EP0973786A1 - Catalyst and use of catalysts in polymerisation - Google Patents
Catalyst and use of catalysts in polymerisationInfo
- Publication number
- EP0973786A1 EP0973786A1 EP98921435A EP98921435A EP0973786A1 EP 0973786 A1 EP0973786 A1 EP 0973786A1 EP 98921435 A EP98921435 A EP 98921435A EP 98921435 A EP98921435 A EP 98921435A EP 0973786 A1 EP0973786 A1 EP 0973786A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- general formula
- mmol
- endo
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 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
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
Katalysator und Verwendung des Katalysators für die PolymerisationCatalyst and use of the catalyst for the polymerization
Die vorliegende Erfindung betrifft einen neuen Katalysator und die Verwendung des Katalysators für die Polymerisation von funktionalisierten und nicht funktionalisierten Cycloolefinen.The present invention relates to a new catalyst and the use of the catalyst for the polymerization of functionalized and non-functionalized cycloolefins.
Bei der vinylischen Polymerisation von Norbornen erhält man ein Polymer, das sich durch eine hohe Glastemperatur, eine hohe Dichte und einen hohen Brechungsindex auszeichnet, vgl. Macromol. Chem. Phys 1886, 197, 3435-3453. Durch die Einführung funktioneller Gruppen am Norbomengerüst sollte es möglich sein, die Eigenschaften des Polymers zu variieren.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. By introducing functional groups on the norbomene skeleton, it should be possible to vary the properties of the polymer.
Ein Polynorbornen, das an der 2-Position mit einer Ester-Gruppe substituiert ist, wie der vinylisch polymerisierte 5-Norbomen-2-carbonsäuremethylester, zeigt bessere Löslichkeitseigenschaften als das unsubstituierte PolynorbornenA 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
wobei n eine Zahl > 1 bedeutet. Er ist im Gegensatz zu Polynorbornen gut in Tetrahydrofuran, Essigsäuremethylester, Aceton und anderen Lösungsmitteln löslich. Das Polymer des Methylesters ist amorph, hat eine Glastemperatur, die über 250 °C liegt und besitzt eine höhere Dichte als Polynorbornen. Polymeranaloge Umsetzungen wie die Verseifung und die Herstellung von Blends sind möglich.where n is a number> 1. In contrast to 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.
Der Ester kann wie viele andere funktionalisierte Norbornenderivate leicht über die Diels-Alder-Reaktion dargestellt werden. Die Polymerisation ist jedoch mit den zur Polymerisation von Norbornen verwendeten Palladium(ll)-Nitril-Katalysatoren nur
sehr langsam möglich. In US-A-3, 330,815 wurde die Polymerisation von verschiedenen Norbornenderivaten mit Pd(ll)-Chloro-Komplexen beschrieben.Like many other functionalized norbornene derivatives, the ester can easily be prepared using the Diels-Alder reaction. However, 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.
Aus Macromolecules 1996, 29, 2755-2763 sind η3-Allylpalladium(ll)- und Palladium(ll)-Nitril Katalysatoren für die Additionspolymerisation von Norbornenverbindungen mit funktionellen Gruppen bekannt. Solche Katalysatoren erzeugen Polymere mit einem Molekulargewicht, das für technische Anwendungen noch nicht hoch genug ist.Macromolecules 1996, 29, 2755-2763 η 3 -Allylpalladium (II) - and Palladium (II) -nitrile catalysts for the addition polymerization of norbornene compounds with functional groups are known. Such catalysts produce polymers with a molecular weight that is not yet high enough for technical applications.
Die Aufgabe der Erfindung liegt darin einen neuen Katalysator für die Polymerisation bereitzustellen, der eine höhere Reaktivität aufweist und Polymere mit höherem Molekulargewicht erzeugt, sowie ein Verfahren zur Herstellung von Homo- und/oder Copolymeren.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.
Die der vorliegenden Erfindung zugrundeliegende Aufgabe wurde durch einen Katalysator gelöst, der die Verbindung mit der allgemeinen Formel (I) enthält:The object on which the present invention is based was achieved by a catalyst which contains the compound of the general formula (I):
R1 R 1
(D.(D.
M1Q X° wobei M 1 Q X ° where
R1 einen mono- oder polycyclischen Kohlenwasserstoff bedeutet,R 1 represents a mono- or polycyclic hydrocarbon,
M1 + ein Übergangsmetall der Gruppe Vlllb bedeutet,M 1 + is a transition metal from group VIIIb,
X" mindestens ein nicht- oder schwachkoordinierendes Anion bedeutet.X "means at least one non- or weakly coordinating anion.
Eine bevorzugte Ausgestaltung der Erfindung liegt in der Verbindung mit der allgemeinen Formel (I), wobeiA preferred embodiment of the invention lies in the compound having the general formula (I),
R1 einen mono- oder polycyclischen Kohlenwasserstoff mit mindestens einer ungesättigten Bindung innerhalb oder außerhalb des Ringes bedeutet, M1 + Rh, Ru, Pd, Co oder Ni bedeutet, X" BF4-, PF6-, SbF6-, AsF6-, CIO4-, BPh4-, wobei die Phenylgruppen durch
Fluor oder Trifluormethyl substituiert sein können, closo-Borane sowie Carborane und deren halogenierten Derivate oder Triflate bedeutet.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.
Eine besonders bevorzugte Ausgestaltung der Erfindung liegt in der Verbindung mit der allgemeinen Formel (I), wobeiA particularly preferred embodiment of the invention lies in the compound having the general formula (I), where
R1 substituiertes oder unsubstituiertes Norbornen, Cycloocten, Tricyclodecen oder exo-Methylencyclohexen, M1+ Pd bedeutet, X" BF4-, PF6-, SbF6-, AsF6- oder Carborane bedeutet.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.
Eine ganz besonders bevorzugte Ausgestaltung der Erfindung liegt in der Verbindung mit der allgemeinen Formel (I), wobei R1 eine Verbindung mit der allgemeinen Formel (II)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)
wobeiin which
R2 ein Wasserstoffatom, eine C1-C20-Alkylgruppe, C6-C20-Arylgruppe, OR3-,R 2 is a hydrogen atom, a C 1 -C 20 alkyl group, C 6 -C 20 aryl group, OR 3 -,
SR3-, OCOR3-, R3OOCCHCOOR3- oder R3OCCHCOR3- Gruppe ist, wobei R3 ein Wasserstoff atom, eine C1-C20-Alkylgruppe oder C6-C20-Arylgruppe bedeutet, eine -CN, -SCN, -NR3 2, N3-Gruppe oder ein Halogenatom bedeutet.SR 3 -, OCOR 3 -, R 3 OOCCHCOOR 3 - or R 3 OCCHCOR 3 - group, where 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.
Die Verbindung mit der allgemeinen Formel (I) ist erfindungsgemäß in mindestens einem halogenierten Kohlenwasserstoff, aliphatischen- oder aromatischen Kohlenwasserstoff gelöst, der gegebenenfalls ein Heteroatom wie Halogen, Sauerstoff oder Stickstoff enthalten können.According to the invention, 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.
Die Verbindung mit der allgemeinen Formel (I) ist bevorzugt in Methylenchlorid, Chloroform, Nitromethan, Dimethylformamid, N-Methylpyrolidon, Dimethylethylenharnstoff, Nitrobenzol, oder Chlorbenzol gelöst.
Erfindungsgemäß ist eine Verbindung mit der allgemeinen Formel (I) und einem Cycloolefin, das mindestens einen Rest R4 aufweist vorgesehen, wobei das Verhältnis der Verbindung mit der allgemeinen Formel (I) zum Cycloolefin von 1 :1 bis 1 :10 beträgt und R4 eine COOR3, oder -NC, COR3- Gruppe bedeutet.The compound having the general formula (I) is preferably dissolved in methylene chloride, chloroform, nitromethane, dimethylformamide, N-methylpyrolidone, dimethylethylene urea, nitrobenzene, or chlorobenzene. According to the invention there is provided 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.
Erfindungsgemäß ist ein Verfahren zur Herstellung der Verbindung mit der allgemeinen Formel (I) vorgesehen, wobeiAccording to the invention there is provided a process for the preparation of the compound having the general formula (I), wherein
M1+R1Har mit M2+X" in mindestens einem Lösungsmittel umgesetzt wird, wobeiM 1+ R 1 Har is reacted with M 2+ X " in at least one solvent, where
Hai" F", CI", Br", J" oder ein Pseudohalogen wie CN" oder SCN" bedeutet undShark means " F " , CI " , Br " , J " or a pseudohalogen such as CN " or SCN " and
M2+ ein Alkali-, Erdalkalimetall, Ag, Tl oder Cu bedeutet.M 2+ is an alkali, alkaline earth metal, Ag, Tl or Cu.
