H =CH), 4.12 (s, 1 H, CH) 3.24 (s, 3H, OCH3), 3.20 (s, 1 H, CH), 2.90 (s, 1 H, CH), 1.87 (s, 1 H, CH), 1.88 (d, J = 10.19 Hz, 1 H, CH2), 1.61 (d, J = 9.85 Hz, 1 H, CH2) Polymerization Example 6 All monomers used were dried over CaH2, distilled under reduced pressure and saturated with nitrogen. The preparation of the catalyst solutions was carried out under nitrogen. All polymerization experiments were likewise carried out in a nitrogen atmosphere with exclusion of moisture and oxygen.
Example 7 Methyl bicyclo[2.2.1]kept-5-ene-2-carboxylate (exolendo=70/30) Polymerization of the methyl ester using an rl3-allylpalladium(II) tetrafluoroborate complex at room temperature, [Pdj:[M]=1:70 1n a 100 ml flask, 14.6 mg (0.064 mmol) of r~3-allylpalladium chloride dimer were dissolved in 2 ml of dichloromethane. 24.0 mg (0.124 mmol) of AgBF4 were added thereto and the mixture was stirred for 20 minutes at room temperature. The yellow catalyst solution was filtered and the filtrate was added to 0.6 ml (0.66 g, 4.3 mmol) of methyl 5-norbornene-2-carboxylate. The reaction mixture was stirred at room temperature for 5 days. The polymer was precipitated from methanol, filtered off, washed with methanol and dried at 100°C for 8 hours. The yield was 647 mg (98%
of theory). The polymer had the following properties:
Mn(GPC)=11,600, M~",(GPC)=22,100.
Example 8 Polymerization at room temperature, [Pdj:[Mj=1:250 In a 100 ml flask, 13.7 mg (0.0377 mmol) of r~3-allylpalladium chloride dimer were dissolved in 2 ml of dichloromethane. 16.3 mg (0.0841 mmol) of AgBF4 were added to the solution and the mixture was stirred at room temperature for 20 minutes, forming a white precipitate. The yellow catalyst solution was filtered and the filtrate was added to a solution of 2.56 g (16.8 mmol) of methyl 5-norbornene-2-carboxylate in 8 ml of dichloromethane. The reaction mixture was stirred at room temperature for 4 days. 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 polymer had the following properties:
M~(GPC)=7200, MW(GPC)=79,000.
Example 9 Polymerization of the methyl ester using di-~-chloro-bis(6 methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) at room temperature, [Pd]:[M]=1:270 In a 100 ml nitrogen flask, 6.7 mg (0.015 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) were dissolved in 4 ml of dichloromethane. The solution was added to 1.09 g (7.17 mmol) of methyl 5-norbornene-2-carboxylate and the mixture was stirred at room øemperature for 5 days. The polymer was precipitated from methanol, filtered off, washed with methanol and dried at 100°G for 8 hours. The yield was 0.43 g (40% of theory). The polymer had the following properties:
Mn(GPC)=4600 M""(GPC)=7800 Example 10 Polymerization of the methyl ester using di-~-chloro-bis(6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) and NaAsFg, at room temperature, [Pd]:[M]=1:250 In a 100 ml flask, 6.5 mg (0.012 mmol of di-~-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2 ml of dichloromethane. 11.2 mg (0.033 mmol) of NaAsFg were added thereto and the mixture was stirred for 30 minutes at room temperature.
The yellow catalyst solution was filtered and the filtrate was added to 1.1 g (7.2 mmol) of methyl 5-norbornene-2-carboxylate. The polymerization solution became orange after half an hour. It was stirred at room temperature for 20 hours. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 0.23 g (21 % of theory) of a white solid was obtained.
Example 11 Polymerization of the methyl ester (endo/exo=50150) using a water-containing Pd catalyst, [Pd]:[M]=1:250 To prepare the catalyst solution, 318 mg (2.72 mmol) of NOBF4 were added to a mixture of 143.9 mg (1.35 mmol) of Pd(0) powder, 25 ml of nitromethane and 0.15 ml (150 mg, 8.3 mmol) of water in a 100 ml flask.
The gas formed was removed by evacuation. The solution was initially yellow, then it became green and finally dark red. In a 100 ml flask, 2.19 g (14.1 mmol) of methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate were dissolved in 10 ml of nitromethane. 1.0 ml of the catalyst solution was added thereto. After a reaction tirne of 4 days, the mixture was precipitated in methanol, the precipitate was filtered off, washed with methanol and dried at 100°C for 8 hours. The yield was 1.77 g (81 % of theory). The polymer had the following properties: M~(GPC)=17,000, MW(GPC)=24,000 Example 12 Polymerization of the methyl ester (endo/exo=70/30) using a 6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-56,2~)palladium(II) tetrafluoroborate complex at room temperature, [Pd]:[M]=1:220 Preparation of the catalyst In a 100 ml flask, 6.9 mg (0.013 mmol) of di-~-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) were dissolved in 4 ml of dichloromethane. 8.0 mg (0.041 mmol) of AgBF4 were added thereto and the mixture was stirred for 5 minutes at room temperature. The yellow catalyst solution was filtered.