Erfindungsgemäß ist ein Verfahren zur Herstellung der Verbindung mit der allgemeinen Formel (I) und einem Cycloolefin vorgesehen, wobei eine Menge von 1 :1 bis 1:10, bezogen auf die Verbindung mit der allgemeinen Formel (I) vorgelegt wird und M1+R1Hal" mit M2+X" in mindestens einem Lösungsmittel umgesetzt wird.According to the invention, 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.
Erfindungsgemäß ist ein Verfahren zur Herstellung von Homo- und/oder Copolymeren mit mindestens einer Verbindung mit der allgemeinen Formel (I) als Katalysatorsystem vorgesehen.According to the invention, 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.
Dabei ist erfindungsgemäß ein Verfahren zur Herstellung eines Homo- und/oder Copolymers vorgesehen durch Polymerisation von 0,1 bis 100 Gew.-%, bezogen auf die Gesamtmenge der Monomeren, mindestens eines polycyclischen Olefins der Formel III, IV, IV, V, VI, VII oder VIIIAccording to the invention, 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
worin R9, R10, R11, R12, R13, R14, R15 und R16 gleich oder verschieden sind und ein Wasserstoffatom oder einen Kohlenwasserstoff rest bedeuten, wobei gleiche Reste in den verschiedenen Formeln eine unterschiedliche Bedeutung haben können, die polycyclischen Olefine sind bevorzugt mindestens einfach substituierte Carbonsäure- und/oder Dicarbonsäurederivate und 0 bis 99,9 Gew.-%, bezogen auf die Gesamtmenge der Monomeren, mindestens eines monocyclischen Olefins der Formel IXin which R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are identical or different and denote a hydrogen atom or a hydrocarbon radical, where the same radicals in the different formulas can have a different meaning, 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
CH : :CHCH:: CH
\ / (IX) (CH2)q worin q eine Zahl von 2 bis 10 ist, und 0 bis 99,9 Gew.-%, bezogen auf die Gesamtmenge der Monomeren, mindestens eines acyclischen 1 -Olefins der Formel X
\ / (IX) ( CH 2) q where q is a number from 2 to 10, and 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula X.
worin R13, R14, R15 und R16 gleich oder verschieden sind und ein Wasserstoffatom oder einen Kohlenwasserstoffrest, bevorzugt einen C6-C10-Arylrest oder einen C -Cβ-Alkylrest bedeuten.wherein 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 β alkyl radical.
Erfindungsgemäß werden Homo- und/oder Copolymere von Norbomencarbonsäurederivaten und Norbomendicarbonsäurederivaten erhalten. Dabei werden Homo- und/oder Copolymere des mindestens einfach durch Carboxyl-, Ester-, Amid- und Nitrilgruppen substituierten Norbornens oder des Norbornencarbonsäureanhydrids sowie -imids erhalten. Bevorzugte Beispiele für Norbomencarbonsäure- und Norbornendicarbonsäurederivate sind: Bicyclo[2.2.1 ]hept-5-en-2-carbonsäuremethylester,According to the invention, 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,
Bicyclo[2.2.1]hept-5-en-2-carbonsäureethylester, Bicyclo[2.2.1]hept-5-en-2- carbonsäure, Bicyclo[2.2.1 ]hept-5-en, 2-Methyl-bicyclo[2.2.1 ]hept-5-en-2- carbonsäuremethylester, Bicyclo[2.2.1]hept-5-en-2,3-dicarbonsäuredimethylester, Bicyclo[2.2.1]hept-5-en-2,3-dicarbonsäurediethylester, Bicyclo[2.2.1]hept-5-en-2,3- dicarbonsäureanhydrid, N-p-tolyl-bicyclo[2.2.1]hept-5-en-2,3-dicarbonsäureimid sowie weitere aliphatische und aromatische N-substituierte Norbornen-2,3- dicarbonsäureimide.Bicyclo [2.2.1] hept-5-en-2-carboxylic acid ethyl ester, bicyclo [2.2.1] hept-5-en-2-carboxylic acid, bicyclo [2.2.1] hept-5-ene, 2-methyl-bicyclo [ 2.2.1] hept-5-en-2-carboxylic acid methyl ester, bicyclo [2.2.1] hept-5-en-2,3-dicarboxylic acid dimethyl ester, bicyclo [2.2.1] hept-5-en-2,3-dicarboxylic acid diethyl ester, Bicyclo [2.2.1] hept-5-en-2,3-dicarboxylic anhydride, Np-tolyl-bicyclo [2.2.1] hept-5-en-2,3-dicarboximide and further aliphatic and aromatic N-substituted norbornen-2 , 3-dicarboximides.
Die Derivate können auch in 7-Position substituiert sein.The derivatives can also be substituted in the 7-position.
Erfindungsgemäß ist die Verwendung einer Verbindung mit der allgemeinen Formel (i) als Katalysatorsystem zur Herstellung von Homo- und/oder Copolymeren vorgesehen.According to the invention, the use of a compound with the general formula (i) is provided as a catalyst system for the production of homopolymers and / or copolymers.
Die Erfindung wird anhand der nachfolgenden Beispiele näher erläutert.
BeispieleThe invention is illustrated by the following examples. Examples
Allgemeine AngabenGeneral Information
Die Analytik wrde mittels der nachstehend aufgeführten Verfahren durchgeführt. Die NMR-Spektren wurden auf einem Bruker AC 300 Spektrometer mit einer Frequenz von 300 MHz bei 1H-NMR und 75 MHz bei 13C-NMR. Die IR-Spektren wurden auf einem FT-IR-Spektrometer 1600 der Fa. Perkin Eimer aufgenommen. Feststoffe wurden als KBr-Preßlinge vermessen, Flüssigkeiten zwischen zwei Natriumchloridplatten. Die GPC-Analysen mittels Gelpermationschromatographie wurden mit einer Lösung von 0.2 g Polymer in 10 ml Tetrahydrofuran auf zwei 10 mm Polymer-Mixed-Gel Säulen (600*8mm) von PSS durchgeführt. Als Detektor diente ein Differential-Refraktometer und Differential-Viskosimeter der Fa. Knauer. Es wurde eine Knauer Pumpe benutzt. Die inhärenten Viskositäten wurden bei einer Temperatur von 25 °C für Polymerlösungen mit 0,5 Gewichtsprozent in Dichlormethan bestimmt. Die GC-Analysen wurden an einem Gaschromatographen des Typs 5890 der Firma Hewlett Packard durchgeführt. Injektor und Detektor hatten eine Temperatur von 300 °C. Das benutzte Temperaturprogramm war: Isotherme von 70 °C für 4 Minuten, danach mit einer Aufheizrate von 15 °C/min auf 280 °C erhitzen. Es wurde die Kapillarsäule HP-5 (vernetzt mit 5 % Ph Me Silikon) der Firma Hewlett Packard mit einer Filmdicke von 25 mm, einer Länge von 30 m und einem Innendurchmesser von 0.32 mm verwendet.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.
Es bedeutenMean it
VZ = Viskositätszahl in cm3/gVZ = viscosity number in cm 3 / g
GC = Gaschromatograph ^, = Molmassengewichtsmittel in g/mol ^ M.. = Molmassenverteilung, ermittelt durchGC = gas chromatograph ^, = molar mass weight average in g / mol ^ M .. = molar mass distribution, determined by
Gelpermeationschromatographie
AusgangsverbindungenGel permeation chromatography Output connections
Beispiel 1example 1
Bicyclo[2.2.1]hept-5-ene-2-carbonsäureethylester (exo/endo=25/75)Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid ethyl ester (exo / endo = 25/75)
In einem 1 I Dreihalskolben wurden unter Eiskühlung 342.53 g (3.42 mol) Acrylsäureethylester zu 268 g (4.05 mol) frisch destilliertem Cyclopentadien gegeben. Das Eisbad wurde entfernt und die Mischung 8 Stunden in einem Wasserbad bei 20 °C gerührt und danach 1 Stunde auf 40 °C erhitzt Nach der Destillation (Kochpunkt 73 °C/6 mbar) wurden 454.4 g (80 % der Theorie) des Ethylesters erhalten. Die GC-Analyse zeigte ein Verhältnis exo/endo=20/80. Bei der Elementaranalyse wurde gefunden C72.27 H8.59 (Berechnet für C10H14O2, C72.26 H8.49).In a 1 liter 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 with ice. The ice bath was removed and the mixture was stirred in a water bath at 20 ° C. for 8 hours and then heated to 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 showed a ratio exo / endo = 20/80. Elemental analysis found C72.27 H8.59 (calculated for C 10 H 14 O 2 , C72.26 H8.49).