~ H-NMR (CDCI3): s = 6.33 (s, 1 H, =CH), 6.15 (s, 1 H, =CH), 4.12 (s, 1 H, CH), 3.36 (d, J = 4.18 Hz, 1 H, CH), 3.29 (s, 3H, OCH3), 3.04 (s, 1 H, CH), 2.95 (S, 1 H, CH), 1.96 (d, J =9.81 Hz, 1 H, CH2), 1.73 (d, J =9.61, Hz, 1 H, CH2) ppm Polymerization The filtrate was added to 0.80 ml (0.88 g, 5.8 mmol) of methyl 5-norbornene-2-carboxylate. The polmerization solution was stirred at room temperature for 5 days. 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 was obtained. The polymer had the following properties:
Mn(GPC)=102,000, M"i,(GPC)=131,000, r~inh=0.366 dl/g, [r~]=0.374 dl/g, 25°C, CH2C12.
Elemental analysis calc. for (CgH~202)g71: C 71.03% H 7.95%
found: C 70.67% H 7.98&
~ H-NMR (CDCI3): 8 = 0.9 - 3.2 (m, CH, CH2, maxima at 1.5, 1.8 and 2.3), 3.6 (m, COOCH3) ppm ~3C-NMR (CDCI3): 8 = 30 - 60 (m, CH, CH2, maxima at 34.1, 37.2, 39.2, 42.3, 45.2, 46.3 and 51.5) 176.1 (m, CO) ppm IR (KBr): v = 2953 (s), 2883 (m), 1732 (s), 1435 (s), 1361 (m), 1197 (s), 1173 (s), 1042 (m) cm Example 13 Polymerization at room temperature, [Pd]:[M]=1:500 In a 100 ml flask, 20.0 mg (0.038 mmol) of di-~-chloro-bis-(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2 ml of dichloromethane. 21.9 mg (0.113 mmol) of AgBF4 were added thereto and the mixture was stirred for 5 minutes at room temperature. The yellow catalyst solution was filtered and the filtrate was added to a solution of 6.32 g (42 mmol) of methyl 5-norbornene-2-carboxylate in 10 ml of dichloromethane. 2 ml of this polymerization solution were removed after 0.5, 1, 2, 3.5 and 5.5 hours and the remainder of the solution was taken after 8 hours, and these samples were precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. The yield was 5% after 0.5 h, 5%
after 1 h, 17.4% after 2 h, 27% after 3.5 h, 41.8% after 5.5 h and 52.9%
after 8 h. The polymer had the following properties: Mn(GPC)=93,000 M~,(GPC)=130,000 after a polymerization time of 8 hours.
for 1 hour. The solution was then cooled to room temperature. 150 ml of ethanol were added to the brown solution, the solution was filtered and the residue was washed with 20 ml of ethanol. 2.5 ml (2.27 g, 25 mmol) of norbornadiene were added to the filtrate whilst stirring. A yellow precipitate was formed and this was filtered off after 10 minutes and washed three times with 30 ml each time of diethyl ether. The product was recrystallized from dichloromethane. After drying, 2.28 g (77% of theory) of a yellow crystalline solid were obtained. Elemental analysis found C 31.38, H 2.98 (calculated for C~HgPdCl2, C 31.20, H 2.99).
~ H-NMR (DMSO-d6): b = 1.87 (t, J = 1.6 Hz, 2H, CH2), 3.56 (quip, J =
1.8Hz,2H,CH),6.76(t,J=l.9Hz,4H,CH)ppm ~3C-NMR (DMSO-d6): a = 50.4 (CH), 74.8 (CH2), 143.1 (CH) ppm IR (KBr): v = 3047 (s), 2956 (w), 2924 (w), 1407 (s), 1304 (s), 1226 (m), 1183 (m), 967 (m~, 939 (m), 898 (m), 828 (m), 792 (s), 769 (s) cm Example 5 Di-~-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a.2n)palla-dium(II) In a 100 ml nitrogen flask, 4 ml of methanol were added under nitrogen to 300 mg (1.11 mmol) of bicyclo[2.2.1]heptadienepalladium chloride and 101 mg (0.95 mmol) of sodium carbonate and the mixture was stirred at room temperature. After one hour, a light-yellow, fine precipitate had formed and this was filtered off and dried under an oil pump vacuum.
289 mg (98% of theory) of a light-yellow solid were obtained. Elemental analysis found C 35.88, H 4.27 (calculated for C~gH22Pd2C12, C 36.25, H
4.18).
~ H-NMR (CDCI3): 8 = 6.09 (t, J = 3.87 Hz, =CH), 5.88 (t, J = 3.87 Hz, 1 H =CH), 4.12 (s, 1 H, CH) 3.24 (s, 3H, OCH3), 3.20 (s, 1 H, CH), 2.90 (s, 1 H, CH), 1.87 (s, 1 H, CH), 1.88 (d, J = 10.19 Hz, 1 H, CH2), 1.61 (d, J = 9.85 Hz, 1 H, CH2) Polymerization Example 6 All monomers used were dried over CaH2, distilled under reduced pressure and saturated with nitrogen. The preparation of the catalyst solutions was carried out under nitrogen. All polymerization experiments were likewise carried out in a nitrogen atmosphere with exclusion of moisture and oxygen.
Example 7 Methyl bicyclo[2.2.1]kept-5-ene-2-carboxylate (exolendo=70/30) Polymerization of the methyl ester using an rl3-allylpalladium(II) tetrafluoroborate complex at room temperature, [Pdj:[M]=1:70 1n a 100 ml flask, 14.6 mg (0.064 mmol) of r~3-allylpalladium chloride dimer were dissolved in 2 ml of dichloromethane. 24.0 mg (0.124 mmol) of AgBF4 were added thereto and the mixture was stirred for 20 minutes at room temperature. The yellow catalyst solution was filtered and the filtrate was added to 0.6 ml (0.66 g, 4.3 mmol) of methyl 5-norbornene-2-carboxylate. The reaction mixture was stirred at room temperature for 5 days. The polymer was precipitated from methanol, filtered off, washed with methanol and dried at 100°C for 8 hours. The yield was 647 mg (98%
of theory). The polymer had the following properties:
Mn(GPC)=11,600, M~",(GPC)=22,100.
Example 8 Polymerization at room temperature, [Pdj:[Mj=1:250 In a 100 ml flask, 13.7 mg (0.0377 mmol) of r~3-allylpalladium chloride dimer were dissolved in 2 ml of dichloromethane. 16.3 mg (0.0841 mmol) of AgBF4 were added to the solution and the mixture was stirred at room temperature for 20 minutes, forming a white precipitate. The yellow catalyst solution was filtered and the filtrate was added to a solution of 2.56 g (16.8 mmol) of methyl 5-norbornene-2-carboxylate in 8 ml of dichloromethane. The reaction mixture was stirred at room temperature for 4 days. 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 polymer had the following properties:
M~(GPC)=7200, MW(GPC)=79,000.
Example 9 Polymerization of the methyl ester using di-~-chloro-bis(6 methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) at room temperature, [Pd]:[M]=1:270 In a 100 ml nitrogen flask, 6.7 mg (0.015 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) were dissolved in 4 ml of dichloromethane. The solution was added to 1.09 g (7.17 mmol) of methyl 5-norbornene-2-carboxylate and the mixture was stirred at room øemperature for 5 days. The polymer was precipitated from methanol, filtered off, washed with methanol and dried at 100°G for 8 hours. The yield was 0.43 g (40% of theory). The polymer had the following properties:
Mn(GPC)=4600 M""(GPC)=7800 Example 10 Polymerization of the methyl ester using di-~-chloro-bis(6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) and NaAsFg, at room temperature, [Pd]:[M]=1:250 In a 100 ml flask, 6.5 mg (0.012 mmol of di-~-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2 ml of dichloromethane. 11.2 mg (0.033 mmol) of NaAsFg were added thereto and the mixture was stirred for 30 minutes at room temperature.
The yellow catalyst solution was filtered and the filtrate was added to 1.1 g (7.2 mmol) of methyl 5-norbornene-2-carboxylate. The polymerization solution became orange after half an hour. It was stirred at room temperature for 20 hours. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 0.23 g (21 % of theory) of a white solid was obtained.
Example 11 Polymerization of the methyl ester (endo/exo=50150) using a water-containing Pd catalyst, [Pd]:[M]=1:250 To prepare the catalyst solution, 318 mg (2.72 mmol) of NOBF4 were added to a mixture of 143.9 mg (1.35 mmol) of Pd(0) powder, 25 ml of nitromethane and 0.15 ml (150 mg, 8.3 mmol) of water in a 100 ml flask.
The gas formed was removed by evacuation. The solution was initially yellow, then it became green and finally dark red. In a 100 ml flask, 2.19 g (14.1 mmol) of methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate were dissolved in 10 ml of nitromethane. 1.0 ml of the catalyst solution was added thereto. After a reaction tirne of 4 days, the mixture was precipitated in methanol, the precipitate was filtered off, washed with methanol and dried at 100°C for 8 hours. The yield was 1.77 g (81 % of theory). The polymer had the following properties: M~(GPC)=17,000, MW(GPC)=24,000 Example 12 Polymerization of the methyl ester (endo/exo=70/30) using a 6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-56,2~)palladium(II) tetrafluoroborate complex at room temperature, [Pd]:[M]=1:220 Preparation of the catalyst In a 100 ml flask, 6.9 mg (0.013 mmol) of di-~-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) were dissolved in 4 ml of dichloromethane. 8.0 mg (0.041 mmol) of AgBF4 were added thereto and the mixture was stirred for 5 minutes at room temperature. The yellow catalyst solution was filtered.
~ H-NMR (CDCI3): s = 6.33 (s, 1 H, =CH), 6.15 (s, 1 H, =CH), 4.12 (s, 1 H, CH), 3.36 (d, J = 4.18 Hz, 1 H, CH), 3.29 (s, 3H, OCH3), 3.04 (s, 1 H, CH), 2.95 (S, 1 H, CH), 1.96 (d, J =9.81 Hz, 1 H, CH2), 1.73 (d, J =9.61, Hz, 1 H, CH2) ppm Polymerization The filtrate was added to 0.80 ml (0.88 g, 5.8 mmol) of methyl 5-norbornene-2-carboxylate. The polmerization solution was stirred at room temperature for 5 days. 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 was obtained. The polymer had the following properties:
Mn(GPC)=102,000, M"i,(GPC)=131,000, r~inh=0.366 dl/g, [r~]=0.374 dl/g, 25°C, CH2C12.