1HMR (CDCI3): δ = 1.2 (4H, m, exo/endo-CH3, 1/2 endo-CH2), 1.3 (2H, m, exo/endo-CH2), 1.4 (1 H, m, 1/2 exo-CH2), 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: δ = 14.1 (1C, s, CH3), 30.1 (1 C, s, CH2), 41.5 (1 C, s, (1 C, 1s, =CH), 137.8 (1 C, 1s, =CH), 175.9 (1 C, 1 s, CO) ppm endo: δ = 14.1 (1 C, 1s, CH3), 29.0 (1 C, 1 s, CH2), 2.4 (1 C, 1 s, CH), 43.4 (1C, 1s, CHCOO), 45.5 (1C, 1s, CH), 49.4 (1 C, 1s, CH2), 59.8 (1 C, 1 s, OCH2), 132.2 (1C, 1 s, =CH), 137.4 (1 C, 1s, =CH), 174.4 (1C, 1s, CO) ppm IR (Kbr): v = 3061 (m), 2978 (s), 2956 (s), 2903 (m), 2874 (m), 1733 (s), 1 HMR (CDCI 3 ): δ = 1.2 (4H, m, exo / endo-CH 3 , 1/2 endo-CH 2 ), 1.3 (2H, m, exo / endo-CH 2 ), 1.4 (1 H, m, 1/2 exo-CH 2 ), 1.8 (1 H, m, 1/2 exo / endo-CH 2 ), 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-COOCH 2 ), 5.8 (1 H , dd, endo = CH), 6.0 (2H, dd, exo = CH), 6.1 (1 H, dd, endo = CH) ppm 13 C-NMR (CDCI3): exo: δ = 14.1 (1C, s, CH 3 ), 30.1 (1 C, s, CH 2 ), 41.5 (1 C, s, (1 C, 1s, = CH), 137.8 (1 C, 1s, = CH), 175.9 (1 C, 1 s, CO) ppm endo: δ = 14.1 (1 C, 1s, CH 3 ), 29.0 (1 C, 1 s, CH 2 ), 2.4 (1 C, 1 s, CH), 43.4 (1C, 1s, CHCOO), 45.5 (1C, 1s, CH), 49.4 (1 C, 1s, CH 2 ), 59.8 (1 C, 1 s, OCH 2 ), 132.2 (1C, 1 s, = CH), 137.4 (1 C, 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), 1 186 (s), 11 10 (s), 1039 (s), 862 (m), 838 (m), 712 (s) cm"1
Beispiel 21447 (m), 1370 (s), 1335 (s), 2171 (s), 1 186 (s), 11 10 (s), 1039 (s), 862 (m), 838 (m), 712 (s ) cm "1 Example 2
Bicyclo[2.2.1]hept-5-en-2-carbonsäureethylester (exo/endo=60/40)Bicyclo [2.2.1] hept-5-en-2-carboxylic acid ethyl ester (exo / endo = 60/40)
In einem 200 ml Kolben wurden 1.65 g (24.2 mmol) Natriumethanolat zu 80.51 g (0.485 mol) 5-Norbornen-2-carbonsäureethylester (exo/endo=25/75) gegeben und bei einer Temperatur von 100 °C 20 Stunden gerührt. Anschließend wurde der Ester in Gegenwart des Natriumethanolats über eine 60 cm Vigreux-Kolonne mit einem Rücklaufverhältnis von 1 :20 im Vakuum destilliert. Nach der Destillation (Kochpunkt gefunden 86 bis 88 °C/16 mbar) wurden 73.3 g (91 % der Theorie) einer farblosen Flüssigkeit erhalten. Die GC-Analyse zeigte ein Verhältnis exo/endo=20/80=60/40.1.65 g (24.2 mmol) of sodium ethanolate were added to 80.51 g (0.485 mol) of 5-norbornene-2-carboxylic acid ethyl ester (exo / endo = 25/75) in a 200 ml flask and stirred at a temperature of 100 ° C. for 20 hours. The ester was then distilled in the presence of the sodium ethanolate in a 60 cm Vigreux column with a reflux ratio of 1:20 in vacuo. After distillation (boiling point found 86 to 88 ° C / 16 mbar), 73.3 g (91% of theory) of a colorless liquid were obtained. GC analysis showed a ratio exo / endo = 20/80 = 60/40.
Beispiel 3Example 3
B icyclo[2.2.1 ]hept-5-en-2-carbonsäuremethylester (exo/endo=70/30)B icyclo [2.2.1] hept-5-en-2-carboxylic acid methyl ester (exo / endo = 70/30)
In einem 1 I Dreihalskolben wurden unter Eiskühlung 239.43 g (2.78 mol) Acrylsäuremethylester zu 218.91 g (3.31 mol) frisch destilliertem Cyclopentadien gegeben. Das Eisbad wurde entfernt und die Mischung 8 Stunden in einem Wasserbad bei 20 °C gerührt und danach 1 Stunde auf 40 °C erhitzt. Nach der Destillation (Kochpunkt 73 °C/14 mbar) wurden 377.8 g (89 % der Theorie) des Methylesters erhalten. Die GC-Analyse zeigte ein Verhältnis exo/endo=20/80.239.43 g (2.78 mol) of methyl acrylate were added to 218.91 g (3.31 mol) of freshly distilled cyclopentadiene in a 1 liter three-necked flask while cooling with ice. The ice bath was removed and the mixture was stirred in a water bath at 20 ° C for 8 hours and then heated to 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 showed a ratio exo / endo = 20/80.
Zu 377.8 g (2.48 mol) 5-Norbornen-2-carbonsäuremethylester (exo/endo=20/80) wurden 8.0 g (0.15 mmol) Natriummethanolat gegeben und 20 Stunden bei einer Temperatur von 105 °C gerührt. Anschließend wurde der Ester in Gegenwart des Natriummethanolats über eine 100 cm Füllkörperkolonne mit Drahtgeflechtröllchen bei einem Rücklauf-Verhältnis von 1 :100 im Vakuum destilliert. Nach der Destillation (Kochpunkt gefunden 75 °C bis 77 °C/19 mbar) wurden 280.9 g (74 % der Theorie) einer farblosen Flüssigkeit erhalten. Die GC-Analyse zeigte ein Verhältnis exo/endo=70/30. Bei der Elementaranalyse wurde gefunden C71.02 H8.04 (Berechnet für C9H12O2, C71.03 H7.94).
Beispiel 48.0 g (0.15 mmol) of sodium methoxide were added to 377.8 g (2.48 mol) of 5-norbornene-2-carboxylic acid methyl ester (exo / endo = 20/80) and the mixture was stirred at a temperature of 105 ° C. for 20 hours. The ester was then distilled in the presence of the sodium methoxide through a 100 cm packed column with wire mesh rolls at a reflux ratio of 1: 100 in vacuo. After distillation (boiling point found 75 ° C to 77 ° C / 19 mbar), 280.9 g (74% of theory) of a colorless liquid were obtained. GC analysis showed an exo / endo = 70/30 ratio. Elemental analysis found C71.02 H8.04 (calculated for C 9 H 12 O 2 , C71.03 H7.94). Example 4
Bicyclo[2.2.1 jheptadien-palladium-chloridBicyclo [2.2.1 jheptadiene palladium chloride
In einem 200 ml Kolben wurden 2.00 g (11.3 mmol) Palladium(ll)chlorid in 5 ml konzentrierter Salzsäure durch Rühren bei 50 °C innerhalb 1 Stunde gelöst. Danach wurde die Lösung auf Zimmertemperatur abgekühlt. Zu der braunen Lösung wurden 150 ml Ethanol gegeben, die Lösung wurde filtriert und der Rückstand mit 20 ml Ethanol gewaschen. Zu dem Filtrat wurden unter Rühren 2.5 ml (2.27 g, 25 mmol) Norbomadien gegeben. Es fiel ein gelber Niederschlag aus, der nach 10 Minuten abfiltriert und dreimal mit je 30 ml Diethylether gewaschen wurde. Das Produkt wurde aus Dichlormethan umkristallisiert. Nach dem Trocknen wurden 2.28 g (77 % der Theorie) eines gelben kristallinen Feststoffs erhalten. Bei der Elementaranalyse wurde gefunden C31.38 H2.98 ( Berechnet für C7H8PdCI2, C31.20 H2.99). 1 H-NMR (DMSO-d6): δ = 1.87 (t, J = 1.6 Hz, 2H, CH2), 3.56 (quin, J = 1.8 Hz,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. within 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 norbomadiene were added to the filtrate with stirring. A yellow precipitate precipitated out, which was filtered off after 10 minutes and washed three times with 30 ml of diethyl ether each time. The product was recrystallized from dichloromethane. After drying, 2.28 g (77% of theory) of a yellow crystalline solid were obtained. Elemental analysis found C31.38 H2.98 (calculated for C 7 H 8 PdCI 2 , C31.20 H2.99). 1 H-NMR (DMSO-d 6 ): δ = 1.87 (t, J = 1.6 Hz, 2H, CH 2 ), 3.56 (quin, J = 1.8 Hz,
2H, CH), 6.76 (t, J = 1.9 Hz, 4H, CH) ppm 13C-NMR (DMSO-d6): δ = 50.4 (CH), 74.8 (CH2) 143,1 (CH) ppm2H, CH), 6.76 (t, J = 1.9 Hz, 4H, CH) ppm 13 C-NMR (DMSO-d 6 ): δ = 50.4 (CH), 74.8 (CH 2 ) 143.1 (CH) ppm
IR (KBr): v = 3047 (s), 2965 (w), 2924 (w), 1407 (s), 1304 (s), 1226IR (KBr): v = 3047 (s), 2965 (w), 2924 (w), 1407 (s), 1304 (s), 1226
(m), 1183 (m), 967 (m), 939 (m), 898 (m), 828 (m), 792(m), 1183 (m), 967 (m), 939 (m), 898 (m), 828 (m), 792
(s), 769 (s) cm"1 (s), 769 (s) cm "1
Beispiel 5Example 5
Di-μ-chloro-bis-(6-methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll)Di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II)
In einem 100 ml Stickstoffkolben wurde unter Stickstoff 4 ml Methanol zu 300 mg (1.11 mmol) Bicyclo[2.2.1]heptadien-palladium-chlorid und 101 mg (0.95 mmol) Natriumcarbonat gegeben und die Mischung bei Raumtemperatur gerührt. Nach einer Stunde hatte sich ein hellgelber feiner Niederschlag gebildet, der abfiltriert und im Ölpumpenvakuum getrocknet wurde. Es wurden 289 mg (98 % der Theorie) eines leicht gelben Feststoffs erhalten. Bei der Elementaranalyse wurde gefunden C35.88 H4.27 (Berechnet für C16H22Pd2CI2, C36.25 H4.18).