Elemental analysis calc. for (CgH~202)g71: C 71.03% H 7.95%
found: C 70.67% H 7.98&
~ H-NMR (CDCI3): 8 = 0.9 - 3.2 (m, CH, CH2, maxima at 1.5, 1.8 and 2.3), 3.6 (m, COOCH3) ppm ~3C-NMR (CDCI3): 8 = 30 - 60 (m, CH, CH2, maxima at 34.1, 37.2, 39.2, 42.3, 45.2, 46.3 and 51.5) 176.1 (m, CO) ppm IR (KBr): v = 2953 (s), 2883 (m), 1732 (s), 1435 (s), 1361 (m), 1197 (s), 1173 (s), 1042 (m) cm Example 13 Polymerization at room temperature, [Pd]:[M]=1:500 In a 100 ml flask, 20.0 mg (0.038 mmol) of di-~-chloro-bis-(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2 ml of dichloromethane. 21.9 mg (0.113 mmol) of AgBF4 were added thereto and the mixture was stirred for 5 minutes at room temperature. The yellow catalyst solution was filtered and the filtrate was added to a solution of 6.32 g (42 mmol) of methyl 5-norbornene-2-carboxylate in 10 ml of dichloromethane. 2 ml of this polymerization solution were removed after 0.5, 1, 2, 3.5 and 5.5 hours and the remainder of the solution was taken after 8 hours, and these samples were precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. The yield was 5% after 0.5 h, 5%
after 1 h, 17.4% after 2 h, 27% after 3.5 h, 41.8% after 5.5 h and 52.9%
after 8 h. The polymer had the following properties: Mn(GPC)=93,000 M~,(GPC)=130,000 after a polymerization time of 8 hours.
Example 14 Polymerization at room temperature, [Pd]:[M]=1:1000 In a 100 ml flask, 8.3 mg (0.0157 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-56,2~)palladium(II) were dissolved in 2.2 ml of dichloromethane. 9.2 mg (0.047 mmol) of AgBF4 were added thereto and the mixture was stirred for 5 minutes at room temperature. The yellow catalyst solution was filtered and added to a solution of 5.09 g (33 mmol) of methyl 5-norbornene-2-carboxylate in 8 ml of chlorobenzene.
The polymerization solution was stirred at room temperature for 20 hours.
The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 1.21 g (24% of theory) of a white solid were obtained.
The polymer had the following properties: M~(GPC)=95,000 MW(GPC)=203,000.
Example 15 Polymerization at 40°C, [Pd]:[M]=1:500 In a 100 ml flask, 4.4 mg (0.0083 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2 ml of dichloromethane. 110 mg (0.72 mmol) of methyl 5-norbornene-2-carboxylate and 4.7 mg (0.024 mmol) of AgBF4 were added thereto. The mixture was stirred at room temperature for 3 minutes, filtered and the filtrate was added to 1.29 g (8.5 mmol) of methyl 5-norbornene-2-carboxylate. The polymerization solution was stirred at room temperature for half an hour. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 0.70 g (54% of theory) of a white solid was obtained. The polymer had the following properties:
Mn(GPC)=65,000 MN,(GPC)=98,000.
Example 16 Polymerization at 40°C, [Pd]:[M]=1:1000 In a 100 ml flask, 24.0 mg (0.0455 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2.4 ml of chlorobenzene. 26.5 mg (0.137 mmol) of AgBF4 were added thereto and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered and the 0.33 ml of filtrate was added to a solution of 2.2 g (14 mmol) of methyl 5-norbornene-2-carboxylate in 4 ml of chlorobenzene. The polymerization solution was stirred at a temperature of 40°C for 3 hours. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 194.8 mg (8.9% of theory) of a white solid were obtained. The polymer had the following properties:
Mn(GPC)=64,000 M""(GPC)=91,000 Example 17 Polymerization at 60°C, [Pd]:[M]=1:500 in a '100 ml flask, 24.0 mg (0.0455 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-ene-endo-5a,2n)palladium(II) were dissolved in 2.4 ml of chlorobenzene. 26.5 mg (0.137 mmol) of AgBF4 were added thereto and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered and 0.67 ml of the filtrate was added to a solution of 2.2 g (14 mmol) of methyl 5-norbornene-2-carboxylate in 3.6 ml of chlorobenzene. The yellow polymerization solution was stirred at a temperature of 60°C 'for half an hour. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 251.6 mg (11.4% of theory) of a white solid were obtained. The polymer had the following properties: M~(GPC)=18,000 MW(GPC)=3600 Example 18 Polymerization of the methyl ester (endo/exo=70/30) using a 6-methoxy bicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) hexafluoroantimonate complex Polymerization at room temperature, [Pd]:[M]=1:600 In a 100 ml flask, 20.0 mg (0.038 mmol) of di-N-chloro-bis(6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2 ml of dichloromethane. 38.7 mg (0.113 mmol) of AgSbFg were added thereto and the mixture was stirred at room temperature for 3 minutes. The orange-brown colored solution was filtered and 0.66 ml of the filtrate was added to a solution of 2.28 g (15 mmol) of methyl 5-norbornene-2-carboxylate in 3.3 ml of dichloromethane. The yellow polymerization solution was stirred at room temperature for 5 days. The solution became green after 10 minutes. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 0.43 g (18.8% of theory) of a white solid was obtained. The polymer had the following properties:
M~(GPC)=82,000 MW(GPC)=101,000.
Example 19 Homopolymerization of ethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate using a 6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) tetrafluoro-borate complex, (endo/exo=60/40), [Pd]:[M]=1:500 In a 100 ml flask, 8.9 mg (0.046 mmol) of AgBF4 were added to a solution of 8.8 mg (0.017 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) in 2.4 ml of dichloromethane and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution .
was filtered through a Millipore filter and the filtrate was added to a solution o. 3.'16 g (19.0 mmol) of ethyl 5-norbornene-2-carboxylata in 3.2 ml of dichloromethane. The polymerization mixture was stirred at room temperature for 8 hours. The polymer was precipitated from methanol, filtered off and washed with methanol. The product was dried at 100°C
for 8 hours. 1.49 g (47% of theory) of polymer were obtained. Tlie polymer had the following properties: Mn(GPC)=12,700 MW(GPC)=37,300.
Example 20 Polymerization of the ethyl ester (endo/exo=25/75), [Pd]:[M]=1:550 In a 100 ml flask, 10.5 mg (0.054 mmol) of AgBF4 were added to a solution of 9.6 mg (0.018 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-en-endo-5a,2~)palladium(II) in 2.6 ml of dichloromethane and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered through a Millipore filter and the filtrate was added to 3.34 g (22.0 mmol) of ethyl 5-norbornene-2-carboxylate 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 and washed with methanol. The product was dried at 100°C
for 8 hours. 0.47 g (14% of theory) of polymer was obtained. The polymer had the following properties: Mn(GPC)=9400 MW(GPC)=11,600.
Example 21 Polymerization of the ethyl ester (endo/exo = 60/40), [Pd]:[M]=1:500 In a 100 ml flask, 8.9 mg (0.046 mmol) of AgBF4 were added to a solution of 8.8 mg (0.017 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) in 2.4 ml of dichloromethane and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered through a Millipore filter and the filtrate was added to a solution of 3.16 g (19.0 mmol) of ethyl 5-norbornene-2-carboxylate in 3.2 ml of dichloromethane. The polymerization mixture was stirred at room temperature for 8 hours. The polymer was precipitated from methanol, filtered off and washed with methanol. The product was dried at 100°C
for 8 hours. 1.49 g (47% of theory) of polymer were obtained.
M~(GCP)=12,700 M""(GCP)=37,300 Elemental analysis calc. for (C~pH1402)76~ C 72.75% H 8.49%
found: C 71.80% H 8.59%
~H-NMR (CDCI3): 8 = 1.1-2.9 (m, CH, CH2, CH3; maxima at 1.2, 1.6 and 2.3), 4.1 (m, COOCH2) ppm ~3C-NMR (CDCI3): 8 = 14.2 (s, CH3), 30-60 (m, CH, CH2, maxima at 33.9, 36.8, 38.8, 42.2, 45.5, 46.9 and 50.7), 60.2 (s, OCH2), 175.7 (m, CO) ppm IR (KBr): v = 2976 (s). 2954 (s), 2904 (s), 2878 (s), 1728 (s), 1449 (m), 1371 (m), 1347 (m), 1300 (m), '1182 (s), '1043 (m) cm Example 22 Homopolymerization of bicyclo[2.2.1]hept-5-ene using a 6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) tetrafluoroborate complex, at room temperature, [Pd]:[M]=1:600 In a 100 ml flask, 24.0 mg (0.0455 mmol) of di-N-chloro-bis(6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) were dissolved in 2.4 ml of chlorobenzene. 26.5 mg (0.137 mmol) of AgBF4 were added thereto and the mixture was stirred at room temperature for 3 min. The yellow catalyst solution was filtered and the 0.63 ml of filtrate was added to 1.35 g (0.014 mol) of norbornene. The polymerization solution was stirred at room temperature for 1 hour. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 20 mg (1.5% of theory) of a white solid were obtained.
The polymerization solution was stirred at room temperature for 20 hours.
The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 1.21 g (24% of theory) of a white solid were obtained.
The polymer had the following properties: M~(GPC)=95,000 MW(GPC)=203,000.
Example 15 Polymerization at 40°C, [Pd]:[M]=1:500 In a 100 ml flask, 4.4 mg (0.0083 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2 ml of dichloromethane. 110 mg (0.72 mmol) of methyl 5-norbornene-2-carboxylate and 4.7 mg (0.024 mmol) of AgBF4 were added thereto. The mixture was stirred at room temperature for 3 minutes, filtered and the filtrate was added to 1.29 g (8.5 mmol) of methyl 5-norbornene-2-carboxylate. The polymerization solution was stirred at room temperature for half an hour. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 0.70 g (54% of theory) of a white solid was obtained. The polymer had the following properties:
Mn(GPC)=65,000 MN,(GPC)=98,000.