1H-NMR (CDCI3): δ = 6.09 (t, J = 3.87Hz, 1 H, =CH), 5.88 (t, J = 3.87 Hz, 1 H,4 ml of methanol were added to 300 mg (1.11 mmol) of bicyclo [2.2.1] heptadiene-palladium chloride and 101 mg (0.95 mmol) of sodium carbonate in a 100 ml nitrogen flask under nitrogen and the mixture was stirred at room temperature. After an hour a light yellow fine precipitate had formed which was filtered off and dried in an oil pump vacuum. 289 mg (98% of theory) of a slightly yellow solid were obtained. Elemental analysis found C35.88 H4.27 (calculated for C 16 H 22 Pd 2 CI 2 , C36.25 H4.18). 1 H-NMR (CDCI 3 ): δ = 6.09 (t, J = 3.87Hz, 1 H, = 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)= CH), 4.12 (s, 1 H, CH) 3.24 (s, 3H, OCH 3 ), 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, CH 2 ), 1.61 (d, J = 9.85 Hz, 1 H, CH 2 )
PolymerisationPolymerization
Beispiel 6Example 6
Alle eingesetzten Monomere wurden über CaH2 getrocknet, im Vakuum destilliert und mit Stickstoff gesättigt. Die Herstellung der Katalysatorlösungen wurde unter Stickstoff durchgeführt. Alle Polymerisationsversuche wurden ebenfalls in Stickstoffatmosphäre unter Ausschluß von Feuchtigkeit und Sauerstoff durchgeführt.All monomers used were dried over CaH 2 , distilled in vacuo and saturated with nitrogen. The catalyst solutions were prepared under nitrogen. All polymerization experiments were also carried out in a nitrogen atmosphere with the exclusion of moisture and oxygen.
Beispiel 7Example 7
Bicyclo[2.2.1]hept-5-en-2-carbonsäuremethylester (exo/endo=70/30)Bicyclo [2.2.1] hept-5-en-2-carboxylic acid methyl ester (exo / endo = 70/30)
Polymerisation des Methylesters mit einem η3-Allylpalladium(ll)tetrafluoroborat- komplex bei Raumtemperatur, [Pd]:[M]=1 :70Polymerization of the methyl ester with an η 3 -Allylpalladium (II) tetrafluoroborate complex at room temperature, [Pd]: [M] = 1:70
In einem 100 ml Kolben wurden 14.6 mg (0.064 mmol) η3-Allyl-Palladium-chlorid Dimer, in 2 ml Dichlormethan gelöst. Dazu wurden 24.0 mg (0.124 mmol) AgBF4 gegeben und 20 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde filtriert und das Filtrat zu 0.6 ml (0.66g, 4,3 mmol) 5-Norbornen-2- carbonsäuremethylester gegeben. Die Reaktionsmischung wurde 5 Tage bei Raumtemperatur gerührt. Das Polymer wurde aus Methanol ausgefällt, abfiltriert, mit Methanol gewaschen und 8 Stunden bei 100 °C getrocknet. Die Ausbeute betrug 647 mg (98 % der Theorie). Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=11600, MW(GPC)=22100.
Beispiel 8In a 100 ml flask, 14.6 mg (0.064 mmol) of η 3 -allyl-palladium chloride dimer were dissolved in 2 ml of dichloromethane. 24.0 mg (0.124 mmol) of AgBF 4 were added and the mixture was stirred at room temperature for 20 minutes. The yellow catalyst solution was filtered and the filtrate was added to 0.6 ml (0.66g, 4.3 mmol) of 5-norbornene-2-carboxylic acid methyl ester. The reaction mixture was stirred for 5 days at room temperature. 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: M n (GPC) = 11600, M W (GPC) = 22100. Example 8
Polymerisation bei Raumtemperatur, [Pd]:[M]=1 :250Polymerization at room temperature, [Pd]: [M] = 1: 250
In einem 100 ml Kolben wurden 13.7 mg (0.0377 mmol) η3-Allyl-Palladium-chlorid Dimer, in 2 ml Dichlormethan gelöst. Zu de Lösung wurden 16.3 mg (0.0841 mmol) AgBF4 gegeben und 20 Minuten bei Raumtemperatur gerührt wobei ein wießer Niederschlag ausfiel. Die gelbe Katalysatorlösung wurde filtriert und das Filtrat zu einer Lösung von 2.56 g, (16.8 mmol) 5-Norbomen-2-carbonsäuremethylester in 8 ml Dichlormethan gegeben. Die Reaktionsmischung wurde 4 Tage bei Raumtemperatur gerührt. Das Polymer wurde aus Methanol ausgefällt, abfiltriert, mit Methanol gewaschen und 8 Stunden bei 100 °C getrocknet. Es wurden 1.82 g (71 % der Theorie) eines weißen Feststoffs erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=7200, MW(GPC)=79000.In a 100 ml flask, 13.7 mg (0.0377 mmol) η 3 -allyl-palladium chloride dimer were dissolved in 2 ml dichloromethane. 16.3 mg (0.0841 mmol) of AgBF 4 were added to the solution and the mixture was stirred at room temperature for 20 minutes, during which a precipitate formed. The yellow catalyst solution was filtered and the filtrate was added to a solution of 2.56 g, (16.8 mmol) of 5-norbomene-2-carboxylic acid methyl ester in 8 ml of dichloromethane. The reaction mixture was stirred for 4 days at room temperature. 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 n (GPC) = 7200, M W (GPC) = 79000.
Beispiel 9Example 9
Polymerisation des Methylesters mit Di-μ-chloro-bis-(6-methoxybicyclo[2.2.1]hept- 2-en-endo-5σ,2π)-palladium(ll) bei Raumtemperatur, [Pd]:[M]=1 :270Polymerization of the methyl ester with di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) at room temperature, [Pd]: [M] = 1 : 270
In einem 100 ml Stickstoffkolben wurden 6.7 mg (0.015 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 4 ml Dichlormethan gelöst. Die Lösung wurde zu 1.09 g (7.17 mmol) 5-Norbornen-2- carbonε äuremethylester gegeben und 5 Tage bei Raumtempe-atur gerührt. Das Polymer wurde aus Methanol ausgefällt, abfiltriert, mit Methanol gewaschen und 8 Stunden bei 100 °C getrocknet. Die Ausbeute betrug 0.43 g (40% der Theorie). Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=4600 MW(GPC)=7800
Beispiel 106.7 mg (0.015 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 4 ml dichloromethane were placed in a 100 ml nitrogen flask solved. The solution was added to 1.09 g (7.17 mmol) of 5-norbornene-2-carbonate, methyl ester, and the 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 0.43 g (40% of theory). The polymer had the following properties: M n (GPC) = 4600 M W (GPC) = 7800 Example 10
Polymerisation des Methylesters mit Di-μ-chloro-bis-(6-methoxybicyclo[2.2.1]hept- 2-en-endo-5σ,2π)-palladium(ll) und NaAsF6, bei Raumtemperatur, [Pd]:[M]=1 :250Polymerization of the methyl ester with di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) and NaAsF 6 , at room temperature, [Pd]: [ M] = 1: 250
In einem 100 ml Kolben wurden 6.5 mg (0.012 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2 ml Dichlormethan gelöst. Dazu wurden 11.2 mg (0.033 mmol) NaAsF6 gegeben und 30 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde filtriert und das Filtrat zu 1.1 g (7.2 mmol) 5-Norbornen-2-carbonsäuremethylester gegeben. Die Polymerisationslösung färbte sich nach einer halben Stunde orange. Sie wurde 20 Stunden bei Raumtemperatur gerührt. Das Polymer wurde in Methanol ausgefällt, abfiltriert, gewaschen und 8 Stunden bei 100 °C getrocknet. Es wurden 0.23 g (21 % der Theorie) eines weißen Feststoffs erhalten.6.5 mg (0.012 mmol) of di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2 ml of dichloromethane were placed in a 100 ml flask solved. 11.2 mg (0.033 mmol) of NaAsF 6 were added and the mixture was stirred at room temperature for 30 minutes. The yellow catalyst solution was filtered and the filtrate was added to 1.1 g (7.2 mmol) of 5-norbornene-2-carboxylic acid methyl ester. The polymerization solution turned 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 were obtained.