Example 16 Polymerization at 40°C, [Pd]:[M]=1:1000 In a 100 ml flask, 24.0 mg (0.0455 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2.4 ml of chlorobenzene. 26.5 mg (0.137 mmol) of AgBF4 were added thereto and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered and the 0.33 ml of filtrate was added to a solution of 2.2 g (14 mmol) of methyl 5-norbornene-2-carboxylate in 4 ml of chlorobenzene. The polymerization solution was stirred at a temperature of 40°C for 3 hours. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 194.8 mg (8.9% of theory) of a white solid were obtained. The polymer had the following properties:
Mn(GPC)=64,000 M""(GPC)=91,000 Example 17 Polymerization at 60°C, [Pd]:[M]=1:500 in a '100 ml flask, 24.0 mg (0.0455 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-ene-endo-5a,2n)palladium(II) were dissolved in 2.4 ml of chlorobenzene. 26.5 mg (0.137 mmol) of AgBF4 were added thereto and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered and 0.67 ml of the filtrate was added to a solution of 2.2 g (14 mmol) of methyl 5-norbornene-2-carboxylate in 3.6 ml of chlorobenzene. The yellow polymerization solution was stirred at a temperature of 60°C 'for half an hour. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 251.6 mg (11.4% of theory) of a white solid were obtained. The polymer had the following properties: M~(GPC)=18,000 MW(GPC)=3600 Example 18 Polymerization of the methyl ester (endo/exo=70/30) using a 6-methoxy bicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) hexafluoroantimonate complex Polymerization at room temperature, [Pd]:[M]=1:600 In a 100 ml flask, 20.0 mg (0.038 mmol) of di-N-chloro-bis(6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) were dissolved in 2 ml of dichloromethane. 38.7 mg (0.113 mmol) of AgSbFg were added thereto and the mixture was stirred at room temperature for 3 minutes. The orange-brown colored solution was filtered and 0.66 ml of the filtrate was added to a solution of 2.28 g (15 mmol) of methyl 5-norbornene-2-carboxylate in 3.3 ml of dichloromethane. The yellow polymerization solution was stirred at room temperature for 5 days. The solution became green after 10 minutes. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 0.43 g (18.8% of theory) of a white solid was obtained. The polymer had the following properties:
M~(GPC)=82,000 MW(GPC)=101,000.
Example 19 Homopolymerization of ethyl bicyclo[2.2.1]hept-5-ene-2-carboxylate using a 6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) tetrafluoro-borate complex, (endo/exo=60/40), [Pd]:[M]=1:500 In a 100 ml flask, 8.9 mg (0.046 mmol) of AgBF4 were added to a solution of 8.8 mg (0.017 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) in 2.4 ml of dichloromethane and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution .
was filtered through a Millipore filter and the filtrate was added to a solution o. 3.'16 g (19.0 mmol) of ethyl 5-norbornene-2-carboxylata in 3.2 ml of dichloromethane. The polymerization mixture was stirred at room temperature for 8 hours. The polymer was precipitated from methanol, filtered off and washed with methanol. The product was dried at 100°C
for 8 hours. 1.49 g (47% of theory) of polymer were obtained. Tlie polymer had the following properties: Mn(GPC)=12,700 MW(GPC)=37,300.
Example 20 Polymerization of the ethyl ester (endo/exo=25/75), [Pd]:[M]=1:550 In a 100 ml flask, 10.5 mg (0.054 mmol) of AgBF4 were added to a solution of 9.6 mg (0.018 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-en-endo-5a,2~)palladium(II) in 2.6 ml of dichloromethane and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered through a Millipore filter and the filtrate was added to 3.34 g (22.0 mmol) of ethyl 5-norbornene-2-carboxylate 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 and washed with methanol. The product was dried at 100°C
for 8 hours. 0.47 g (14% of theory) of polymer was obtained. The polymer had the following properties: Mn(GPC)=9400 MW(GPC)=11,600.
Example 21 Polymerization of the ethyl ester (endo/exo = 60/40), [Pd]:[M]=1:500 In a 100 ml flask, 8.9 mg (0.046 mmol) of AgBF4 were added to a solution of 8.8 mg (0.017 mmol) of di-N-chloro-bis(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) in 2.4 ml of dichloromethane and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered through a Millipore filter and the filtrate was added to a solution of 3.16 g (19.0 mmol) of ethyl 5-norbornene-2-carboxylate in 3.2 ml of dichloromethane. The polymerization mixture was stirred at room temperature for 8 hours. The polymer was precipitated from methanol, filtered off and washed with methanol. The product was dried at 100°C
for 8 hours. 1.49 g (47% of theory) of polymer were obtained.
M~(GCP)=12,700 M""(GCP)=37,300 Elemental analysis calc. for (C~pH1402)76~ C 72.75% H 8.49%
found: C 71.80% H 8.59%
~H-NMR (CDCI3): 8 = 1.1-2.9 (m, CH, CH2, CH3; maxima at 1.2, 1.6 and 2.3), 4.1 (m, COOCH2) ppm ~3C-NMR (CDCI3): 8 = 14.2 (s, CH3), 30-60 (m, CH, CH2, maxima at 33.9, 36.8, 38.8, 42.2, 45.5, 46.9 and 50.7), 60.2 (s, OCH2), 175.7 (m, CO) ppm IR (KBr): v = 2976 (s). 2954 (s), 2904 (s), 2878 (s), 1728 (s), 1449 (m), 1371 (m), 1347 (m), 1300 (m), '1182 (s), '1043 (m) cm Example 22 Homopolymerization of bicyclo[2.2.1]hept-5-ene using a 6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-5a,2~)palladium(II) tetrafluoroborate complex, at room temperature, [Pd]:[M]=1:600 In a 100 ml flask, 24.0 mg (0.0455 mmol) of di-N-chloro-bis(6-methoxy-bicyclo[2.2.1]hept-2-ene-endo-5a,2n)palladium(II) were dissolved in 2.4 ml of chlorobenzene. 26.5 mg (0.137 mmol) of AgBF4 were added thereto and the mixture was stirred at room temperature for 3 min. The yellow catalyst solution was filtered and the 0.63 ml of filtrate was added to 1.35 g (0.014 mol) of norbornene. The polymerization solution was stirred at room temperature for 1 hour. The polymer was precipitated in methanol, filtered off, washed and dried at 100°C for 8 hours. 20 mg (1.5% of theory) of a white solid were obtained.
Claims (11)
1. A compound of the formula (I):
where R1 is a monocyclic or polycyclic hydrocarbon, M1+ is a transition metal of group VIIIb, X- is at least one noncoordinating or weakly coordinating anion.
where R1 is a monocyclic or polycyclic hydrocarbon, M1+ is a transition metal of group VIIIb, X- is at least one noncoordinating or weakly coordinating anion.
2. A compound of the formula (I) as claimed in claim 1, wherein R1 is a monocyclic or polycyclic hydrocarbon having at least one unsaturated bond within or outside the ring, M1+ is Rh, Ru, Pd, Co or Ni, X- is BF4-, PF6-, SbF6-, AsF6-, ClO4-, BPh4-, where the phenyl groups may be substituted by fluorine or trifluoromethyl, closoboranes and also carboranes and their halogenated derivatives or triflates.
3. A compound of the formula (I) as claimed in claim 1 or 2, wherein R1 is substituted or unsubstituted norbornene, cyclooctene, tricyclodecene or exo-methylenecyclohexene, M1+ is Pd, X- is BF4-, PF6-, SbF6-, AsF6- or a carborane.
4. A compound of the formula (I) as claimed in one or more of claims 1 to 3, wherein R1 is a compound of the formula (II) where R2 is a hydrogen atom, a C1-C20-alkyl group, a C6-C20-aryl group, OR3, SR3, OCOR3, R3OOCCHCOOR3 or R3OCCHCOR3, where R3 is a hydrogen atom, a C1-C20-alkyl group or a C6-C20-aryl group, -CN, -SCN, -NR3 2, N3 or a halogen atom.
5. A compound of the formula (I) as claimed in one or more of claims 1 to 4 dissolved in at least one halogenated hydrocarbon, aliphatic hydrocarbon or aromatic hydrocarbon, which may contain at least one heteroatom such as oxygen or nitrogen.
6. A compound of the formula (I) as claimed in claim 5 dissolved in methylene chloride, chloroform, nitromethane, dimethylformamide, N-methylpyrrolidone, dimethylethyleneurea, nitrobenzene or chlorobenzene.
7. A compound of the formula (I) as claimed in one or more of claims 1 to 6 and a cycloolefin which has at least one radical R4 where the ratio of the compound of the formula (I) to the cycloolefin is from 1:1 to 1:10 and R4 is a COOR5, -NC or COR3 group.
8. A process for preparing a compound of the formula (I) as claimed in one or more of claims 1 to 6, which comprises reacting M1+R1Hal- with M2+X-in at least one solvent, where Hal- is F-, Cl-, Br-, I- or a pseudohalogen such as CN- or SCN- and M2+ is an alkali metal, an alkaline earth metal, Ag, Tl or Cu.
9. A process for preparing a compound of the formula (I) and a cycloolefin as claimed in claim 7, which comprises initially charging an amount of from 1:1 to 1:10, based on the compound of the formula (I) and reacting M1+R1Hal- with M2+X- in at least one solvent.
10. A process for preparing homopolymers and/or copolymers using at least one compound of the formula (I) as claimed in one or more of claims 1 to 7 as catalyst system.