Beispiel 11Example 11
Polymerisation des Methylesters (endo/exo=50/50) mit einem Wasser enthaltendem Pd-Katalysator, [Pd]:[M]=1 :250Polymerization of the methyl ester (endo / exo = 50/50) with a water-containing Pd catalyst, [Pd]: [M] = 1: 250
Zur Herstellung der Katalysatorlösung wurde in einem 100 ml Kolben zu einer Mischung von 143.9 mg (1.35 mmol) Pd(0)-Pulver, 25 ml Nitromethan und 0.15 ml (150 mg, 8.3 mmol) Wasser 318 mg (2.72 mmol) NOBF4 gegeben. Das entstehende Gas wurde durch Evakuieren entfernt. Die Lösung war anfangs gelb und wurde dann grün und schließlich dunkelrot. In einem 100 ml Kolben wurden 2.19 g (14.1 mmol) Bicyclo[2.2.1]hept-5-en-2-carbonsäuremethylester in 10 ml Nitromethan gelöst. Dazu wurde 1.0 ml der Katalysatorlösung gegeben. Nach 4 Tagen Reaktionsdauer wurde in Methanol ausgefällt, der Niederschlag abfiltriert, mit Methanol gewaschen und 8 h bei 100 °C getrocknet. Die Ausbeute betrug 1.77 g (81 % der Theorie). Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=17000 MW(GPC)=24000
Beispiel 12To prepare the catalyst solution, 318 mg (2.72 mmol) NOBF 4 was added to a mixture of 143.9 mg (1.35 mmol) Pd (0) powder, 25 ml nitromethane and 0.15 ml (150 mg, 8.3 mmol) water in a 100 ml flask . The resulting gas was removed by evacuation. The solution was initially yellow and then turned green and finally dark red. 2.19 g (14.1 mmol) of methyl bicyclo [2.2.1] hept-5-ene-2-carboxylic acid were dissolved in 10 ml of nitromethane in a 100 ml flask. 1.0 ml of the catalyst solution was added. After a reaction time of 4 days, the mixture was precipitated in methanol, the precipitate was filtered off, washed with methanol and dried at 100 ° C. for 8 h. The yield was 1.77 g (81% of theory). The polymer had the following properties: M n (GPC) = 17000 M W (GPC) = 24000 Example 12
Polymerisation des Methylesters (endo/exo=70/30) mit einem 6- Methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll)tetrafluoroborat-Komplex bei Raumtemperatur, [Pd]:[M]=1 :220Polymerization of the methyl ester (endo / exo = 70/30) with a 6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) tetrafluoroborate complex at room temperature, [Pd]: [ M] = 1: 220
Darstellung des KatalysatorsRepresentation of the catalyst
In einem 100 ml Kolben wurden 6.9 mg (0.013 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 4 ml Dichlormethan gelöst. Dazu wurden 8.0 mg (0.041 mmol) AgBF4 gegeben und 5 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde filtriert. 1H-NMR (CDCI3): δ = 6.33 (s, 1 H, =CH), 6.15 (s, 1 H, =CH), 4.12 (s, 1 H, CH),6.9 mg (0.013 mmol) of di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 4 ml of dichloromethane were placed in a 100 ml flask solved. 8.0 mg (0.041 mmol) of AgBF 4 were added and the mixture was stirred at room temperature for 5 minutes. The yellow catalyst solution was filtered. 1 H-NMR (CDCI 3 ): δ = 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) ppm3.36 (d, J = 4.18 Hz, 1 H, CH), 3.29 (s, 3H, OCH 3 ), 3.04 (s, 1 H, CH), 2.95 (s, 1 H, CH), 1.96 (d, J = 9.81 Hz, 1 H, CH 2 ), 1.73 (d, J = 9.61 Hz, 1 H, CH 2 ) ppm
PolymerisationPolymerization
Das Filtrat wurde zu 0.80 ml (0.88 g, 5.8 mmol) 5-Norbornen-2- carbonsäuremethylester gegeben. Die Polymerisationslösung wurde 5 Tage bei Raumtemperatur gerührt. Das Polymer wurde in Methanol ausgefällt, abfiltriert, gewaschen und 8 Stunden bei 100 °C getrocknet. Es wurden 0.84 g (96 % der Theorie) eines weißen Feststoffs erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=102000 MW(GPC)=131000, ηinh=0.366 dl/g, [η]=0.374 dl/g, 25 X, CH2CI2. Elementaranalyse ber. für (C9H12O2)671: C 71.03 % H 7.95 % gef. C 70.67 % H 7.98 % 1 H-NMR (CDCI3): δ = 0.9 - 3.2 (m, CH, CH2, Maxima bei 1.5, 1.8 und 2.3), 3.6The 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 had the following properties: M n (GPC) = 102000 M W (GPC) = 131000, η inh = 0.366 dl / g, [η] = 0.374 dl / g, 25 X, CH 2 CI 2 . Elemental analysis calculated for (C 9 H 12 O 2 ) 671 : C 71.03% H 7.95% found C 70.67% H 7.98% 1 H-NMR (CDCI 3 ): δ = 0.9 - 3.2 (m, CH, CH 2 , maxima at 1.5, 1.8 and 2.3), 3.6
(m, COOCH3) ppm 13C-NMR (CDCI3): δ = 30 - 60 (m, CH, CH2, Maxima bei 34.1 , 37.2, 39.2, 42.3,(m, COOCH 3 ) ppm 13 C-NMR (CDCI 3 ): δ = 30 - 60 (m, CH, CH 2 , maxima at 34.1, 37.2, 39.2, 42.3,
45.2, 46.3 und 51.5), 176,1 (m, CO) ppm
IR (KBr): v = 2953 (s), 2883 (m), 1732 (s), 1435 (s), 1361 (m), 119745.2, 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"1 (s), 1173 (s), 1042 (m) cm "1
Beispiel 13Example 13
Polymerisation bei Raumtemperatur, [Pd]:[M]=1 :500Polymerization at room temperature, [Pd]: [M] = 1: 500
In einem 100 ml Kolben wurden 20.0 mg (0.038 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2 ml Dichlormethan gelöst. Dazu wurden 21.9 mg (0.113 mmol) AgBF4 gegeben und 5 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde filtriert und das Filtrat zu einer Lösung von 6.32 g (42 mmol) 5-Norbomen-2-carbonsäuremethylester in 10 ml Dichlormethan gegeben. Von dieser Polymerisationslösung wurden nach 0.5, 1 , 2, 3.5 und nach 5.5 Stunden je 2 ml und nach 8 Stunden der Rest der Lösung entnommen, in Methanol ausgefällt, abfiltriert, gewaschen und 8 Stunden bei 100 X getrocknet. Die Ausbeute betrug nach 0.5 h: 5 %, nach 1 h: 5 %, nach 2 h: 17.4 %, nach 3.5 h: 27 %, nach 5.5 h: 41.8 % und nach 8 h: 52.9 %. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=93000 MW(GPC)=130000 nach 8 Stunden Polymerisationszeit20.0 mg (0.038 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2 ml dichloromethane were placed in a 100 ml flask solved. 21.9 mg (0.113 mmol) of AgBF 4 were added and the mixture was stirred at room temperature for 5 minutes. The yellow catalyst solution was filtered and the filtrate was added to a solution of 6.32 g (42 mmol) of 5-norbomene-2-carboxylic acid methyl ester in 10 ml of dichloromethane. After 0.5, 1, 2, 3.5 and after 5.5 hours, 2 ml portions of this polymerization solution and the rest of the solution after 8 hours were removed, precipitated in methanol, filtered off, washed and dried at 100 × for 8 hours. The yield after 5 h: 5%, after 1 h: 5%, after 2 h: 17.4%, after 3.5 h: 27%, after 5.5 h: 41.8% and after 8 h: 52.9%. The polymer had the following properties: M n (GPC) = 93,000 M W (GPC) = 130,000 after 8 hours of polymerization
Beispiel 14Example 14
Polymerisation bei Raumtemperatur, [Pd]:[M]=1 :1000Polymerization at room temperature, [Pd]: [M] = 1: 1000
In einem 100 ml Kolben wurden 8.3 mg (0.0157 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2.2 ml Dichlormethan gelöst. Dazu wurden 9.2 mg (0.047 mmol) AgBF4 gegeben und 5 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde filtriert und zu einer Lösung von 5.09 g (33 mmol) 5-Norbornen-2-carbonsäuremethylester in 8 ml Chlorbenzol gegeben. Die Polymerisationslösung wurde 20 Stunden bei Raumtemperatur gerührt. Das Polymer wurde in Methanol ausgefällt, abfiltriert, gewaschen und 8 Stunden bei 100 X getrocknet. Es wurden 1.21 g (24 % der
Theorie) eines weißen Feststoffs erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=95000 MW(GPC)=2030008.3 mg (0.0157 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2.2 ml dichloromethane were placed in a 100 ml flask solved. 9.2 mg (0.047 mmol) of AgBF 4 were added and the mixture was stirred at room temperature for 5 minutes. The yellow catalyst solution was filtered and added to a solution of 5.09 g (33 mmol) of 5-norbornene-2-carboxylic acid methyl ester 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 100X for 8 hours. 1.21 g (24% of the Theory) of a white solid. The polymer had the following properties: M n (GPC) = 95000 M W (GPC) = 203000
Beispiel 15Example 15
Polymerisation bei 40 X, [Pd]:[M]=1:500Polymerization at 40 X, [Pd]: [M] = 1: 500
In einem 100 ml Kolben wurden 4.4 mg (0.0083 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2 ml Dichlormethan gelöst. Dazu wurden 110 mg (0.72 mmol) 5-Norbornen-2-carbonsäuremethylester und 4.7 mg (0.024 mmol) AgBF4 gegeben. Die Mischung wurde 3 Minuten bei Raumtemperatur gerührt, filtriert und das Filtrat zu 1.29 g (8.5 mmol) 5-Norbornen- 2-carbonsäuremethylester gegeben. Die Polymerisationsiösung wurde eine halbe Stunde bei Raumtemperatur gerührt. Das Polymer wurde in Methanol ausgefällt, abfiltriert, gewaschen und 8 Stunden bei 100 X getrocknet. Es wurden 0.70 g (54 % der Theorie) eines weißen Feststoffs erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=65000 MW(GPC)=980004.4 mg (0.0083 mmol) of di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2 ml of dichloromethane were placed in a 100 ml flask solved. 110 mg (0.72 mmol) of 5-norbornene-2-carboxylic acid methyl ester and 4.7 mg (0.024 mmol) of AgBF 4 were added. The mixture was stirred for 3 minutes at room temperature, filtered and the filtrate was added to 1.29 g (8.5 mmol) of 5-norbornene-2-carboxylic acid methyl ester. 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 polymer had the following properties: M n (GPC) = 65000 M W (GPC) = 98000
Beispiel 16Example 16
Polymerisation bei 40 X, [Pd]:[M]=1 :1000Polymerization at 40 X, [Pd]: [M] = 1: 1000
In einem 100 ml Kolben wurden 24.0 mg (0.0455 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2.4 ml Chlorbenzol gelöst. Dazu wurden 26.5 mg (0137 mmol) AgBF4 gegeben und 3 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde filtriert und das 0.33 ml des Filtrats zu einer Lösung von 2.2 g (14 mmol) 5-Norbornen-2- carbonsäuremethylester in 4 ml Chlorbenzol gegeben. Die Polymerisationsiösung wurde drei Stunden bei einer Temperatur von 40 X gerührt. Das Polymer wurde in Methanol ausgefällt, abfiltriert, gewaschen und 8 Stunden bei 100 X getrocknet. Es wurden 194.8 mg (8.9 % der Theorie) eines weißen Feststoffs erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=64000 MW(GPC)=91000
Beispiel 1724.0 mg (0.0455 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2.4 ml chlorobenzene were placed in a 100 ml flask solved. 26.5 mg (0137 mmol) of AgBF 4 were added and the mixture was stirred at room temperature for 3 minutes. The yellow catalyst solution was filtered and the 0.33 ml of the filtrate was added to a solution of 2.2 g (14 mmol) of 5-norbornene-2-carboxylic acid methyl ester in 4 ml of chlorobenzene. 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 polymer had the following properties: M n (GPC) = 64000 M W (GPC) = 91000 Example 17
Polymerisation bei 60 X, [Pd]:[M]=1:500Polymerization at 60 X, [Pd]: [M] = 1: 500
In einem 100 ml Kolben wurden 24.0 mg (0.0455 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2.4 ml Chlorbenzol gelöst. Dazu wurden 26.5 mg (0137 mmol) AgBF4 gegeben und 3 min bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde filtriert und 0.67 ml des Filtrats zu einer Lösung von 2.2 g (14 mmol) 5-Norbornen-2- carbonsäuremethylester in 3.6 ml Chlorbenzol gegeben. Die gelbe Polymerisationsiösung wurde eine halbe Stunde bei einer Temperatur von 60 X gerührt. Das Polymer wurde in Methanol ausgefällt, abfiltriert, gewaschen und 8 Stunden bei 100 X getrocknet. Es wurden 251.6 mg (11.4 % der Theorie) eines weißen Feststoffs erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=18000 MW(GPC)=360024.0 mg (0.0455 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2.4 ml chlorobenzene were placed in a 100 ml flask solved. 26.5 mg (0137 mmol) of AgBF 4 were added and the mixture was stirred at room temperature for 3 min. 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 5-norbornene-2-carboxylic acid methyl ester in 3.6 ml of chlorobenzene. 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 polymer had the following properties: M n (GPC) = 18000 M W (GPC) = 3600
Beispiel 18Example 18
Polymerisation des Methylesters (endo/exo=70/30) mit einem 6-Polymerization of the methyl ester (endo / exo = 70/30) with a 6-
Methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll)hexafluoroantimonat-Methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) hexafluoroantimonate-
Komplexcomplex
Polymerisation bei Raumtemperatur, [Pd]:[M]=1 :600Polymerization at room temperature, [Pd]: [M] = 1: 600
In einem 100 ml Kolben wurden 20.0 mg (0.038 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2 ml Dichlormethan gelöst. Dazu wurden 38.7 mg (0.113 mmol) AgSbF6 gegeben und 3 Minuten bei Raumtemperatur gerührt. Die orangebraune Katalysatorlösung wurde filtriert und 0.66 ml des Filtrats zu einer Lösung von 2.28 g, (15 mmol) 5-Norbornen-2- carbonsäuremethylester in 3.3 ml Dichlormethan gegeben. Die gelbe Polymerisationsiösung wurde 5 Tage bei Raumtemperatur gerührt. Die Lösung färbte sich nach 10 Minuten grün. Das Polymer wurde in Methanol ausgefällt,
abfiltriert, gewaschen und 8 Stunden bei 100 X getrocknet. Es wurden 0.43 g (18.8 % der Theorie) eines weißen Feststoffs erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=82000 MW(GPC)=10100020.0 mg (0.038 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2 ml dichloromethane were placed in a 100 ml flask solved. 38.7 mg (0.113 mmol) of AgSbF 6 were added and the mixture was stirred at room temperature for 3 minutes. The orange-brown catalyst solution was filtered and 0.66 ml of the filtrate was added to a solution of 2.28 g, (15 mmol) of 5-norbornene-2-carboxylic acid methyl ester in 3.3 ml of dichloromethane. 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 had the following properties: M n (GPC) = 82000 M W (GPC) = 101000
Beispiel 19Example 19
Homopolymerisation von Bicyclo[2.2.1]hept-5-en-2-carbonsäureethylester mit einem 6-Methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll)tetrafluoroborat- Komplex, (endo/exo=60/40), [Pd]:[M]=1:500Homopolymerization of bicyclo [2.2.1] hept-5-en-2-carboxylic acid ethyl ester with a 6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) tetrafluoroborate complex, (endo / exo = 60/40), [Pd]: [M] = 1: 500
In einem 100 ml Kolben wurde zu einer Lösung von 8.8 mg (0.017 mmol) Di-μ- chloro-bis-(6-methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2.4 ml Dichlormethan 8.9 mg (0.046 mmol) AgBF4 gegeben und 3 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde durch einen Milliporfilter filtriert und das Filtrat zu einer Lösung von 3.16 g (19.0 mmol) 5-Norbornen-2-carbonsäureethylester in 3.2 ml Dichlormethan gegeben. Die Polymerisationsmischung wurde 8 Stunden bei Raumtemperatur gerührt. Das Polymer wurde aus Methanol ausgefällt, abfiltriert und mit Methanol gewaschen. Das Produkt wurde 8 Stunden bei 100 X getrocknet. Es wurden 1.49 g (47 % der Theorie) des Polymers erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=12700 MW(GPC)=37300In a 100 ml flask, a solution of 8.8 mg (0.017 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) added to 2.4 ml dichloromethane 8.9 mg (0.046 mmol) AgBF 4 and stirred for 3 minutes at room temperature. The yellow catalyst solution was filtered through a Millipor filter and the filtrate was added to a solution of 3.16 g (19.0 mmol) of 5-norbornene-2-carboxylic acid ethyl ester 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 100X for 8 hours. 1.49 g (47% of theory) of the polymer were obtained. The polymer had the following properties: M n (GPC) = 12700 M W (GPC) = 37300
Beispiel 20Example 20
Polymerisation des Ethylesters (endo/exo=25/75), [Pd]:[M]=1:550 In einem 100 ml Kolben wurde zu einer Lösung von 9.6 mg (0.018 mmol) Di-μ- chloro-bis-(6-methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2.6 ml Dichlormethan 10.5 mg (0.054 mmol) AgBF4 gegeben und 3 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde durch einen Milliporfilter filtriert und das Filtrat zu 3.34 g (22.0 mmol) 5-Norbornen-2- carbonsäureethylester in 3.6 ml Dichlormethan gegeben. Die gelbe Polymerisationsmischung wurde 20 Stunden bei Raumtemperatur gerührt. Das
Polymer wurde aus Methanol ausgefällt, abfiltriert, mit Methanol gewaschen. Das Produkt wurde 8 Stunden bei 100 X getrocknet. Es wurden 0.47 g (14 % der Theorie) des Polymers erhalten. Das Polymer wies folgende Eigenschaften auf: Mn(GPC)=9400 MW(GPC)=11600Polymerization of the ethyl ester (endo / exo = 25/75), [Pd]: [M] = 1: 550 In a 100 ml flask, a solution of 9.6 mg (0.018 mmol) di-μ-chloro-bis- (6 -methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2.6 ml dichloromethane 10.5 mg (0.054 mmol) AgBF 4 and stirred for 3 minutes at room temperature. 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. The polymer had the following properties: M n (GPC) = 9400 M W (GPC) = 11600
Beispiel 21Example 21
Polymerisation des Ethylesters (endo/exo = 60/40), [Pd] : [M] = 1 : 500Polymerization of the ethyl ester (endo / exo = 60/40), [Pd]: [M] = 1: 500
In einem 100 ml Kolben wurde zu einer Lösung von 8.8 mg (0.017 mmol) Di-μ- chloro-bis-(6-methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2.4 ml Dichormethan 8.9 mg (0.046 mmol) AgBF4 gegeben und 3 Minuten bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde durch einen Milliporfilter filtriert und das Filtrat zu einer Lösung von 3.16 g (19,0 mmol) 5-Norbornen-2-carbonsäureethylester in 3.2 ml Dichlormethan gegeben. Die Polymerisationsmischung wurde 8 Stunden bei Raumtemperatur gerührt. Das Polymer wurde aus Methanol ausgefällt abfiltriert und mit Methanol gewaschen. Das Produkt wurde 8 Stunden bei 100X getrocknet. Es wurden 1.49 g (47 % d. Th.) des Polymers erhalten. Mn(GCP) = 12700 MW(GCP) = 37300 Elementaranalyse ber. für (C10H14O2)76: C 72.25 % H 8.49 % gef.: C 71.80 % H 8.59 %In a 100 ml flask, a solution of 8.8 mg (0.017 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) placed in 2.4 ml dichloromethane 8.9 mg (0.046 mmol) AgBF 4 and stirred for 3 minutes at room temperature. The yellow catalyst solution was filtered through a Millipor filter and the filtrate was added to a solution of 3.16 g (19.0 mmol) of 5-norbornene-2-carboxylic acid ethyl ester in 3.2 ml of dichloromethane. The polymerization mixture was stirred at room temperature for 8 hours. The polymer was filtered off from methanol and washed with methanol. The product was dried at 100X for 8 hours. 1.49 g (47% of theory) of the polymer were obtained. M n (GCP) = 12700 M W (GCP) = 37300 Elemental analysis calc. For (C 10 H 14 O 2 ) 76 : C 72.25% H 8.49% found: C 71.80% H 8.59%
1H-NMR (CDCI3): δ = 1.1 - 2.9 (m, CH, CH2, CH3; Maxima bei 1.2, 1.6 und 1 H-NMR (CDCI 3 ): δ = 1.1 - 2.9 (m, CH, CH 2 , CH 3 ; maxima at 1.2, 1.6 and
2.3), 4.1 (m, COOCH2) ppm 13C-NMR (CDCI3): δ = 14.2 (s, CH3), 30 - 60 (m, CH, CH2, Maxima bei 33.9,2.3), 4.1 (m, COOCH 2 ) ppm 13 C-NMR (CDCI 3 ): δ = 14.2 (s, CH 3 ), 30 - 60 (m, CH, CH 2 , maxima at 33.9,
36.8, 38.8, 42.2, 45.5, 46.9 und 50.7), 60.2 (s, OCH2), 175,736.8, 38.8, 42.2, 45.5, 46.9 and 50.7), 60.2 (s, OCH 2 ), 175.7
(m, CO) ppm IR (KBr): v = 2976 (s), 2954 (s), 2904 (s), 2878 (s), 1728 (s), 1449(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"1
Beispiel 22(m), 1371 (m), 1347 (m), 1300 (m), 1182 (s), 1043 (m) cm "1 Example 22
Homopolymerisation von Bicyclo[2.2.1]hept-5-en mit einem 6- Methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll)tetrafluoroborat-Komplex, bei Raumtemperatur, [Pd]:[M]=1 :600Homopolymerization of bicyclo [2.2.1] hept-5-ene with a 6-methoxybicyclo [2.2.1] hept-2-ene-endo-5σ, 2π) -palladium (II) tetrafluoroborate complex, at room temperature, [Pd] : [M] = 1: 600
In einem 100 ml Kolben wurden 24.0 mg (0.0455 mmol) Di-μ-chloro-bis-(6- methoxybicyclo[2.2.1]hept-2-en-endo-5σ,2π)-palladium(ll) in 2.4 ml Chlorbenzol gelöst. Dazu wurden 26.5 mg (0.137 mmol) AgBF4 gegeben und 3 min bei Raumtemperatur gerührt. Die gelbe Katalysatorlösung wurde filtriert und das 0.63 ml des Filtrats zu 1.35 g (0.014 mol) Norbornen gegeben. Die Polymerisationsiösung wurde eine Stunde bei Raumtemperatur gerührt. Das Polymer wurde in Methanol ausgefällt, abfiltriert, gewaschen und 8 Stunden bei 100 X getrocknet. Es wurden 20 mg (1.5 % der Theorie) eines weißen Feststoffs erhalten.
24.0 mg (0.0455 mmol) di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-en-endo-5σ, 2π) -palladium (II) in 2.4 ml chlorobenzene were placed in a 100 ml flask solved. 26.5 mg (0.137 mmol) of AgBF 4 were added and the mixture was stirred at room temperature for 3 min. The yellow catalyst solution was filtered and the 0.63 ml of the filtrate was added to 1.35 g (0.014 mol) of norbornene. The polymerization solution was stirred at room temperature for one hour. The polymer was precipitated in methanol, filtered off, washed and dried at 100X for 8 hours. 20 mg (1.5% of theory) of a white solid were obtained.
Claims
Patentansprücheclaims
Verbindung mit der allgemeinen Formel (I):Compound with the general formula (I):
wobeiin which
R1 einen mono- oder polycyclischen Kohlenwasserstoff bedeutet,R 1 represents a mono- or polycyclic hydrocarbon,
M1+ ein Übergangsmetall der Gruppe Vlllb bedeutet,M 1+ is a transition metal from group VIIIb,
X" mindestens ein nicht- oder schwachkoordinierendes Anion bedeutet.X "means at least one non- or weakly coordinating anion.
2. Verbindung mit der allgemeinen Formel (I) nach Anspruch 1 , wobei2. A compound having the general formula (I) according to claim 1, wherein
R1 einen mono- oder polycyclischen Kohlenwasserstoff mit mindestens einer ungesättigten Bindung innerhalb oder außerhalb des Ringes bedeutet,R 1 denotes a mono- or polycyclic hydrocarbon with at least one unsaturated bond inside or outside the ring,
M 1 + Rh, Ru, Pd, Co oder Ni bedeutet,M 1 denotes Rh, Ru, Pd, Co or Ni,
BF4-, PF6-, SbF6-, AsF6-, CIO4-, BPh4-, wobei die Phenylgruppen durch Fluor oder Trifluormethyl substituiert sein können, closo-Borane sowie Carborane und deren halogenierten Derivate oder Triflate bedeutet.BF 4 -, PF 6 -, SbF 6 -, AsF 6 -, CIO 4 -, BPh 4 -, where the phenyl groups can be substituted by fluorine or trifluoromethyl, means closo-boranes and carboranes and their halogenated derivatives or triflates.
3. Verbindung mit der allgemeinen Formel (I) nach Anspruch 1 oder 2, wobei R1 substituiertes oder unsubstituiertes Norbornen, Cycloocten,3. A compound having the general formula (I) according to claim 1 or 2, where R 1 is substituted or unsubstituted norbornene, cyclooctene,
Tricyclodecen oder exo-Methylencyclohexen, M1+ Pd bedeutet, X" BF4-, PF6-, SbF6-, AsF6- oder Carborane bedeutet.Tricyclodecene or exo-methylenecyclohexene, M 1+ Pd means X " BF 4 -, PF 6 -, SbF 6 -, AsF 6 - or carboranes.
Verbindung mit der allgemeinen Formel (I) nach einem oder mehreren der Ansprüche 1 bis 3, wobei
R1 eine Verbindung mit der allgemeinen Formel (II)Compound with the general formula (I) according to one or more of claims 1 to 3, wherein R 1 is a compound of the general formula (II)
wobeiin which
R2 ein Wasserstoffatom, eine C C^-Alkylgruppe, C6-C20-Arylgruppe,R 2 is a hydrogen atom, a CC ^ alkyl group, C 6 -C 20 aryl group,
OR3-, SR3-, OCOR3-, R3OOCCHCOOR3- oder R3OCCHCOR3-Gruppe ist, wobei R3 ein Wasserstoffatom, eine C1-C20-Alkylgruppe oder C6-C20-Arylgruppe bedeutet, eine -CN, -SCN, -NR3 2, N3-Gruppe oder ein Halogenatom bedeutet.OR 3 -, SR 3 -, OCOR 3 -, R 3 OOCCHCOOR 3 - or R 3 OCCHCOR 3 group, where R 3 represents a hydrogen atom, a C 1 -C 20 alkyl group or C 6 -C 20 aryl group, represents a -CN, -SCN, -NR 3 2 , N 3 group or a halogen atom.
5. Verbindung mit der allgemeinen Formel (I) nach einem oder mehreren der Ansprüche 1 bis 4 gelöst in mindestens einem halogenierten Kohlenwasserstoff, aliphatischen- oder aromatischen Kohlenwasserstoff, die mindestens ein Heteroatom wie Sauerstoff oder Stickstoff enthalten können.5. A compound with the general formula (I) according to one or more of claims 1 to 4 dissolved in at least one halogenated hydrocarbon, aliphatic or aromatic hydrocarbon, which may contain at least one heteroatom such as oxygen or nitrogen.
6. Verbindung mit der allgemeinen Formel (I) nach Anspruch 5 gelöst in Methylenchlorid, Chloroform, Nitromethan, Dimethylformamid, N-Methylpyrolidon, Dimethylethylenharnstoff, Nitrobenzol, oder Chlorbenzol.6. Compound with the general formula (I) according to claim 5 dissolved in methylene chloride, chloroform, nitromethane, dimethylformamide, N-methylpyrolidone, dimethylethylene urea, nitrobenzene, or chlorobenzene.
7. Verbindung mit der allgemeinen Formel (I) nach einem oder mehreren der Ansprüche 1 bis 6 und einem Cycloolefin, das mindestens einen Rest R4 aufweist, wobei das Verhältnis der Verbindung mit der allgemeinen Formel (I) zum Cycloolefin von 1:1 bis 1:10 beträgt und R4 eine COOR3, oder -NC, COR3-Gruppe bedeutet.7. A compound having the general formula (I) according to one or more of claims 1 to 6 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 Is 1:10 and R 4 is a COOR 3 , or -NC, COR 3 group.
8. Verfahren zur Herstellung der Verbindung mit der allgemeinen Formel (I), nach einem oder mehreren der Ansprüche 1 bis 6, wobei8. A process for the preparation of the compound of general formula (I) according to one or more of claims 1 to 6, wherein
M1+R1Hal" mit M2+X" in mindestens einem Lösungsmittel umgesetzt wird, wobei
Hai" F", CI", Br", J" oder ein Pseudohalogen wie CN" oder SCN" bedeutet und M2+ ein Alkali-, Erdalkalimetall, Ag, Tl oder Cu bedeutet.M 1+ R 1 Hal " with M 2+ X " is reacted in at least one solvent, where Shark means " F " , CI " , Br " , J " or a pseudohalogen such as CN " or SCN " and M 2+ means an alkali, alkaline earth metal, Ag, Tl or Cu.
9. Verfahren zur Herstellung der Verbindung mit der allgemeinen Formel (I) und einem Cycloolefin nach Anspruch 7, wobei eine Menge von 1 :1 bis 1 :10, bezogen auf die Verbindung mit der allgemeinen Formel (I) vorgelegt wird und M1+R1Hal" mit M2+X" in mindestens einem Lösungsmittel umgesetzt wird.9. A process for the preparation of the compound having the general formula (I) and a cycloolefin according to claim 7, wherein an amount of 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.
10. Verfahren zur Herstellung von Homo- und/oder Copolymeren mit mindestens einer Verbindung mit der allgemeinen Formel (I) nach einem oder mehreren der Ansprüche 1 bis 7 als Katalysatorsystem.10. A process for the preparation of homopolymers and / or copolymers with at least one compound of the general formula (I) according to one or more of claims 1 to 7 as a catalyst system.
11. Verwendung einer Verbindung mit der allgemeinen Formel (I) nach einem oder mehreren der Ansprüche 1 bis 7 als Katalysatorsystem zur Herstellung von Homo- und/oder Copolymeren.
11. Use of a compound with the general formula (I) according to one or more of claims 1 to 7 as a catalyst system for the production of homo- and / or copolymers.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19715104 | 1997-04-11 | ||
DE19715104 | 1997-04-11 | ||
DE19716312A DE19716312A1 (en) | 1997-04-11 | 1997-04-18 | Catalyst and use of the catalyst for the polymerization |
DE19716312 | 1997-04-18 | ||
PCT/EP1998/002003 WO1998046614A1 (en) | 1997-04-11 | 1998-04-07 | Catalyst and use of catalysts in polymerisation |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0973786A1 true EP0973786A1 (en) | 2000-01-26 |
Family
ID=26035688
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98921435A Withdrawn EP0973786A1 (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
Non-Patent Citations (1)
Title |
---|
See references of WO9846614A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2286695A1 (en) | 1998-10-22 |
AU7429498A (en) | 1998-11-11 |
WO1998046614A1 (en) | 1998-10-22 |
JP2001519821A (en) | 2001-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE19654074C2 (en) | Process for the preparation of hydrogenated ring-opened metathesis polymers | |
Breunig et al. | Transition‐metal‐catalyzed vinyl addition polymerizations of norbornene derivatives with ester groups | |
DE1770491C3 (en) | Process for the preparation of trans-Polynentenamer | |
DE2729196A1 (en) | METHOD FOR PRODUCING POLYMERS OR COPOLYMERS OF OLEFINS WITH AT LEAST 3 CARBON ATOMS | |
Heinz et al. | Poly (norbornene carboxylic acid ester) s: Synthesis and properties | |
DE112020002202T5 (en) | Novel diaroylcarbazole compound and use of the same as a sensitizer | |
DE1945358C3 (en) | Low molecular weight polyalkenamers and processes for their preparation | |
EP0973786A1 (en) | Catalyst and use of catalysts in polymerisation | |
US3081334A (en) | Bicyclo-[2.2.2]oct-2-ene-1, 4-dicarboxylic acid, its preparation and functional derivatives | |
EP0694568A2 (en) | Cycloolefincopolymers and a process for their preparation | |
DE60024682T2 (en) | COPOLYMERS MANUFACTURED BY RING OPENING POLYMERIZATION, HYDROGENATION PRODUCT BY COPOLYMERS MADE BY RING OPENING POLYMERIZATION, AND METHOD FOR THE PRODUCTION THEREOF | |
DE19716312A1 (en) | Catalyst and use of the catalyst for the polymerization | |
Pittman Jr et al. | Organometallic polymers. XXX. Synthesis and copolymerization of η6-(2-phenylethyl methacrylate) tricarbonylchromium with organic monomers | |
CH434761A (en) | Process for converting olefinic polymers into polymers containing hydroxyl groups | |
MXPA06006495A (en) | Linear functional copolymers of ethylene with precise and minimum run length distributions and methods of making thereof. | |
DE1954255C3 (en) | Polymers with a system of conjugated double bonds in the main chain and process for their preparation | |
DE4344514A1 (en) | Cycloolefin copolymers and process for their manufacture | |
DE2521152A1 (en) | POLYMERS FROM CIS-5-NORBORNEN-2,3-DICARBOXY-ANHYDRIDE | |
DE2036405A1 (en) | New polymers | |
EP0973813A1 (en) | Production of homocopolymers, co-copolymers or block copolymers from cycloolefinic monomer units | |
DE1520013A1 (en) | Poly (2-butynediol-1,4) and process for its preparation | |
DE69605754T2 (en) | Derivatives of bridged cyclopentadienyl compounds and process for their preparation | |
Qureshi et al. | Investigations into the free radical polymerizations of allyl carbonates—I. The reaction of t-butoxyl radical | |
DE2334606A1 (en) | POLYMERIZATION OF NORBORN DERIVATIVES | |
DE2316112A1 (en) | PROCESS FOR THE PRODUCTION OF MIXED POLYMERIZES FROM MALE ACID AND CONJUGATED SERVICES |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19991111 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB IT |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Withdrawal date: 20000413 |