11. The use of a compound of the formula (I) as claimed in one or more of claims 1 to 7 as catalyst system for preparing homopolymers and/or copolymers.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19715104 | 1997-04-11 | ||
| DE19716312.2 | 1997-04-18 | ||
| DE19715104.3 | 1997-04-18 | ||
| DE19716312A DE19716312A1 (en) | 1997-04-11 | 1997-04-18 | Catalyst and use of the catalyst for the polymerization |
| PCT/EP1998/002003 WO1998046614A1 (en) | 1997-04-11 | 1998-04-07 | Catalyst and use of catalysts in polymerisation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2286695A1 true CA2286695A1 (en) | 1998-10-22 |
Family
ID=26035688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002286695A Abandoned CA2286695A1 (en) | 1997-04-11 | 1998-04-07 | Catalyst and use of catalysts in polymerisation |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0973786A1 (en) |
| JP (1) | JP2001519821A (en) |
| AU (1) | AU7429498A (en) |
| CA (1) | CA2286695A1 (en) |
| WO (1) | WO1998046614A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60311103T2 (en) * | 2002-07-10 | 2007-10-25 | Lg Chem, Ltd. | NORBOROLE BASED POLYMERISATE AND METHOD FOR THE PRODUCTION THEREOF |
| JP4242833B2 (en) | 2002-07-10 | 2009-03-25 | エルジー・ケム・リミテッド | Method for producing norbornene-based addition polymer containing ester group or acetyl group |
| KR100526403B1 (en) | 2002-07-10 | 2005-11-08 | 주식회사 엘지화학 | Method for preparing norbornene based addition polymer containing ester or acetyl functional group |
| 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 |
| KR101046430B1 (en) * | 2008-09-11 | 2011-07-05 | 삼성전기주식회사 | Norbornene-based polymers with low dielectric constant and low loss characteristics, insulating materials, printed circuit boards and functional devices using them |
| US7700529B1 (en) * | 2008-10-14 | 2010-04-20 | International Flavors & Fragrances Inc. | Isomers of bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, ethyl ester and their use in perfume compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5468819A (en) * | 1993-11-16 | 1995-11-21 | The B.F. Goodrich Company | Process for making polymers containing a norbornene repeating unit by addition polymerization using an organo (nickel or palladium) complex |
| DE4447066A1 (en) * | 1994-12-29 | 1996-07-04 | Hoechst Ag | Metal complex compounds containing heterocyclic carbenes |
-
1998
- 1998-04-07 AU AU74294/98A patent/AU7429498A/en not_active Abandoned
- 1998-04-07 CA CA002286695A patent/CA2286695A1/en not_active Abandoned
- 1998-04-07 WO PCT/EP1998/002003 patent/WO1998046614A1/en not_active Application Discontinuation
- 1998-04-07 JP JP54343798A patent/JP2001519821A/en active Pending
- 1998-04-07 EP EP98921435A patent/EP0973786A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0973786A1 (en) | 2000-01-26 |
| AU7429498A (en) | 1998-11-11 |
| WO1998046614A1 (en) | 1998-10-22 |
| JP2001519821A (en) | 2001-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Breunig et al. | Transition‐metal‐catalyzed vinyl addition polymerizations of norbornene derivatives with ester groups | |
| JP5816128B2 (en) | Photoreactive polymer and method for producing the same | |
| EP1200503B1 (en) | Process for the polymerisation of cycloolefins and polymerisable cycloolefins | |
| Pomerantz et al. | Poly (alkyl thiophene-3-carboxylates). Synthesis and characterization of polythiophenes with a carbonyl group directly attached to the ring | |
| US4011386A (en) | Process for producing polymers or copolymers of norbornene-carboxylic acid amides | |
| JP5708538B2 (en) | Ring-opening copolymer hydride | |
| CA2286695A1 (en) | Catalyst and use of catalysts in polymerisation | |
| He et al. | Ni (II) and Pd (II) complexes bearing benzocyclohexane–ketoarylimine for copolymerization of norbornene with 5‐norbornene‐2‐carboxylic ester | |
| Wang et al. | Homo-and copolymerizaton of norbornene and norbornene derivative with Ni-and Pd-based β-ketoiminato complexes and MAO | |
| Ihara et al. | Palladium-mediated polymerization of diazoacetamides | |
| Avci et al. | Ester derivatives of α‐hydroxymethylacrylates: Itaconate isomers giving high molecular weight polymers | |
| Liu et al. | Synthesis of vinyl-type functionalized polynorbornenes with cyclic pendant imide side groups by using palladium-based catalyst for low dielectric constant materials | |
| Cianga et al. | Polystyrene macromonomer with boronic acid propanediol diester functionality prepared by ATRP for synthesis of comb-like polyphenylenes | |
| Vijayanand et al. | Synthesis and characterization of homopolymer of 3, 5-dimethylphenyl methacrylate and its copolymers with glycidyl methacrylate | |
| Watkins et al. | Synthesis and photophysical characterization of aryl-substituted polynorbornenediol acetal and ketal multiblock copolymers | |
| Pittman Jr et al. | Organometallic polymers. XXX. Synthesis and copolymerization of η6-(2-phenylethyl methacrylate) tricarbonylchromium with organic monomers | |
| JP5187314B2 (en) | Norbornene polymer or copolymer and method for producing the same | |
| MXPA06006495A (en) | Linear functional copolymers of ethylene with precise and minimum run length distributions and methods of making thereof. | |
| Nakano et al. | Homo-and copolymerizations of 3-(N-carbazolyl)-1-propyne and its homologues by Mo and W catalysts | |
| WO2012057135A1 (en) | Catalyst for norbornene monomer polymerization and method for producing norbornene polymer | |
| Ueda et al. | Polymerization of α‐methyleneindane: A cyclic analog of α‐methylstyrene | |
| Grutke et al. | Poly (phenylene oxide) macromonomers for graft copolymer synthesis via ring‐opening olefin metathesis polymerization | |
| DE19716312A1 (en) | Catalyst and use of the catalyst for the polymerization | |
| JP2004359704A (en) | Transparent norbornene resin having excellent heat resistance | |
| JPH10330429A (en) | Ethylene/polar group-containing cyclic olefin copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |