MXPA97003318A - Procedure for the polymerization of cyclic olefins and photopolimerization composition - Google Patents
Procedure for the polymerization of cyclic olefins and photopolimerization compositionInfo
- Publication number
- MXPA97003318A MXPA97003318A MXPA/A/1997/003318A MX9703318A MXPA97003318A MX PA97003318 A MXPA97003318 A MX PA97003318A MX 9703318 A MX9703318 A MX 9703318A MX PA97003318 A MXPA97003318 A MX PA97003318A
- Authority
- MX
- Mexico
- Prior art keywords
- alkyl
- substituted
- unsubstituted
- alkoxy
- halogen
- Prior art date
Links
- -1 cyclic olefins Chemical class 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims description 37
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 96
- 150000002367 halogens Chemical class 0.000 claims abstract description 94
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000010936 titanium Substances 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000010955 niobium Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 24
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 21
- 239000010937 tungsten Substances 0.000 claims abstract description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003197 catalytic Effects 0.000 claims abstract description 12
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 180
- 125000003545 alkoxy group Chemical group 0.000 claims description 99
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 71
- 239000000460 chlorine Substances 0.000 claims description 69
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 59
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 38
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 36
- 229910052731 fluorine Inorganic materials 0.000 claims description 36
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 32
- 229910052801 chlorine Inorganic materials 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 125000001188 haloalkyl group Chemical group 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 23
- 125000004848 alkoxyethyl group Chemical group 0.000 claims description 22
- 125000002723 alicyclic group Chemical group 0.000 claims description 21
- 125000004429 atoms Chemical group 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 20
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229910052794 bromium Inorganic materials 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 239000001301 oxygen Chemical group 0.000 claims description 18
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 150000001925 cycloalkenes Chemical class 0.000 claims description 17
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 125000005842 heteroatoms Chemical group 0.000 claims description 14
- 230000001264 neutralization Effects 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000011593 sulfur Chemical group 0.000 claims description 14
- 239000000969 carrier Substances 0.000 claims description 12
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 12
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 11
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 10
- JFNLZVQOOSMTJK-UHFFFAOYSA-N Norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 150000003658 tungsten compounds Chemical class 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 5
- 150000002822 niobium compounds Chemical class 0.000 claims description 5
- 150000002848 norbornenes Chemical class 0.000 claims description 5
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 5
- 150000003482 tantalum compounds Chemical class 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 4
- 125000005885 heterocycloalkylalkyl group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 4
- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical compound [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002619 bicyclic group Chemical group 0.000 claims description 3
- 230000027455 binding Effects 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 150000003003 phosphines Chemical group 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 2
- 125000005469 ethylenyl group Chemical group 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 16
- 125000002431 aminoalkoxy group Chemical group 0.000 claims 1
- 229910052803 cobalt Inorganic materials 0.000 claims 1
- 238000005649 metathesis reaction Methods 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000007142 ring opening reaction Methods 0.000 abstract description 8
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- JFDZBHWFFUWGJE-UHFFFAOYSA-N Benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000008079 hexane Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000003287 optical Effects 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-Trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N Benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N Benzyl cyanide Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N Chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N Dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N Indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N Propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N Trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N Triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SJRJJKPEHAURKC-UHFFFAOYSA-N n-methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- KYQCOXFCLRTKLS-UHFFFAOYSA-N pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
A process for the photocatalytic polymerization of a cyclic olefin or at least two different cyclic olefins in the presence of a metal compound as a catalyst in which a metathesis polymerization is carried out with photochemical ring opening in the presence of a catalytic amount of at least one thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen are bonded to the metal. The process can also be carried out in such a way that the polymerization is first irradiated and terminated by heating. The process is suitable, for example, for the preparation of thermoplastic molded masses, coatings and configurations in real
Description
Process for the polymerization of cyclic olefins and photopolymerizable composition. The present invention relates to a process for the polymerization of cyclic olefins through a polymerization of photochemical metathesis with ring opening, under application of catalytic amounts of a molybdenum, tungsten, titanium, niobium or tantalum catalyst, in which they are found. linked a silylmethyl group and at least one halogen to the metal, and also concerns compositions containing these olefins together with a catalytic amount of this catalyst. The polymerization by metathesis and ring opening, thermally induced, under the application of catalytic amounts of metal catalysts has been known for quite some time and has been described in multiple forms in the literature [see for example Ivin, KJ, olefin metathesis 1- 12, Acade ic Press, London (1983)]. The polymers thus elaborated are obtained by industrial means and can be obtained in the market. On the other hand, little has been known about polymerization by metathesis and ring opening, photochemically induced, and to date there are no commercial applications. From US Pat. No. 4,060,468 it is known to carry out a polymerization of olefin metathesis in such a way that a two-component mixture consisting of a metal salt, selected from the salts of tungsten, molybdenum, rhenium and tantalum, is introduced. and a substituted phenol or benzyl alcohol as cocatalysts in a reaction vessel with the monomeric olefin, then irradiating the entire reaction mixture with ultraviolet light. As olefins, only cyclic and acyclic hydrocarbons without functional groups or substituents are mentioned. The separate deposition of the catalyst components and the step of the process of mixing the catalyst components immediately before the actual reaction make the process known technically expensive and laborious. Tanielan and collaborators [Tanielan, C, Kieffer, R. Harfouch, A., Tetrahedron Letters 52: 4589-4592 (1977)] describe the catalyst system of W (CO) 6 / CC14, which after irradiation with ultraviolet light can take advantage of the polymerization of cyclopentene and norbornene metathesis. Metal carbonyls are volatile and toxic so that their use makes it necessary for physiological reasons, the taking of expensive protective measures. In addition, a radical addition reaction under formation of monomeric l-chloro-2-trichloromethyl-cycloalkanes is observed as a competitive reaction. From Thoi et al [Thoi, H.H., Ivin, K.J., Rooney, J.J., J. Mol. Catal. 15: 245-270 (1982)] it is known that the tungsten pentacarbonylcarteno complex of the formula
Feniio
it constitutes a thermal catalyst for the polymerization by metathesis, ring opener, of dimethylnorbornene and which together with the phenylacetylene as cocatalyst also constitutes a photocatalyst system for the same polymerization. This catalyst system has the serious advantage that as a ready-to-use formulation, it only has a low storage stability, the carbonyl compound has physiological problems and tolerance to functional groups in the cycloolefins is too low. Feldmann et al. [Feldmann, C, et al., In: Stephen J. Lippard (De.) Progress in Inorganic Chemistry, 39: 3-73 (1991)] describe molybdenum and tungsten alkylidene complexes which are weak catalysts alone, but in conjunction with Lewis acids they constitute effective thermal catalysts for the polymerization of cycloolefins.
The known, photochemically activatable catalysts therefore require a cocatalyst, whereby the quality of the processed polymers can fluctuate strongly due to the selected class and sequence of the reactants. With the known processes, the cyclic olefin polymers can be prepared by metathesis polymerization with ring opening, photochemical type, only with high investment and in an economically unsatisfactory way. Particular disadvantages are the poor stability during storage, which allows mixing of the components only immediately before preparation, insufficient tolerance to functionalized cyclic olefins and the need for the use of two components as a catalyst system. Therefore, there is a need to have an improved process, generally useful, from the technical, economic and ecological point of view, in order to prepare polymers starting from cyclic olefins by means of a photochemical polymerization with ring opening, of photochemical type. International patent WO 93/13171 discloses one-component and two-component catalysts, stable in air and water, based on molybdenum and tungsten compounds containing carbonyl groups, as well as ruthenium compounds and of osmium, at least with a polyene ligature for the polymerization of thermal metathesis and a polymerization of photoactivated metathesis of tightened cyclolefins, especially norbornene and norbornene derivatives. Other polycyclic cycloolefins are not mentioned, and above all, non-condensed polycyclic cycloolefins are not mentioned. The catalysts used, based on a single component, of the ruthenium compounds, namely [Ru (Cu ene) C12] 2 and [(C6H6) Ru (CH3CN) 2Cl] + PF6, are true that they can be activated by ultraviolet irradiation , but the stability capacities during the storage of the compositions with norbornene are totally insufficient. These catalysts can not sufficiently replace the known two-component catalysts. Petasis and Fu [Petasis, NA, Fu, D., J. Am. Chem. Soc. 115: 7208-7214 (1993)] describe the polymerization of ring-opening metathesis, of thermal type, of norbornene using biscyclopentadienyl -bis (trimethylsilyl) methyl-titanium (IV) as a thermally active catalyst. However, the catalytic activity is low, which means that long reaction times are needed and above all, relatively low polymer yields are achieved. It is not disclosed that these catalysts are suitable for polymerization by ring-opening, photo-induced metathesis of the cyclo-olefins under tension. It was found that the tensed cycloolefin compositions and a single component catalyst are photochemically polymerizable when the composition contains a compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI) in that at least one halogen is bonded as well as a silylmethyl group to the metal. Surprisingly, these thermally stable compounds have proved to be effective catalysts for photo-induced ring-opening metathesis polymerization in which, despite the photochemical reactivity, the storage stability of cycloolefin mixtures and titanium compounds ( IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI). In addition, it has surprisingly been found that the catalysts mentioned already after a short time of irradiation, work, in the presence of cycloolefins, as thermal catalysts, so that the photochemical and thermal polymerization can be applied in combination. An object of the present invention is a process for the photocatalytic polymerization of a cyclic olefin or at least two different cyclic olefins in the presence of a metal compound as a catalyst, which is characterized in that a polymerization by metathesis and opening of a polymer is carried out. ring, photochemical, in the presence of a catalytic amount of a thermosetting compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen are bound to metal. The other valences of titanium, niobium, tantalum, molybdenum and tungsten are preferably saturated with neutral thermostable bonds which are known in large quantities. The number of neutral bonds can also exceed the amount stoichiometrically (solvates). As regards the cyclic olefins, they may be fused and / or bridged, monocyclic or polycyclic ring systems, for example containing two to four rings, which are unsubstituted or substituted and which may comprise heteroatoms such as 0, S , N or Si in one or more rings and / or in aromatic or heteroaromatic rings, condensed, such as for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyridinylene. The individual cyclic rings may contain from 3 to 16, preferably 3 to 12 and particularly preferably from 3 to 8 members in the ring. The cyclic olefins may contain other non-aromatic double bonds, according to the ring size preferably 2 to 4 of such additional double bonds. The ring substituents are those that are inert, that is to say, that do not influence the chemical stability and thermal stability of the titanium, niobium, tantalum, molybdenum and tungsten compounds. The cycloolefins are the tensioned rings and corresponding ring systems. The thermal stability or thermostability means within the framework of the invention that the photocatalytically active compounds of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VII) under heating do not form any active species for polymerization by metathesis with ring opening. The catalyst, for example at an ambient temperature up to a slightly increased temperature of about + 40%, within weeks and under the exclusion of light, is not capable of initiating a ring-opening metathesis polymerization. During this time only an insignificant amount of monomer (less than 0.2% by weight) is reacted. The thermostability for example can be determined when a solution of toluene with 20% by weight of monomer and 0.33% by weight of titanium, molybdenum, wolfranium, niobium or tantalum catalyst is stored in the dark at 50 ° C and for a time of 96 hours and when a polymeric amount eventually formed, recognizable in the structuring of the viscosity and by its precipitation in a precipitating agent such as for example ethanol, filtration and drying is determinable quantitatively and does not amount to more than 0.5% by weight and preferably, ro is greater than 0.2% by weight. When the cyclic olefins contain more than one double bond, such as for example 2 to 4 double bonds, crosslinked polymers can also be formed, depending on the reaction conditions, the selected monomer and the amount of catalyst.
In a preferred embodiment of the process according to the invention, the cycloolefins correspond to Formula I
in which Q? represents a radical with at least one carbon atom, which together with the group -CH = CQ2 forms a ring
alicyclic containing at least three members, which optionally contains one or more heteroatoms selected from the group consisting of silicon, phosphorus, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, = 0, - CN, -NO, R1R2R3SÍ- (O) u-, -COOM, -SO3M, -PO3M, -COO (M1) 1/2, - PO (M), alkyl with C to C, hydroxyalkyl with C to
C,, haloalkyl with C to C, cyanoalkyl with C to C ", cycloalkyl with C 3 to C8, aryl with C6 to C16, aralkyl with
C 'a C16, heterocycloalkyl with C3 to C6, heteroaryl with
C 3 to C 16, heteroaralkyl with C 4 to C 16 or R 4 -X-; or in which two adjacent atoms of carbon are substituted with -CO-O-CO- or with -CO-NR -CO-; or in which eventually
in adjacent carbon atoms of the alicyclic ring, an alicyclic, aromatic or heteroaryl atomic ring, which is either unsubstituted or substituted with halogen, is attached by condensation, -CN, -NO 2, R 6R 7R 8Si- (O) u -, COOM, -SO 3M, PO 3M, -COO (M 1) 1 /, 2, -SO 3 (M 1) 1/2, PO (M), alkyl with C to C, halogenoalkyl with C to C , hydroxyalkyl with C to C, cyanoalkyl with C to C_, cycloalkyl with C 3 to Co, aryl with C6 to C16, aralkyl to
C 3 to C 16, 'heteroaralkyl with C 4 to C 16,' or R 13 -X 1 -; X and XI, independently of each other represent -O-, -S-, -C0-, -SO-, -SO-, -0-C (0) -, -C (0) -0-, -C (0 ) -NR-, - NR 10-C (0) -, -SO 2 -O- or -O-SO 2; R, R7 and R independently of each other represent alkyl with C to C _, perfluoroalkyl with C to C, phenyl or benzyl;
R4 and -R13 independently means alkoxy with C1 to C20, haloalkyl with C1 to C20, hydroxyalkyl with Ci to C20, cycloalkyl with C3 to C8, aryl with C6 to C16 or arals and R and R independently they represent hydrogen, alkyl with C to C ^, phenyl or benzyl in which the groups
alkyl for their part are unsubstituted or are substituted with C 1 to C 12 alkoxy or cycloalkyl with C 3 R 6, R J and R 8 independently represent C 1 to C 12 alkyl, C to C 12 cerfluoroalkyl, phenyl or benzyl; M represents an alkali metal and M denotes a metal
alkaline earth; and u means 0 or 1; wherein the alicyclic ring formed with Q contains eventually non-aromatic double bonds; Q2 represents hydrogen, alkyl with C 1 to C 20, haloalkyl with C I to C 20, alkoxy with C 1 to C 12, halogen, -CN, or R 11 -X-; R represents alkyl with C to C, halogenalkyl with C to C 20, hydroxyalkyl with C 1 to C 20, cycloalkyl with C 3 to C 8, aryl with C 6 to C 16, or aralkyl with C 7 to C 16; X represents -C (0) -0- or -C (0) -NR; R stands for hydrogen, alkyl with C to C? ^, Phenyl and benzyl; in which the aforementioned groups of cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or are substituted with alkyl with C 1 to C 12, alkoxy with C 1 to C 1, -NO, -CN or halogen, and that the heteroatoms of the
Previous groups of heterocycloalkyl, heteroaryl and heteroalkyl are selected from the group of -0-, -S-, -NR- and -N =; Y
R represents hydrogen, alkyl with C to C, phenyl or benzyl. The alicyclic rings attached by condensation preferably contain from 3 to 8 atoms, particularly preferably from 4 to 7 atoms and particularly preferably 5 or 6 carbon atoms in the ring. When it is present in the compounds of Formula I, an asymmetric center, this has the consequence that the compounds can be present in optically isomeric forms. Some compounds of Formula I may be present in their tautomeric forms (for example in a keto-enol tautomerism). When an aliphatic double bond of C = C is present, then a geometric isomerism (form E or form Z) can also be presented. In addition, the exo-endo configurations are also possible. Formula I comprises the following all possible stereoisomers which are present in the form of enantiomers, tautomers, diastereomers, E / Z isomers or their mixtures. In the definitions of the substituents, the alkyl, alkenyl and alkinyl groups can be straight or branched chain. The same can also be said for the portion or any alkyl portion of the alkoxy, alkylthio, alkoxycarbonyl or other alkyl-containing groups. These alkyl groups preferably contain from 1 to 12 carbon atoms and preferably from 1 to 8 and particularly preferably from 1 to 4 carbon atoms. These alkenyl and alkynyl groups preferably contain 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 4 carbon atoms. Alkyl comprises, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, secondary butyl, tertiary butyl as well as the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl radicals, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. The hydroxyalkyl comprises, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-isobutyl, 1-hydroxy-butyl secondary, 1-hydroxybutyl tertiary, as well as the different isomeric radicals of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. Alkyl halogen comprises, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, and also halogenated alkanes, particularly fluorinated ones or chlorinated ones, such as, for example, isopropyl, n-propyl, n-butyl, isobutyl, secondary butyl, tertiary butyl radicals and the different isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl radicals , tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. The alkenyl comprises, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2. -enyl, iso-dodecenyl, n-octadec-2-enyl, n-octadec-4-enyl. The alkyl cycle is preferably cycloalkyl with C 5 to C 8, especially cycloalkyl with
C or C Some examples are cyclopropyl,
dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
The cyanoalkyl comprises, for example, cyanomethyl
(methylnitrile), cyanoethyl (ethylnitrile), 1-cyanoisopropyl, 1- cyano-n-propyl, 2-cyano-n-butyl, 1-cyano-iso-butyl, 1- cyano-butyl secondary, 1-cyano-tertiary butyl , as well as the different isomeric radicals of cyanopentyl and cyanohexyl. The aralkyl preferably contains from 7 to 2 carbon atoms and more preferably from 7 to 10 carbon atoms. It can be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, phenylbutyl or a, a-dimethylbenzyl. The aryl preferably contains from 6 to 10 carbon atoms. It can be, for example, phenyl, pentaline, indene, naphthalene, buccal or anthracene. The heteroaryl preferably contains 4 or 6 carbon atoms and one or two heteroatoms selected from the group O, S and N. It can be, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indene, purine. or quinoline. The heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the group of O, S and N. It can be, for example, oxirane, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or tetrahydrothiophen. Alkoxy is for example methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, secondary butyloxy and t-butyloxy. An alkali metal of the scope of the present invention should be understood as lithium, sodium, potassium, rubidium and cesium, in particular lithium, sodium and potassium. By alkaline earth metal within the framework of the present invention should be understood beryllium, magnesium, calcium, strontium and barium, especially magnesium and calcium. In the above definitions, halogen should be understood as meaning fluorine, chlorine, bromine and iodine, and preferably fluorine, chlorine and bromine. The compounds perfectly suitable for the process according to the invention according to Formula I are those in which Q "represents hydrogen.
Also preferred for polymerization are compounds of Formula I in which the alicyclic ring, which forms Q together with the group -CH = CQ-, contains 3 to 16 atoms and preferably 3 to 12 atoms and most preferably 3 to 8. atoms in the ring, it being possible here to treat a monocyclic, bicyclic, tricyclic or tetracyclic ring system. With particular advantage, the process according to the invention can be carried out with those compounds of Formula I in which Q represents a radical with at least one carbon atom which, together with the group -CH = CQ-, forms an alicyclic ring with 3-carbon atoms. to 20 members, optionally containing one or more heteroatoms selected from the group of silicon, oxygen, and sulfur; and which is unsubstituted or is substituted with halogen, = 0, -CN, -NO, RRR Si- (0) -, -COOM, -SO M, - P03M, -C00 (Ma)? /;, -S03 (M?)? / 2, -PO ^) ^, alkyl with C? to
C ,, Halogenoalkyl with C to C, hydroxyalkyl with C a
C, cyanoalkyl with C to C, cycloalkyl with C to C, aryl with C 6 to C12, aralkyl with C7 to C12, heterocycloalkyl with C3 to C6, 'heteroaryl with C3 to C12, heteroaralkyl with C4 to C12 or R4-X-; or in which two adjacent atoms of carbon are substituted in this radical Q with -C0-0-C0- or with -CO-NR -CO-; or in that
optionally an alicyclic, aromatic or heteroaromatic ring, which is unsubstituted or substituted by halogen, -CN, -NO 2, R6R7R8Si- is attached to the adjacent carbon atoms.
alkyl with C1 to C12, 'halogenalkyl with C 1 to C12,' cycloalkyl with C to C, aryl with C to C, aralkyl with C to C 7, heterocycloalkyl with C to C, heteroaryl with Ci to C12, heteroaralkyl with C4 to C12 or R13X1-; X independently between them represent -O-, -S-, - CO-, -SO-, -SO-, -OC (O) -, -C (0) -0-, -C (0) -NR5-, -NR10- C (O) -, -SO -O- or -O-SO-; R 1, R 2, R 3, and R 3, independently of each other represent alkoxyl with C 1 to C 6, perfluoroalkyl with C 1 to C 6, phenyl or benzyl; M represents an alkali metal and M denotes an alkaline earth metal; R4 and R13 independently from each other mean alkyl with
C a Ci 2, haloalkyl with C to C, hydroxyalkyl with C 1 to C 12, cycloalkyl 1 to C 3 to C 8, aryl to C 6 to C 12, or aralkyl to C 7 to C 12; R and R independently from each other mean hydrogen, alkyl with C to C, phenyl or benzyl in which the alkyl groups for their part are unsubstituted or are substituted with C 1 to C 6 alkoxy or in cycloalkyl with
R, R and R independently of each other represent alkyl with C 1 to C 6, perfluoroalkyl with C 1 to C 6, phenyl or benzyl; u represents 0 or 1; wherein the alicyclic ring formed with Q in its case contains other non-aromatic double bonds; Q2 represents hydrogen, alkyl with C 1 to C 12, haloalkyl with C to C, alkoxy with C to C, halogen, -CN, or R 11 -X 2 -;
C 12, hydroxyalkyl with C 1 to C 12, cycloalkyl with C 3 to C 6, aryl with C 6 to C 12, or aralkyl with C 7 to C 12; X means -C (0) -0- or -C (0) -NR-; and R 12 means hydrogen, alkyl with C 1 to C, phenyl or
benzyl; wherein the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or are substituted with alkyloxy with C1 to C6, alkoxy with C1 to C6, -NO2, -CN or halogen, and wherein heteroatoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group consisting of -O-, -S-, NRa- and-
N =; R represents hydrogen, alkyl with C to C, phenyl or benzyl.
Within this group preference is given to those compounds of Formula I in which Q represents a radical with at least one carbon atom, which together with the group -CH = CQ, - forms an alicyclic ring with 3 to 10 members, which optionally contains a heteroatom selected from the group of silicon, oxygen, nitrogen and sulfur, and which is unsubstituted or is substituted with halogen, -CN, -NO, RRR Si-, -COOM-, -SO M, PO M, - COO (M?), -PO (M), alkyl with C to C, haloalkyl with C 1 to C6, hydroxyalkyl with C 1 to C 6, cyanoalkyl with
C to C, cycloalkyl with C to C, phenyl, benzyl or R -X-; or else that an alicyclic, aromatic or heteroaromatic ring, which is of the unsubstituted type or is substituted by halogen, -CN, -NO 2, R6R7R8Si-, 'COOM,' - is optionally bonded by condensation to the adjacent carbon atoms. SO3M, -PO3M, '-COO (M1) 1/2,' -SO3 (Ml) 'l / 2
-PO 3 (M1) 1/2. alkyl with C1 to C6, haloalkyl with C1 to
C 6, hydroxyalkyl with C 1 to C 6, cyanoalkyl with C 1 to C 4, cycloalkyl with C 3 to C 6, phenyl, benzyl or R 13 -X 1 -; R, R and R independently of each other means alkyl having 1 to 4 perfluoroalkyl carbon atoms with C 1 to C,
phenyl or benzyl; M represents an alkali metal and M denotes an alkaline earth metal; R and R independently between them mean alkyl with
C 1 to C 6, haloalkyl with C 1 to C 6, hydroxyalkyl with C 1 to C 6 or cycloalkyl with C 3 to C 6; X and X independently between them represent -0-, -S-, - CO-, -SO- or -SO-; R 6, R 7 and R 8 independently of each other, mean alkyl with C to C, perfluoroalkyl with C to C, phenyl or
benzyl;
and Q2 represents hydrogen.
In particular, the process according to the present invention is suitable for the polymerization of norbornene and norbornene derivatives. Of these norbornene derivatives those which correspond to either Formula II are particularly preferred.
in which X 3 represents -CHR. , -, oxygen or sulfur; Ri4 and R? S independently from each other represent hydrogen, -CN, trifluoromethyl, (CH) Si-O-, (CH) Si- or R16 and Ri7 independently represent hydrogen, alkyl with C? C, phenyl or benzyl; or to Formula III
(neither)
in which X represents -CHR. 1c6-, oxygen or sulfur; t19 is hydrogen, alkyl with C. to C? 2, phenyl or benzyl; and IB represents hydrogen, rent with C? C. or halogen; or to Formula IV
wherein X5 represents -CHR?, -, oxygen or sulfur; R is hydrogen, alkyl with C? to CJ2, phenyl or benzyl-o; R 0 and R 21 independently of each other represent hydrogen, CN, tri fluoromethyl, (CH) Si-O-, (CH) Si- or 3 3 R., signifies hydrogen, alkyl with C 12 phenyl benzyl; or that correspond to Formula V
(V),
wherein X 6 represents -CHR24-, oxygen or sulfur; R represents hydrogen, alkyl with C to 12 phenyl or benzyl;
Y represents oxygen or N-R; Y
R represents hydrogen, methyl, ethyl or phenyl. The following compounds of the Formula I are particularly well suited for the polymerization process according to the invention, in which the bicyclic and polycyclic systems are accessible through the Diels-Alder reactions:
As for the titanium (IV), niobium (V) and tantalum (V) compounds to be used according to the invention, they are those containing a metal atom. As for the molybdenum (VI) and tungsten (VI) compounds to be used according to the invention, they may be those containing one metal atom or two metal atoms linked through a single bond, double or triple. The other valences of titanium, niobium, tantalum, molybdenum and tungsten are preferably saturated with thermostable neutral bonds, the definition of thermostability having already been given at the beginning. As for the halogen bound to the metal atom, it is preferably F, Cl, Br and I, and preferably F, Cl and Br and with particular preference of F or Cl. Silylmethyl ligation corresponds preferably to Formula VII,
wherein R 29, R 30 and J R 31, independently of each other, represent alkyl with C 1 to C 18, cycloalkyl with C 5 or C 6 or is phenyl unsubstituted or substituted with alkyl with C 1 to C 6 or alkoxy with C 1 to C 6 or in his case benzyl. When R 29 to R31 represent alq-iuil, r then the
The chain can be linear or branched or it will preferably contain from 1 to 12, and particularly preferably from 1 to 8 and very particularly from 1 to 4 carbon atoms. Particularly preferred alkyl is methyl and ethyl. Preferred substituents for R 2"9 to R 31 as phenyl and benzyl are, within the framework of the definitions: methyl, ethyl, methoxy and ethoxy. In a preferred embodiment within the group of Formula VII, R 39 to R.l.l represent alkyl with C l a
C 4, phenyl or benzyl.
Some examples for the group of Formula VII are -CH 2 -Si (CHO J, -CH 2 -Si (C 2 H 5) 3, -CH 2 -Si (n-C 3 H 7) 3, -CH 2 -Si (n-C 4 H 9) 3,
-CH.-Si (CH3), (n-C4Hg), -CH "-Si (CH3) 2 (tC" 4Hg), -CH2-Si (CH) {EC), -CH9-Si (CH) , [C (CH) "CH (CH), -CH -Si (CH). (NC, H), -CH- Si (CH 3) - (n-C18H3 /), -CH-Si (CsHO) J ., -CH2, -Si (CH2-CbH5) 3. -CH1- Si (C6H5) (CH3) 2 and -CH2-Si (CH2, -Cb.H5 (CH3) 2.
The other valences of the atoms of Ti (IV), Nb (V) -,
Mo (VI) - and W (VI) - may be saturated with the same or different neutral bonds, for example from the group consisting of = 0, = NR 33, secondary amines with 2 to 18 carbon atoms, R 0-, R S-, halogen, optionally substituted cyclopentadienyl, bridged biscyclopentadienyl, tridentate monoanionic ligands and neutral bonds such as for example ethers, nitriles, CO, tertiary phosphines and amines, in which the R represent, independently of each other, the alkyl with C to C " _, straight or branched chain, unsubstituted or substituted by alkoxy with C 1 to C 6 or halogen, cycloalkyl with C 5 or
C 6, unsubstituted or substituted with C 1 to C alkyl, C 1 to C 6 alkoxy or phenyl halogen, unsubstituted or substituted with C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 alkoxymethyl, alkoxyethyl with C 1 to C 6 or halogen, or the benzyl or phenylethyl unsubstituted or substituted with C 1 to C 6 alkyl, C 1 to C 6 alkoxy, alkoxymethyl with
C to C_, alkoxyethyl with C to C or halogen; and R represents the straight or branched chain C 1 to C 18 alkyl substituted or substituted with C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C5 or C6 cycloalkyl unsubstituted or substituted with C 1 to C6, C 1 to C 6 alkoxy or halogen, unsubstituted aliphenyl or substituted with C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C alkoxymethyl
C 6, alkoxyethyl with C 1 to C 6, di (C 1 to C 6 alkyl) amino, di (C 1 to C alkyl) amino-alkyl with C 1 to C 3, or
substituted by halogen or also benzyl or phenylethyl unsubstituted or substituted by alkyl with C to C, alkoxy with C 1 to C 6, alkoxymethyl with C 1 to C 6, alkoxyethyl with C 1 to C 6 or halogen, with the indication that in the case of titanium compounds, the ligature is not = 0 or = NR.
The secondary amines are preferably those of the formula R 34R 35 N-, in which R 34 and R 35 independently represent C 1 to C 18 alkyl, straight or branched chain, C 5 or C 6 cycloalkyl, benzyl or phenylethyl unsubstituted or substituted with alkoxy with C 1 to C 6 or by halogen or (alkyl with CL to C 6) 3 Si; or jointly
they mean tetramethylene, pentamethylene or 3-oxapentan-l, 5-diyl. The alkyl preferably contains from 1 to 12 and particularly preferably from 1 to 6 carbon atoms. Some examples are dimethyl-, diethyl-, di-n-propyl-, di-i-propyl-, di-n-butyl-, methyl-ethyl-, dibenzyl-, benzyl-methyl-, diphenyl-, phenyl-methylamino and di (trimethylsilyl) amino. The halogen as another bond to the metal atoms or as a substituent is preferably fluorine or chlorine and particularly preferably chlorine. The cyclopentadienyl can be unsubstituted or can be substituted with 1 to 5 alkyl units with Cn 1 to C 4, especially methyl or -Si (alkyl with C 1 to C 4), especially -Si (CH). Bridged cyclopentadienyls are particularly those of Formula R 36-A-R36, in which
R 36 rep represents methyl unsubstituted or substituted with 1 to
copies of C 1 to C 4 alkyl, especially methyl or -Si (C to C alkyl), especially cyclopentadienyl substituted with Si (CH 3) 3 and A represents -CH 2, -CH 2 -CH 2, - S ((CH 3) 2 -, -S i (CH 3) 2 -S i (CH 3) 2 - or -Si (CH 3) 2 -OS i (CH 3) 2.
In the case of ethers as neutral bonds, it can be a dialkyl ether with 2 to 8 carbon atoms or a cyclic ether with 5 or 6 members in the ring. Some examples are diethyl ether, methylethyl ether, diethyl ether, di-n-propyl ether, di-i-propyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane. In the case of nitriles as neutral bonds it can be aliphatic or aromatic nitriles with 1 to 2 atoms and preferably 1 to 8 carbon atoms. Some examples are: acetonitrile, propionitrile, butylnitrile, benzonitrile and benzylnitrile. In the case of tertiary amines and phosphines as neutral bonds, these may be those with 3 to 24 and preferably 3 to 18 carbon atoms. Examples are trimethylamine and trimethylphosphine, triethylamine and triethylphosphine, tri-n-propylamine and tri-n-propylphosphine, tri-n-butylamine and tri-n-butylphosphine, triphenylamine and triphenylphosphine, tricyclohexylamine and tricyclohexylphosphine, phenyldimethylamine and phenyldimethylphosphine, benzyldimethylamine and benzyldimethylphosphine. , 3, 5-dimethyl-phenyl-dimethylamine and 3,5-dimethyl-phenyl-dimethyl-phosphine. The tridentate monoanionic ligands can be, for example, hydro (trispyrazol-1-yl) borates or alkyl (trispyrazol-1-yl) borates, which are either unsubstituted or substituted with one to three alkyl units with C a C [see Trofimenko, S., Chem. Rev., 93: 943-980 (1993)], or else of [C 5 (R '5) Co (R37R38P = 0) 3], where R' represents H or methyl and R 37 as well as R38 independently of each rep represent alkyl with C 1 to C, C 1 to C 4 alkoxy or phenyl (see Kláui, C, Angew, Chem. 102: 661-670 (1990)].
In the case of halogen as a substituent for the radicals R and R, it is preferably fluorine and very
particular chlorine. Alkyl, alkoxy or alkoxy substituents in alkoxymethyl or alkoxyethyl preferably contain from 1 to 4 and particularly 1 or 2 carbon atoms. Examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, methoxy, ethoxy, n- and i-propyloxy as well as n-, i- and t-butyloxy. R 32 and R33 contain as alkyl-yl p-referentially from 1 to
12 atoms, with particular preference of 1 to 8 atoms and very particularly of 1 to 4 carbon atoms. Preferably it is branched alkyl. Some examples of R are methoxy, ethoxy, n- and i-propyloxy, n- i- and t-butyloxy, hexafluoro-i-propyloxy and hexa- as well as perfluorobutyloxy. Some examples of substituted phenyl and benzyl for R and R are p-methylphenyl or benzyl, p-fluoro- or p-chlorophenyl or -benzyl, p-ethylphenyl or -benzyl, pn- or i-propylphenyl or -benzyl, pi-butylphenyl or -benzyl, 3-methylphenyl or -benzyl, 3-i-propylphenyl or -benzyl, 3,5-dimethylphenyl or -benzyl, 3-5-i-propylphenyl or -benzyl, 3,5-n- or -t- butylphenyl or -benzyl. R represents, with particular preference, phenyl unsubstituted or substituted p cor alkyloyl with Ci to C; or alkoxy with C1 to C.
In a preferred embodiment, the metal compounds correspond in particular to Formulas VIII, Villa or VlIIb,
which represents Me (IV) or W (VI); Me7 represents Nb (V) or Ta (V); the radicals R 39 to R44 represent a radical -CH 2 -SiR 29 R 30 R 31 of the Formula VII; at least one of the radicals R q to R represents F, Cl or Br;
R, R3Q and R independently of each other denote alkyl with C 1 to C 6, cycloalkyl with C 5 or C 6, or phenyl or benzyl unsubstituted or substituted by alkyl with C 1 to C 6 or alkoxy with C 1 to C 6;
in Formula VIII two or in each case two as well as in the Formula Villa two, of the other radicals of R 39 to R44 each as a whole represent = 0 or = NR 33, and J R33 represents alkyl with C 1 to C 18 of linear chain or
branched, unsubstituted or substituted by alkoxy with C 1 to C 6, or cycloalkyl with C 5 or C 6 unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to
C 6 or halogen, the phenyl unsubstituted or substituted by C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 alkoxymethyl, C 1 to C 6 alkoxyethyl, di (C 1 to C 6 alkyl) amino, di (alkoxy with C1 to C6) amino-alkyl with C1 to C3 or substituted by halogen, or also represents benzyl or phenylethyl unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to C, alkoxymethyl with C 1 to C 6 , alkoxyethyl with C to C6, di (C 1 to C 6 alkoxy) amino, di (C 1 to C -alkyl) -alkyl-1-alkyl with C 1 to C 3 or halogen, and the other radicals R to R represent secondary amino with 2 to 18 carbon atoms, R 32O- or
R S-, halogen, unsubstituted cyclopentadienyl or
substituted either the bridged biscyclopentadienyl or a neutral linkage in which the exemplars of R independently of each other represent alkyl with C to C 18 unsubstituted, straight or straight chain, or substituted with C 1 to C 6 alkoxy or halogen, cycloalkyl with C 5 or C 6 unsubstituted or substituted by alkyl with C to C, alkoxy with C to C or halogen,
phenyl unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to C 6, alkoxymethyl with C 1 to C 6, alkoxyethyl with C 1 to C 6, di (C 1 to C 6 alkyl) amino, di (alkyl with C to C) amino-alkyl with C to C or
halogen, or the benzyl or phenylethyl unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to
C 6, C 1 to C 6 alkoxymethyl, C 1 to C 6 alkoxyethyl, di (C 1 to C 6 alkyl) amino, di (C 1 to C alkyl)
C) amino-alkyl with C to C or halogen; or else Formulas VIII, Villa and VlIIb the other radicals of R 39 to R independently between them represent secondary amino with 2 to 18 carbon atoms, R 32O- or R32S-,
halogen, the unsubstituted or substituted cyclopentadienyl or the bridged biscyclopentadienyl or means a neutral bond, in which the R independently of each other denote alkyl with C to C 18, unsubstituted or substituted with C1 to C6 alkoxy or halogen, linear in character or branched, the cycloalkyl with C 5 or C 6 unsubstituted or substituted with C 1 to C 6 alkyl, C 1 to C 6 alkoxy or halogen, the
phenyl unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to C 6, alkoxymethyl with C 1 to C 6, alkoxyethyl with C 1 to C 6", di (C 1 to C 6 alkyl) amino, di (alkyl with C 1 to C6) amino-alkynyl with C1 to C3 or
halogen, or the benzyl or phenethyl unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to
C, C 1 to C 6 alkoxymethyl, C 1 to C alkoxyethyl, di (C 1 to C) alkyl, amino, di (C 1 to C) alkyl
C 6) amino-alkyl with C 1 to C 3 or substituted by halogen. For the radicals R 29 to R 33 the preferred forms indicated above serve. In a particularly preferred embodiment, the titanium, niobium, tantalum, molybdenum or tungsten compounds of Formulas VIII, Villa and VlIIb are used within the process according to the invention in which R 39 represents a radical of Formula VII -CH2-Si (R29R30R31),
R ^ represents F, Cl or Br; and (a) in Formula R1 and R42 as well as R43 and R44 in each case in combination represent the radical = NR 33 or R41 and J R42 conj together with the radical = N-R33 and R43 and R44 independently of each other represent unsubstituted cyclopentadienyl or substituted, R 32-0- or halogen, or (b) in the Formula Villa R and R, together they mean the radical = NR 33 R 43 represents unsubstituted or substituted cyclopentadienyl, R 32-0- or halogen, or the
The formula VI is R 41, R '42 and R "43, independently of them represent cyclopentadienyl unsubstituted or substituted R32-0- or halogen, or (c) Formula Vlllb R and R42 independently represent cyclopentadienyl insub = substituted or substituted, R 32-0- or halogen, in which R up to R 33 have the definitions presented above for R? g, R3Q, R3i, R_ _ and R33 the forms are applied
preferences indicated above. Very particularly preferred are in the process according to the invention the metal compounds of Formulas IX, Ixa, IXb, IXc, or IXd,
in which Me represents Mo (VI) or W (VI); It represents Nb (V) or Ta (V); R represents -Si (alkyl with C, a C); Z denotes Cl or Br; R means phenyl or phenyl substituted with 1 to 3 radicals alkynyl of C1 to C4, alkoxy C1 to C, (a) Rf, and R44 in Formula IX together represent the group = NR33 or individually and independently between them mean F , Cl, Br, C 1-4 alkoxy, unsubstituted or substituted by fluorine, straight-chain or in particular branched, phenyloxy unsubstituted or substituted by Cl to C4 or C1 to C4 alkoxy or denote the unsubstituted or substituted cyclopentadienyl (b) R 41., R42 and R43 and R44 in the Formula Ixa independently of each other mean F, Cl,. Br, alkoxy with C 1 to C 4 of
linear or particularly branched chain, unsubstituted or substituted with fluorine, phenyloxy unsubstituted or substituted by alkynyl with C1 to C4, or alkoxy with C1 to C4 or else the unsubstituted or substituted cyclopentadienyl (c) R 43 in Formula IXb, signi fica, F, Cl, Br, and denotes
• p "• articulate the alkoxy with unsubstituted C1 to C or
fluoro-substituted, straight-chain or in particular branched, phenyloxy unsubstituted or substituted by alkyloxy with C1 to C4 or alkoxy with C1 to C4 or rep- resentative
the cyclopentadienyl unsubstituted or substituted by (d) R 41, R 42 and R43 in Formula IXc, independently of each other, mean F, Cl, Br, alkoxy with C to C chain
straight or in particular branched, unsubstituted or substituted with fluorine, phenyloxy unsubstituted or substituted by C 1 to C 4 alkyl, or C 1 to C alkoxy, or represents cyclopentadienyl unsubstituted or substituted by C to C alkyl; and (e) R and R in Formula IXd, independently of each other means F, Cl, Br, straight chain or particularly branched C to C alkoxy, unsubstituted or substituted by fluorine, unsubstituted phenyloxy or substituted by alkyl with. to C, alkoxy with C to C or either the cyclopentadienyl unsubstituted or substituted with alkyl with C to C 4.
The alkoxy represents, in a particularly preferred manner, the branched alkoxy which is optionally substituted wholly or partially with F, for example, i-propyloxy, i- and t-butyloxy, hexafluoropropyloxy and ncnafluoropropyloxy. As for the phenyloxy radical, it is particularly phenyloxy which is substituted at the 2,6-positions with C 1 -C 4 alkyl by C 4 -C 4 alkyl, eg, 2,6-dimethylphenyloxy. Examples of substituted cyclopentadienyl radicals are mono- to pentamethylcyclopentadienyl and trimethylsilylcyclopentadienyl. R33 preferably represents phenyl or phenyl substituted by alkyl with C, to C., particularly phenyl, 3-dimethylphenyl, 2,6-dimethylphenyl, 3,5-diethylphenyl and 2,6-diethylphenyl. The compounds which are very particularly preferred in the process according to the invention are those of the formulas X, Xa, Xb, Xc and Xd
(R33-N =) 2Me? Xa [CH2Si (CH3) 3] (X),
(R33-N =) R41Me1Xa (OR32) CH2Si (CH3) 3 (Xa), R42R43Me2Xa (OR32) CH2Si (CH3 3 (Xc),
R41-TiXa (OR32) CH2Si (CH3) 3 (Xd),
where Mel represents Mo (VI) or W (VI); Me2 represents Nb (V) or Ta (V); X ^ represents F or Cl; R33 means phenyl or phenyl substituted with 1 or 2 C 1 to C 4 alkyl groups; R32 represents alkyl with C3 to C4, branched chain and
optionally substituted partially or completely with fluorine, or also phenyloxy or phenyloxy substituted with 1 to 3 methyl or ethyl groups; R42 and R43 independently represent cyclopentadienyl unsubstituted or substituted with 1 to 5 methyl groups, Xa or R32O-. R n represents cyclopentadienyl unsubstituted or substituted with 1 to 5 methyl groups, X or R_, 0-.
Some examples of the compounds of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) and tungsten (VI) are: [Cp means cyclopentadienyl and Me means Nb (V) or Ta (V)]: TifCH Si (CH;) 3] Cl3, Ti [CH Si (CH Br; / Cp "TÍ [CH, Si (CH) _] Cl, (CH3) 2TÍ [CH2SÍ (CH3) 3] Cl, Cp2TÍ [CH2SÍ ( CH3) 3] Br, Cp2TI [CH2Si (CH3) 3] I, CpTi [CH2Si (CH3) 3] [CH C1, CpTi [CH2Si (CH3) 3] Br2, [(CH3) 2CHO] 2Ti [CH2SÍ (CH3) 3J Cl, [(CF O) ¿CHO] t. [CH.] YES (CH) C1, [(CF oJ. CHO] CpTi [CH ¿. Si (CH 3) 3] C1,
[(CH o) CHO] CpTi [CH YES (CH 0) 1C1, (C bH O) CpTi [CH 2 Si (CH 3) 3] Cl, (2,6-dimethyl-C 6 H 50) CpTi [CH 2 Si (CH 3) 3] C1, (2,6-dimethyl-C 6 H 5cO) 2 Ti [CH 2 Si (CH 3 J 31 Cl, (2,6-dimethyl-C 6 H 5 O) Ti [CH 2 Si (CH 3 ) 3] 2Br,
[(CH 3) 3 CO] CpTi [CH 2 Si (CH 3) 3] Cl, [(CF), (CH) CO] CpTi [CH Si (CH 3) 3] "Cl, Me (= NC H) [OCH (CH)] [(CH Si (CH)] C1, Cp Me [(CH Si (CH)] Cl,
Me (= N-C3H5) [OCH (CF3) 2] [(CH2Si (CH3) 3] C1, Me (= N-2,6-diisopropylC 6 H 3) [(CH 2 Si (CH 3) 3] Cl 2, Me (= N-2, 6-diisopropylC 6 H 3) [(CH 3) 2 CHO] [(CH 2 Si (CH 3) 3] Cl, Me (= N-2,6-dimethylC 6H 3) (2, ß-dimethyl-C 6H 5o) [CH 2 Si (CH 3) 3] Cl, Me (= N-2,6-dimethylC 6 H 3) ((CF 3) 2 CHO) [(CH 2 Si ( CH 3) 3] Cl, (= N-2, 6-dimethylC 6 H 3) CpMe [(CH 2 Si (CH 3) 3] Cl, (C b H 5 O) CpMe [(CH 2 Si (CH 3 ) 3] C1, (= N-3,5-dimethylC6H3) Me [2,6-dimethylC6H30)] [(CH2Si (CH)] C1, CpMe [OCH (CH3) 2] 2 [(CH2Si (CH3) Br, CpMe [OCH (CH)] [(CH Si (CH)] C1, CpMe [OCH (CF o) J- [(CH) Si (CHJ 1C1, Cp 2Me (methyl) [(CH 2 Si (CH 3 ) 3] C1,
CpMe [OCH (CH)] [(CH Si (CH)] Cl, [OCH (CH) 1 Me [CH Si (CH)] Cl,
Me (2,6-dimethylphenyloxy) (CH30) 2 [(CH2Si (CH)] C1, Me [CH Si (CH 3) 3] [OCH (CH j)] (CF 3 O) 2, C1, W (= NC t- H 5) [(OC (CH 3) J] [CH _ '- Si (CH 3) 3] Cl 2, (2,6-diisopropylphenyloxy) Me [CH Si (CHJ 3] "C1, CpMe [ 0C (CH 3) 3] [(CH Si) (CHJ JCl, CpMe [OC (CH 3J (CF 3J J [(CH 2 Si (CH 3) 3] C1, Mo [[CH -, - Si (CH o)] 3 J (OCH? _ C (CH 3) 3 JCl] .._, Mo (= N-2, 6-diisopropylC 6 H 3) 2 [CH 2 -Si (CH 3) 3] C1, W (= NC hH5) [(OC (CH 3) 3] 2 [CH 2 -YES (CH 3) 3] C1, Mo (= NC.Hc) 2 [CH 2 -Si (CH)] Cl, Mo (= N-2 , 6-diisopropylC H) [OCH C (CH)] CH2-YES (CH)] Cl. 6 3 _. 3 3 2 3 3 The titanium, niobium, tantalum, molybdenum and tungsten compounds to be used in accordance with present invention are known or can be obtained according to known and analogous processes starting from the metal halides optionally substituted in a corresponding manner by Grignar reactions [Schroc, RR, Murdzeck, JS, Bazan, GC, Robbins, J., DiMar e, M., O'Regan, M., J. Am. Chem. Soc., 112: 3875-3886 (1990)]. The process according to the invention can be carried out in the presence of an inert solvent. A particular advantage of the process according to the invention is that with liquid monomers the process can be carried out without the use of a solvent. Inert means that the choice of solvents depends on the reactivity of the metal catalysts, for example that polar solvents are not used protically when certain substitution reactions can be expected such as the exchange of halogen by alkoxy. In addition, it must be taken into account that solvents containing C = 0 groups can react with metal catalysts. Suitable inert solvents are, for example, the polar and aprotic solvents which can be used alone or in mixtures consisting of at least two solvents. Examples are: ether (dibutyl ether), tetrahydrofuran, dioxane, ethylene glycol monomethyl- or -dimethyl ether, ethylene glycol monomethyl- or -diethylether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether), the halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, 1,1-trichloroethane, 1, 1, 2, 2-tetrachloroethane), carboxylic acid esters and lactones (acetic acid ethyl ester, propionic acid methyl ester, benzoic acid ethyl ester, 2-methoxyethyl acetate, -butyrolactone, valerolactone, pivalolactone), carboxylic acid amides and lactams (N, N-dimethylformamide, N, N-diethylformamide, N, N, dimethylacetamide, tetramethylurea, hexamethylphosphoric triamide, -butyrolactam, caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam), sulfoxides (dimethylsulfoxide), sulfones
(dimethylsulphone, diethylsulphone, trimethylene sulfone, tetramethylene sulfone), tertiary amines (N-methylpiperadine,
N-methylpiperadine, N-methylmorpholine) aliphatic and aromatic hydrocarbons such as petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene or substituted benzenes (chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene) , xylene) and nitriles (acetonitrile, propionitrile, benzonitrile and phenylacetonitrile). The preferred solvents are polar and non-polar, aprotic solvents. The preferred solvents are aliphatic and aromatic hydrocarbons as well as mixtures of such solvents. It is particularly noteworthy that the compositions which are used in the process according to the invention of a cycloolefin optionally substituted with a catalyst are often insensitive to oxygen, which makes it possible to store and carry out the reaction without protective gas. However, it is recommended to exclude moisture, ie the use of dry reaction and storage conditions. The monomers of Formula I and the catalysts used for the process according to the present invention can be stored separately as well as together as a mixture since the catalyst employed possesses a particularly high stability. The mixture can be stored before the photochemical polymerization with a ready-to-use formulation, which is advantageous for the large-scale application of the process according to the invention. The storage is carried out due to the high photosensitivity, in particular under ultraviolet light, effectively under the exclusion of light.
Another object of the invention is a photopolymerizable composition containing (a) a cyclic olefin or at least two different cyclic olefins and (b) a catalytically effective amount of at least one thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen are bonded to the metal. The composition according to the invention can additionally contain other non-volatile open-chain comonomers which form copolymers with the cycloolefins which are tightened. With the concomitant use of for example dienes, cross-linked polymers can be formed. Examples of such comonomers are olefinically monounsaturated or di-unsaturated compounds such as olefins and dienes from the group of pentene, hexene, heptene, octene, decene, dodecylene, acrylic and methacrylic acids, their esters and amides, vinyl ether, styrene, butadiene , isoprene and chlorobutadiene. The other olefins capable of entering into metathesis polymerization are contained in the composition according to the invention, for example, in an amount of up to 80% by weight, preferably 0.1 to 80% by weight, preferably between 0.5 and 60% by weight, and with particular preference between 5% and 40% by weight, with respect to the total amount of the compounds of Formula I and with other olefins capable of entering the polymerization by metathesis. The composition according to the invention may contain auxiliaries for the formulation. Known auxiliaries are antistatic, antioxidants, light-protecting agents, softeners, dyes, pigments, fillers, fillers, slip promoters, adhesion promoters, viscosity-increasing agents and mold release aids. The fillers can be present in surprisingly high portions, without unfavorably influencing the polymerization, for example in amounts up to 70%, preferably between 1% and 70% by weight, preferably between 5 and 60% by weight, very particularly between 10 and 50% by weight and with special preference between 10 and 40% by weight, with respect to the composition. The fillers and intensifier fillers that serve to improve the optical, physical, mechanical and electrical properties have become popular in large quantities.
Some examples are glass and quartz in the form of powders, spheres and fibers, oxides of metals and semi-metals, carbonates such as MgCO 3, CaCO 3, dolomite, metal sulphates, such as gypsum and heavy spar, natural and synthetic silicates, such as talc, zeolite, wollastonite, feldspar, aluminum clays as well as China clay, stone flour, "Whisker", carboxylic fibers, synthetic fibers or their powders as well as soot. The agents that increase the viscosity are particularly the metathesis polymers, which contain olefinically unsaturated groups and which can be incorporated into the polymer during the polymerization. Such metathesis polymers are known and sold, for example, under the trade name Vertenamere. Other agents that increase the viscosity are polybutadiene, polyisoprene or polychlorobutadiene, as well as the copolymers of butadiene, isoprene and chloroprene with olefins. Agents that increase the viscosity may be contained in the material in an amount of 0.1% to 50%, preferably 1% to 30% and particularly preferably between 1% and 20% by weight, based on the composition. As regards the use of the fillers, it is effective to obtain an optical transparency for the polymerization or to carry out the polymerization in thin layers. In the process according to the invention, it is not necessary to maintain the irradiation of the reaction mixture throughout the reaction time. Once the polymerization is initiated photochemically, the rest of the reaction is carried out independently even in the dark. Advantageously, irradiation is carried out with light having a wavelength in the range of 50 nm to 1,000 nm, preferably in the range of 200 nm to 500 nm and very particularly preferably in the ultraviolet field. The irradiation time depends on the class of the light source. Preferably, laser and ultraviolet-type lamps or ultraviolet light lamps are used according to the invention. The irradiation of the catalyst can be carried out both before, during or also after the addition of the monomer. Appropriate irradiation times are from a few minutes to 8 hours, especially from 5 minutes to 4 hours. The sequence of the addition of the monomers and the catalyst is not a critical factor. The monomer can be charged instantly or also introduced after applying the catalyst. It is also possible to previously irradiate the catalyst and then add the monomer. It is also possible to irradiate the solution containing the catalyst and the monomer. The process according to the invention is preferably carried out at room temperature up to slightly increased temperature. An increase in temperature serves to increase the reaction rate. The catalysts used only start in exceptional cases, already a thermal polymerization. As regards the temperatures chosen to accelerate the reaction, a photopolymerization is predominantly present in such a case. However, it should be noted that the catalysts by sufficient irradiation can be converted into thermoactive catalysts. In particular, the process according to the invention is carried out at temperatures between -20 ° C and + 110 ° C. A very particular and surprising advantage of the process according to the invention is that the used compounds of titanium (IV), niobium (V), tantalum (V), molybdenum and tungsten after irradiation work as thermal catalysts. This results in the possibility of continuing and finishing the polymerization after a short time of irradiation by means of the heat supply, which offers certain economic and technical advantages in different fields or sectors of the system for manufacturing molded articles or coatings. In particular, the combined process for obtaining thermoplastics is favorable. Another object of the invention is a process for the photocatalytically induced and then thermal polymerization of a cyclic olefin or at least two different cyclic olefins in the presence of a metal compound as a catalyst, which is characterized in that a) the cycloolefins in the presence of a catalytic amount of at least one thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen is they are linked to the metal; or a catalytic amount of a thermosetting compound of titanium (IV), niobium (V), or tantalum (V), in which a silylmethyl group and at least one halogen is attached to the metal, is optionally irradiated in an inert solvent and then it is mixed with at least one cycloolefin; and b) then the polymerization is terminated by heating and without irradiation. For the procedure step a) the preferred forms indicated above apply. The irradiation time depends fundamentally on the system of the selected reaction. Irradiation for a short time is chosen, for example, when the polymerization is to be initiated only by irradiation and when it is desired to end up heating. The expression "for a short time" can mean a period of irradiation up to 60 seconds, preferably between 5 and 60 seconds and with particular preference between 10 and 40 seconds. A longer irradiation time is chosen, for example, when the polymerization is to be carried out mainly under irradiation and to finish it definitively only by subsequent quenching. The heating in process step b) may correspond to an application of reaction temperature of 50 to 200 ° C, preferably between 50 and 150 ° C and especially preferably between 70 and 120 ° C. The term "catalytic quantities" in the context of the present invention preferably means an amount of 0.001% up to 20% Molar, with particular preference between 0.01% and 15% Molar and with special preference between 0.01% and 10% Molar respect to the amount of the monomer. Another object of the invention is a process for the preparation of thermal catalysts for the polymerization of metathesis that opens rings of cyclic olefins, which is characterized in that a thermostable compound of titanium (IV), niobium (V), tantalum is irradiated (V), molybdenum (VI) or tungsten, in substance or in a solvent, in which compound a silylmethyl group and at least one halogen is attached to the metal. As regards the olefins which must be used according to the invention, they are tensioned rings. Cyclohexene as an exceptional case, in general terms, can not be homopolymerized with olefin metathesis. This exception is known to the person skilled in the art and has been described, for example, in Ivin [Ivin, K.J. in: Ivin, K.J., Saegusa, T. (Hrsg.), Ring-Opening Polymerization 1: 139-144 Elsevier Applied Science Publishers, London and New York (1984)]. With the process according to the invention, the hardened oligomers can be prepared by irradiation as well as the polymers with the same or different structural units of Formula XI,
, CQ (XI), in which Q_ and Q, have the definitions indicated under the
Formula I. For these polymers the preferential forms indicated above are applicable. They may be homopolymers or copolymers with distribution or statistics of the structural units, of graft polymers or also block polymers. They can have an average molecular weight (M) of for example 500 to 2 million Daltons, preferably between 1,000 and 1 million Daltons (determined with GPC-type chromatography by comparison with a closely distributed standard of polystyrene). With the method according to the invention, thermoplastically deformable materials can be produced for the creation of all types of shaped bodies, coatings and enhancement configurations. Depending on the monomer used in each case, the polymers prepared according to the invention may have very different properties. Some stand out for a very high oxygen permeability, low dielectric constants, good thermal stability and a low degree of water absorption. Others have outstanding optical properties such as a high degree of transparency and low refractive indexes. In addition, the low degree of shrinkage must be emphasized here. Therefore they can be used in very different technical sectors. The compositions according to the invention stand out as layers on surfaces of carrier materials thanks to a high degree of adhesion. Also highlight the materials coated by a smoothness and brightness of very high surface. Among the good mechanical properties, the low degree of shrinkage and the high tenacity under impact and also the thermal resistance must be highlighted. Likewise, the easy demolding capacity and the high resistance to solvents can be mentioned. These polymers stand out for the manufacture of medical devices, implants or contact lenses; for the production of electronic construction parts; as binders for paints; as photocurable compositions for the construction of models or as adhesives for adhering substrates with low surface energies (for example Teflon, polyethylene and polypropylene) as well as a photopolymerizable composition in stereolithography. The compositions according to the invention can also be used for the production of paints by photopolymerization, in which case on the one hand clear compositions (transparent) and at the same time even pigmented can be applied. Both blank and variegated pigments can be used. It is also worth mentioning the preparation of molded bodies according to thermoplastic forming procedures for objects of all kinds. The compositions of the photo-hardenable or photo-thermosetting type according to the invention are particularly suitable for the production of protective layers and embossed configurations. Another object of the invention is a variant of the process according to the invention for the preparation of coated materials or embossed configurations, in which a cyclic olefin composition is applied as catalyst and optionally solvent as a layer on a support, for example by a process immersion, smearing, pouring, rolling, squeegee application or centrifugal emptying, the solvent is eventually removed and the polymerisation layer is irradiated, or the layer is irradiated through a photographic mask and then removed the portions not irradiated with a solvent. With this method substrates surfaces can be modified or protected or printed circuits or printing plates or printing cylinders can also be produced. In the production of the printed circuits, the compositions according to the invention can also be used as stop plates for welding. Other application possibilities are the manufacture of screen printing masks, the use as radiation curable printing inks for offset printing, screen printing and flexo printing. Another object of the present invention is a carrier material which is coated with an oligomer or polymer according to the invention and which contains a crosslinking agent. Another object of the present invention is a carrier material that is coated with an oligomer or polymer according to the invention. These materials are suitable for obtaining protective layers or enhancement configurations by irradiation (possibly under a photographic mask) and subsequent development with a solvent. Suitable crosslinking agents which may be present in the material, for example in an amount of 0.01% to 20% by weight, are all organic bisacids, especially 2,6-bis (4-azidobenzilidene) -4-methyl-cyclohexanone which You can get it in the market. The object of the present invention is furthermore a coated carrier material characterized in that a layer consisting of (a) a cyclic olefin or at least two different cyclic olefins and (b) a catalytically effective amount of at least one of which is applied over a carrier is applied. a thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen is attached to the metal. Suitable carrier materials are, for example, those of glass, minerals, ceramics, plastics, wood, semimetals, metals, metal oxides and metal nitrides. The thicknesses of the layers depend fundamentally on the desired use and can be, for example, 0.1 m to 1,000 m, preferably up to 0.5 to 500 m, and with particular preference these thicknesses will be between 1 m and 100 m. The coated materials stand out for a high degree of adhesion and good thermal and mechanical properties. The production of the coated materials according to the invention can be carried out according to known methods such as coating, squeegee application, casting processes as well as draining or draining systems with a centrifugal system. As far as coatings are concerned, particularly good results are obtained when cycloolefins are used for the polymerization by photometathsis, which also contain 1 to 3 and preferably another double bond and which within the framework of the present invention constitute condensed cyclic systems, ie of polycyclic type. The following examples illustrate the invention in greater detail. A) Preparation of catalysts Example - Al: Preparation of [(H3, C). CHO] 2.TiCl [CH <; ._- Yes (CH5) ^]. The
Processing is carried out in situ by reaction of equimolar amounts of Cl.Ti [OCO (CH) J. and LiCH "Si (CHJ, in diethyl ether Example A2: Preparation of Ta [CH Si (CHJ Cl ^. The title compound is made according to the prescriptions of Moorehouse and ilkinson [Moorehouse, S., ilkinson, G., J. Chem. Soc., Dalton Trans., 2187-2190 (1974)] Example A3: Elaboration of W (= N-C6H5) [OC (CH3) 3] 2 [CH2Si (CH3) 31C1 .A quantity of 2.0 g (3.0 millimoles) of [(CH)] N [W (= NC 6H5) (OC (CH3) 3J CL3J in 50 ml of methylene chloride are cooled to a temperature of 78 ° C and then a solution of 0.36 g is added dropwise. (1.5 mmol) of Zn [CH "Si (CH) and 0.21 g
(1.5 mmol) of ZnCl, for a period of 2 hours. It is left
warm to room temperature and continue stirring for another 2 hours. The solvent is removed in vacuo and the residue is extracted with hexane (2 times 50 ml) and the product is crystallized by cooling the concentrated hexane solution at -30 ° C. 1.01 g (62% of the title compound) B) Preparation of polymers Example 1 to 3: Polymerization of norbornene. The catalyst is charged into 5 ml of toluene in a vessel with a hole. Next, norbornene in toluene is added and the container is closed. The mixture is irradiated with stirring. After about 15 seconds an increase in viscosity is observed. After 5 minutes, the reaction is stopped by adding a drop of benzaldehyde and the reaction mixture is poured into 100 ml of ethanol. The precipitated polymer is removed by filtration, washed with ethanol and then dried under vacuum. The polymer can be characterized by chromatography with gel pemeation
[GPC international abbreviation; solvent: tetrahydrofuran; the numerical values of (M) and the averages er. weight (M) of
Molecular weight is determined in relation to the calibrated norm 1 of polystyrene] and RMN-H (Bruker 300 MHz, solvent CDC1). An identical experiment without illumination at 5 ° C does not generate any increase in viscosity and after adding ethanol no amount of polymer precipitates. The following catalysts are used: A = [(H3C) 2CHO] 2TiCl [CH2-Si (CH3) 3] B = Ta [CH2Si (CH3) 3] Cl4 C = W (= N-C6H5) [OC (CH3) 3] 2 [CH2Si (CH3) 3] Cl
The compound (1) is used as the monomer. The following light source is used: An ultraviolet lamp with medium pressure, with mercury vapor of 200 W (Osram HBO 20C W / 2, manufacturer Spindler and Hoyer, Göttingen). The results are reported in Table 1: Example Norbornene Catalyst Performance MMM 1 500 mg 10 mg A 28% 15 k 1.5 '2 500 mg 10 mg B 78% 32 k 1.6 3 500 mg 10 mg C 90% 60 k 2
Claims (30)
- Claims 1. A process for the photocatalytic polymerization of a cyclic olefin or of at least two different cyclic olefins in the presence of a metal compound as a catalyst, characterized in that a ring-opening metathesis polymerization is carried out by the photochemical route in the presence of a catalytic amount of at least one thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen to metal.
- 2. The process according to claim 1, characterized in that the cyclic olefins are monocyclic rings or polycyclic ring systems, bridged or condensed with 2 to 4 rings, which are unsubstituted or substituted and possibly contain one or more heteroatoms of the group of O, S, N and Si in one or several rings and possibly also condensed rings of aromatic or heteroaromatic type.
- 3. The method according to claim 2, characterized in that the cyclic rings contain from 3 to 16 members in the ring.
- 4. The method according to claim 3, characterized in that the cyclic rings contain from 3 to 12 members in the ring.
- 5. The process according to claim 2, characterized in that the cyclic olefins contain other non-aromatic double bonds.
- 6. The process according to claim 1, characterized in that the cycloolefins correspond to Formula I C wherein Q represents a radical with at least one carbon atom which together with the group -CH = CQ forms an alicyclic ring containing at least three members, optionally containing one or more heteroatoms selected from the group consisting of silicon, phosphorus, oxygen , nitrogen and sulfur; and which is unsubstituted or substituted by halogen, = 0, - CN, -NO, R1R-R3SÍ- (O) u-, -COOM, -SO3M, -PO3M, -COO (M) 1 2, - PO .tM ^^, alkyl with C to C .., hydroxyalkyl with C, a C,?, halogenalkyl with C, aC_, cyanoalkyl with C. a C, cycloalkyl with C to C, aryl with C. a C_ , aralkyl with C_ a C I, heterocycloalkyl with C3 to C6_, heteroaryl with C _. a C1, heteroaralkyl with C4 to C16 or R * 4-X-; or in which two adjacent atoms of carbon are substituted with -CO-O-CO- or with -CO-NR; -CO-; or in which an alicyclic, aromatic or heteroaromatic ring, which is either unsubstituted or is substituted with halogen, -CN, -NO 2, R6R7R8si- (0) or is present in adjacent carbon atoms of the alicyclic ring is attached by condensation. -, COOM, -S03M, P03M, -COOÍM ^^, -SO (M)., PO 3 (M1) 1/2, alkyl with C1 to C20, halogenoalkyl with C1 to C-0, hydroxyalkyl with C1 to C20, cyanoalkyl with C1 to C6, cycloalkyl with C3 to C8, aryl with C6 to C16, aralkyl with C 7 to C16, heterocycloalkyl with C3 to C6, heteroalkyl with C 3 to C 16, heteroaralkyl with C 4 to C 16, or R 13 -X 1 -; X and XI, independently of each other represent -0-, -S-, -CO-, -SO-, -SO 2-, -0-C (0) -, -C (0) -0-, -C ( 0) -NR5-, - NR 10-C (0) -, -SO2-0- or -O-SO2; R, R ^ and R independently of each other represent alkyl with C 1 to C 12, p-fluoroalkyl with C 1 to C 12, phenyl or benzyl; R and R independently mean alkyl with C to C, cycloalkyl with C 3 to C8, aryl with C6 to C16 or aralq ^ uyl R and R independently of each other represent hydrogen, alkyl with C to C, phenyl or benzyl in which the groups alkyl, on the other hand, are unsubstituted or are substituted by alkoxy with C 1 to C 12 or cycloalkyl with C 3 to C 8; G3 R_, R and R. independently of each other represent alkyl with C 1 to C 12, p-fluoroalkyl with C 1 to C 12, phenyl or benzyl; M represents an alkali metal and M denotes an alkaline earth metal; and u means 0 or 1; wherein the alicyclic ring formed with Q contains eventually non-aromatic double bonds; Q2 represents hydrogen, alkyl with C to C, halogenoalkyl with C1 to C20, alkoxy with C1 to C1, halogen, -CN, or R -X "-; R represents alkyl with C to C, haloalkyl with C to C 20, hydroxyalkyl with C 1 to C 20, cycloalkyl with C 3 to C 8, aryl with C 6 to C 1, or aralkyl with C 7 to C 6; X represents -C (0) -0- or -C (0) -NR? 2; R_ means hydrogen, alkyl with C to C, phenyl and benzyl; wherein the aforementioned groups of cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or are substituted with alkyl with C. to C, alkoxy with C to C, - NO, -CN or halogen, and that the heteroatoms of the Previous groups of heterocycloalkyl, heteroaryl and heteroalkyl are selected from the group of -0-, -S-, -NR- and -N =; and R. represents hydrogen, alkyl with C to C, phenyl or benzyl. The method according to claim 6, characterized in that the anicyclic ring formed by Q, together with the group -CH = CQ, contains from 3 to 16 atoms in the ring and in which it is a monocyclic, bicyclic, tricyclic or tetracyclic ring system. 8. The process according to claim 6, characterized in that Q "in Formula I, represents hydrogen. 9. The process according to claim 6, characterized in that in the compounds of the formula IQ represents a radical with at least one carbon atom, which together with the group -CH = CQ forms an alicyclic ring with 3 to 10 members, which optionally contains one heteroatom selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, = 0, -CN, -NO, RRR Si- (0) -, -COOM, -SO M, - PO 3M, -COO (M1) 1/2, - PO3 (M1) 1/2, C1 to C6 alkyl, C1 to C6 hydroxyalkyl, C1 to C6 haloalkyl, cyanoalkyl to C1 to C4, cycloalkyl to C3 to C6, aryl with C 3 to C6, heteroaryl with C3 to C12, heteroaralk ^ uyl with C 4 to C12 or R4-X-; or in which two adjacent atoms of carbon are substituted with -CO-O-CO- or with -CO-NR 5 -CO-; or in which an alicyclic, aromatic or heteroaromatic ring, which is either unsubstituted or substituted by halogen, -CN, -NO 2, R6R7R8Si- (O) or is optionally bonded to the adjacent carbon atoms of the alicyclic ring. -, COOM, -SOM, P03M, -COO (M?)? / 2, -S03 (MJ? / 2, -PO ^) ^, alkyl with C to C, halogenoalkyl with C to C, hydroxyalkyl with C 1 to C12, cyanoalk ? uilo with C1 to C4, cycloalkyl with C3 to C ^, aryl with C6 to C12, aralkyl with C7 to C12, heterocycloalkyl with C3 to C6, heteroalkyl with C3 to C2, heteroaralk ^ uyl with C4 to C12, or R13-X1-; X and XI, independently of each other represent -O-, -S-, -CO-, -SO-, -SO "-, -OC (O) -, -C (0) -0-, -C (0) -NR-, - NR 10-C (O) -, -SO 2 -O- or -O-SO 2; R, R, and R independently of each other represent alkyl with C 1 to C 6, perfluoroalkyl with C 1 to C 6, phenyl or benzyl; R and R. independently mean alkyl with C? to C_, cycloalkyl with C 3 to C8, aryl with C6 to C12 or aralk ^ uyl R and Rn independently between them represent hydrogen, alkyl with C, a C., phenyl or benzyl in which the groups alkyl on the other hand are unsubstituted or are substituted with C 1 to C 6 alkoxy or cycloalkyl 1 to C 2 to C; R6, R 'and R8. independently among them represent alkoxy with C 1 to C 6, perfluoroalkyl with C 1 to C 6, phenyl or benzyl; M represents an alkali metal and M denotes an alkaline earth metal; and u means 0 or 1; wherein the alicyclic ring formed with Q contains eventually non-aromatic double bonds; Q2 represents hydrogen, alkyl with C to C, haloalkyl with C 1 to C12, alkoxy with C 1 to C6, halogen, -CN, or R 1 1 -X ¿".-; R 11 represents alkyl with C1 to C12, haloalkyl with C1 to C ^, hydroxyalkyl with C to C, cycloalkyl with C to C, aryl with C6 to C12, or aralk butyl with C7 to C12; X 2 represents -C (0) -0- or -C (O) -NR 12; R means hydrogen, alkyl with C to C, phenyl or benzyl; wherein the above-mentioned groups of cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or are substituted with alkyl with C 1 to C 6, alkoxy with C 1 to C 6, -NO 2, -CN or halogen, and in which the heteroatoms of the above groups of heterocycloalkyl, heteroaryl and heteroalkyl are selected from the group of -0-, -S-, -NR- and -N =; and R 9 represents hydrogen, alkyl with C 1 to C 6, phenyl or benzyl. The process according to claim 6, characterized in that in the compounds of the formula IQ represents a radical with at least one carbon atom, which together with the group -CH = CQ - forms an alicyclic ring with 3 to 10 members, which contains optionally a heteroatom selected from the group of silicon, oxygen, nitrogen and sulfur, and which is unsubstituted or is substituted with halogen, -CN, -NO ", RR Si-, -COOM-, -SO M, PO M, COO (M),, -PO. MJ ,,, alkyl with C to C, halogenalkyl with C 1 to C ^., Hydroxyalkyl with C1 to C6, cyanoalkyl with C 1 to C 4, cycloalkyl with C 3 to C 6, phenyl, benzyl or R 4 -X-; or in that an alicyclic, aromatic or heteroaromatic ring, which is of the unsubstituted type or is substituted by halogen, -CN, -NO-, R6R / R8Si-, COOM, is optionally bonded by condensation to the adjacent carbon atoms. SO3M, -PO3M, -COO (Ml) i / 2, -SO3 (M1) 1/2 -PO 3 (M 1) 1/2, alkyl with C 1 to C 6, haloalkyl with C: a C 6, hydroxyalk-1-one with C 1 to C 6, cyanoalkyl with C 1 to C 4, cycloalkyl with C 3 to C 6, phenyl, benzyl or R 13 -X 1 -; R? , R_, and R independently of each other means alkyl having 1 to 4 carbon atoms perfluoroalkyl with C to C4, phenyl or benzyl; M represents an alkali metal and M. denotes an alkaline earth metal; R, and R13 independently from each other mean alkyl with C? to Cg, haloalkyl with C. to C, hydroxyalkyl with C to Cg or cycloalkyl with C to C_; X and X? independently they represent -O-, -S-, - CO-, -SO- or -SO 2-; R- / R7 and R8 independently between them, mean alkyl with C 1 to C, perfluoroalkyl with C 1 to C 4, phenyl or benzyl; and Q represents hydrogen. 11. The process according to claim 1, characterized in that the cyclic olefins are norbornene or norbornene derivatives. 12. The process according to claim 11, characterized in that the norbornene derivatives are those of Formula II in which Xo. represents -CHR16.-, oxygen or sulfur; R and R15 independently represent hydrogen, -CN, tri fluoromethyl, (CH3 3 Si-O-, (CH 3) 3 Si- or -COOR-, and R 16 and R 1 'independently represent hydrogen, alkyl with C to C, phenyl or benzyl; or to Formula III in which X represents -CHR. "-, oxygen or sulfur; R 19 is hydrogen, alkyl with C to C., phenyl or benzyl; Y R 18 represents hydrogen, alkyl with C1 to Ct3. or halogen; or to Formula IV wherein X represents -CHR-, oxygen or sulfur; R ^ is hydrogen, alkyl with C to C, phenyl or benzyl; R and R21 / independently of each other represent hydrogen, CN, trifluoromethyl, (CH) Si-O-, (CH) Si- or J • 3 3 R23 signifies hydrogen, alkyl with C? to C ", phenyl or benzyl; or that correspond to Formula V wherein X 6 represents -CHR24-, oxygen or sulfur; R 24 represents hydrogen, alkyl with C to C ", phenyl or benzyl; represents oxygen or N-R ^; R c represents hydrogen, methyl, ethyl or phenyl. 13. The process according to claim 1, characterized in that the halogen bound to the metal atoms is F, Cl, Br or I. The process according to claim 1, characterized in that the silylmethyl group corresponds to Formula VII "CH2" SÍR29R30R31 (Vü), in which R29 'R3o and R3i' independently of each other, represent alkyl with C 1 to C 18, cycloalkyl with C 5 or C 6 or is phenyl unsubstituted or substituted with alkyl with C to C or alkoxy with C 1 to C 6 or benzyl case. 15. The process according to claim 14, characterized in that in the group of Formula VII R a R 29 * 1 means C 1 to C 4 alkyl, phenyl or benzyl. 16. The method according to claim 14, characterized in that the group of Formula VII consists of -CH? -Si (CH o) o, -CH? -Si (CH), -CH ¿".-Si (n-C j H /) 3, -CH 2 -Si (n-C H) *, -CHr-Si (CH3) 2 (n-C Hg), -CH2-Si (CH3). (t-C4H?), -CH, -Si (CH3). (C HJ, -CH -Si (CH -> 2 C (CH JJ CH (CH 3) 2], -CH 2 -Si (CH 3) 2 (nC 12 H ^ 5), -CH _ - YES ( CH -) - nC lo Ho /), -CH _-Si (C HJ ~? O_, -CH _, - Si (CH -C 6 H t) ^, -CH -Si (C HJ (CH 3) and -CH, -Si (CH.-C, HJ (CHJ ,. 17. The process according to claim 14, characterized in that the group of Formula VII represents - 18. The process according to claim 1, characterized in that the other valences of the Ti (IV), Nb (V), Ta (V) atoms, Mo (VI) and (VI) with equal or different neutral bonds are saturated from the group consisting of = 0, = NR 33, secondary amines with 2 to 18 carbon atoms,R, 0-, R, -S-, halogen, optionally substituted cyclopentadienyl, bridged biscyclopentadienyl, tridentate monoanionic ligands and neutral bonds such as for example ethers, nitriles, CO, tertiary phosphines and amines, in which the R represent, independently of each other, the alkyl with C 1 to C 18, straight or branched chain, unsubstituted or substituted with C 1 to C 6 alkoxy or halogen, cycloalkyl with C 5 or C 6, unsubstituted or substituted with C to C alkyl, C to C alkoxy or halogen is phenyl, unsubstituted or substituted by C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 alkoxymethyl, C 1 to C 6 alkoxyethyl or halogen, or benzyl or phenylethyl unsubstituted or substituted by alkyl with C to C 6, alkoxy with C 1 to C 6, alkoxymethyl with C 1 to C 6, alkoxyethyl with C to C or halogen; and R represents straight or branched chain C to C18 alkyl unsubstituted or substituted with C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 5 or C 6 cycloalkyl unsubstituted or substituted with C 1 to C alkyl C., C 1 to C 6 alkoxy or halogen, unsubstituted aliphenyl or substituted with C 1 to C 6 alkyl, C 1 to C alkoxy, C 1 to C 6 alkoxymethyl, C 1 to C alkoxyethyl, di (CI to C alkyl) ) amino, di (C1 to C6 alkyl) amino-alkyl with C to C, or substituted by halogen or also benzyl or phenylethyl unsubstituted or substituted by alkyl with C 1 to C, alkoxy with C ... to C6, alkoxymethyl with C a C 6_, alkoxyethyl with C1 to C6. or halogen, with the indication of that in the case of the titanium compounds, the ligation is not 19. The process according to claim 1, characterized in that the metal compounds correspond to the Formulas VII, VIII, Villa and Vlllb in which in which Me represents Mo (IV) or W (VI); Me7 represents Nb (V) or Ta (V); the radicals R 39 to R44 represent a radical of Formula VII; at least one of the radicals R 3 n 9 to R 44 represents F, Cl or Br; R 29, R 30 and R 31 independently denote alkenyl with C 1 to C 6, cycloalkyl with C 5 or C 6, or phenyl or benzyl unsubstituted or substituted by alkyl with C 1 to CG or alkoxy with C 1 to C 6; in Formula VIII two or in each case two as well as in the Formula Villa two, of the other radicals of R 39 to R44 each as a whole represent = 0 or = NR, and R represents alkyl with C 1 to C 18 straight chain or branched, unsubstituted or substituted by alkoxy with C 1 to C 6, or cycloalkyl with C 5 or C 6 unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to C or halogen, the phenyl unsubstituted or substituted by C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 alkoxymethyl, C 1 to C 6 alkoxyethyl, di (C 1 to C) alkyl C •) amino, di (C1 to C6 alkyl) amino-alkyl with C1 to C " or substituted by halogen, or also represents benzyl or phenylethyl unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to C 6, alkoxymethyl with C 1 to C 6 /, in which Me represents Mo (IV) or W (VI); Meo represents N (V) or Ta (V); the radicals R 39 to R 44 represent a radical -CH 2-SiR 29R 30R 31 of Formula VI I; at least one of the radicals R q to R represents F, Cl or Br; R, R, and R independently thereof denote alkyl with C 1 to C 6, cycloalkyl with C 5 or C 6, or phenyl or benzyl unsubstituted or substituted by alkyl with C 1 to C 6 or alkoxy with C 1 to C 6; in Formula VIII two or in each case two as well as in the Formula Villa two, of the other radicals of R 39 to R44 each as a whole represent = 0 or = N-R, and R, represents alkyl with C 1 to Clß. linear chain or branched, unsubstituted or substituted by alkoxy with C 1 to C 6, or cycloalkyl with C 5 or C 6 unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with C 1 to C or halogen, the phenyl unsubstituted or substituted by alkyl with C 1 to C, alkoxy with C 1 to C 6, alkoxymethyl with C 1 to C 6, alkoxyethyl with C 1 to C 6, di (alkyl with C 1 to C Cf) amino, di (C1 to C6 alkyl) amino-alkoxy with C1 to C3 or substituted by halogen, or also represents benzyl or phenylethyl unsubstituted or substituted by alkyl with C 1 to C 6, alkoxy with CI to C, alkoxymethyl with C1 to C, alkoxyethyl with C 1 to C6_, di (alkyl with C1 to C f) amino, di (alkyl with C to C -alkyl) -alkyl with C to C or halogen, and the other radicals R to R represent secondary amino with 2 to 18 carbon atoms, R 32O- or R? S-, halogen, unsubstituted or substituted cyclopentadienyl or the bridged biscyclopentadienyl or a neutral linkage in which the R "units, independently of each other, represent alkyl with unsubstituted, straight or straight chain C to C 18, or substituted with C 1 to C 6 alkoxy or halogen, the C 5 or C 6 cycloalkyl unsubstituted or substituted by alkyl with C to C, C to C alkoxy or halogen, phenyl unsubstituted or substituted by C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 alkoxymethyl, C 1 to C 6 alkoxyethyl, di (C 1 to C 6 alkyl) amino, di (C to C alkyl) aminoalkyl to C to C or halogen, or benzyl or phenylethyl unsubstituted or substituted by alkyl with C to Cg, alkoxy with C to Co, C 1 to C 6 alkoxymethyl, C 1 to C 6 alkoxyethyl, di (C to C) amino alkyl, di (C to C 6 alkyl) amino to C to C 6 alkyl or halogen; or else Formulas VIII, Villa and Vlllb the other radicals from R to R independently between them represent secondary amino with 2 to 18 carbon atoms, R 320- or R32S-, halogen, the unsubstituted or substituted cyclopentadienyl or the bridged biscyclopentadienyl or means a neutral linkage, in which the R independently of each other denote alkyl with C to C 18, unsubstituted or substituted with C1 to C alkoxy or halogen, of linear character or branched, the cycloalkyl with C 5 or C 6 unsubstituted or substituted with alkyl with CI to C, alkoxy with Cl to Co or halogen, phenyl unsubstituted or substituted by alkyl with C 1 to C, alkoxy with C 1 to C 6, alkoxymethyl with C to C, alkoxyethyl with C 1 to C 6, di (alkyl with CI to C) amino, halogen, or the benzyl or phenethyl unsubstituted or substituted by alkyl with C "to C, alkoxy with C to Cb, alkoxymethyl with CI to C, alkoxyethyl with C1 to C, di (C1 to C6 alkyl) amino, di (C1 to C alkyl) amino-alkyl with C to C, or substituted by halogen. 20. The process according to claim 1, characterized in that the titanium, niobium, tantalum, molybdenum or tungsten compounds of the formulas VIII, Villa and Vlllb in which R 39 represents a radical of Formula VII -CH2-Si (R29R30R31) 3.1 R 40 represents F, Cl or Br; and (a) 'in Formula R, 1 and J R42 as well as R43 and R44 in each case in combination rep resent the radical = N-R33 or R41 and J R4_ jointly signify the radical = N-R33 and R43 and R44 independently of each other they represent unsubstituted or substituted cyclopentadienyl, R_-0- or halogen, or (b) in the formula Villa R and R .. together they mean the radical = N_R33 and R43 represents unsubstituted or substituted cyclopentadienyl, R32-0- or halogen , or in the Formula Villa R 41, R ~ 42 and R43 independently of each other represent cyclopentadienyl unsubstituted or substituted R 32"-0- or halogen, or (c) Formula Vlllb R 41 and R 42 independently represent cyclopentadienyl unsubstituted substituted, R 32-o- or halogen, wherein R 29, R 3 R 31 R 32 R have the definitions presented in claim 19. 21. The process according to claim 1, characterized in that metal compounds of the formulas IX are used. , I xa, IXb, IXc or IXd, in which Mei represents Mo (VI) or W (VI); Me. represents Nb (V) or Ta (V); R represents -Si (alkyl with C. to C); Z denotes Cl or Br; R 33 represents phenyl or phenyl substituted with 1 to 3 alkyl radicals of C 1 to C, C 1 to C 4 alkoxy, R ,. and R44, in Formula IX together represent the group = NR_ or individually and independently between them mean F, Cl, Br, alkoxy with C.-C ?, unsubstituted or substituted with fluorine, straight chain or in particular branched, phenyloxy unsubstituted or substituted with Cl to C4 or alkoxy C to C or 1 4 denote the cyclopentadienyl unsubstituted or substituted with alkyl with C to C; 1 4 (b) R 41, R42 and R43 and R44 in the Formula Ixa independently of each other means F, Cl,. Br, alkoxy with C to C, of 1 straight or particularly branched chain, unsubstituted or substituted with fluorine, phenyloxy unsubstituted or substituted by alkyl with C to C, or alkoxy with C to C 1 4 1 4 or the unsubstituted cyclopentadienyl or substituted with alkyl with C to C; ^ 1 4 (c) R 43 in Formula IXb, means F, Cl, Br, and denotes in particular the alkoxy with unsubstituted C 1 to C or substituted with fluorine, straight-chain or in particular branched, phenyloxy unsubstituted or substituted by alkyl with C 1 to C4 or alkoxy with C1 to C4 or representative the cyclopentadienyl unsubstituted or substituted with (d) R 41, R42 and 43 in Formula IXc, independently of each other, mean F, Cl, Br, alkoxy with C to C chain straight or in particular branched, unsubstituted or substituted by fluorine, the phenyloxy unsubstituted or substituted by C 1 to C 4 alkyl, or C 1 to C t alkoxy, or represents the cyclopentadienyl unsubstituted or substituted by C to C alkyl; and 1 4 (e) R 4i and R 42 in Formula IXd, independently of each other, mean F, Cl, Br, straight chain or particularly branched C 1 -C 4 alkoxy, unsubstituted or substituted by fluorine, unsubstituted phenyloxy or substituted by alkyl with C. to C, alkoxy with C to C or 4 1 4 either the cyclopentadienyl unsubstituted or substituted with alkyl with C 1 to C 4. 22. The process according to claim 1, characterized in that titanium, niobium, tantalum, molybdenum or tungsten compounds of the formulas X, Xa, Xb, Xc and Xd are used, (R33-N =) 2Me1Xa [CH2Si (CH3) 3] (X), (R33-N =) R41Me1Xa (OR32) CH2Si (CH3) 3 (Xa), R42R43Me2Xa (OR32) CH2Si (CH3) 3 (Xc), R33-N = Me2Xa (OR32) CH2Si (CH3) 3 (Xc), R41-TiXa (OR32) CH2Si (CH3) 3 (Xd), where Mel represents Mo (VI) or W (VI); Me, represents Nb (V) or Ta (V); X represents F or Cl; R3. means phenyl or phenyl substituted with 1 or 2 C, a C alkyl groups; R 3 represents alkyl with C, a C, branched chain and optionally substituted partially or fully with fluorine, or also phenyloxy or phenyloxy substituted with 1 to 3 methyl or ethyl groups; R42 and R43 independently represent cyclopentadienyl unsubstituted or substituted with 1 to 5 methyl groups, Xa or R320-. R represents cyclopentadienyl unsubstituted or substituted with 1 to 5 methyl groups, X or R 0-. 23. The process according to claim 1, characterized in that the compounds of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), Ti [CH, Si (CHJ] C1 ,, are used, Ti [CHSi (CH)] Br, Cp Ti [CH Si (CH)] C1, (CH3) .Ti [CH2Si (CH3) 3] Cl, Cp i [CH2Si (CTy 3] Br, Cp2Ti [CH2SÍ (CH3) 3] I, CpTi [CH2SÍ (CH3) β] [CH3] Cl, Cp r- Ti [CH 2 Si (CH 3) 3] Br z, < [- (CH 3) > 2 CHO] z Ti [CH 2 Si (CH 3) 3] Cl, [(CFJ, CH0] Ti [CH , Si (CH) JCl, [(CF) CHO] CpTi [CH Si (CH)] C1, [(CHJ .CHO] CpTi [CH ^ SI (CH)] C1, (C ^ O) CpTi [CH2Si (CH)] C1, (2,6-dimethyl-C, H50) CpTi [CH ^ Si (CH) Cl, (2,6-dimethyl-C 6H50) _, Ti [CH ¿, .Si (CH oJ or JCl, (2,6-dimethyl-C 6H50) Ti [CH 2 Si (CH 3) 3] 2 Br, [(CH3) 3CO] CPTÍ [CH2Si (CH3) 3] Cl, [(CFJ. (CH3) COJCpTÍ [CHS Si (CH) 3] Cl, Me (= NC HJ [OCH (CH) J [(CH Si (CH 3) 3 J "Cl, CpMe [(CH Si (CH)] C1 .., 3 3" Yes (CH3) 3] C1, Me (= N-2, 6-diisopropylC or H or J [((CH 3 ) 3] Cl 2, Me (= N-2, 6-diisopropyl C HJ [(CH) .CHO] [(CH.Si (CH) JCl, Me (= N-2, 6-dimethylC 6 H 3) (2 , 6-dimethyl-C 6 H 5 o) [CH 2 Si (CH 3) 3] Cl, Me (= N-2, 6-dimethylC H) ((CF) CHO) [(CH Si (CH) JCl, 6 3 3 *. I. 3 3 (= N-2, 6-dimethylC 6 H 3) CpMe [(CH 2 Si (CH 3) 3 JCl, (C ^ 6H 5cO) CpMe [(CH 2 Si (CH 3 ) 3 JCl, (= N-3, 5-dimethylC 6 H 3) Me [2,6-dimethylC 6 H 3 O)] [(CH 2 Si (CH 3) 3 JCl, Cp i-Me [OCH (CH 3) 2] 2 [(CH 2 Si (CH 3) 3 JBr, CpMe [OCH (CH 3) 2J 2 [(CH, Si (O 3 J Cl, CpMe [OCH (CF 3) 2] 2 [(CH 2 Si (CH 3) 3] C1, Cp ..- Me (methyl) [(CH 2 Si (CH 3) or JCl, Cp < ##################################################################################################### CH30) 2 [(CH ^ Si (CH3) 3J Cl, Me [CH 2 Si (CH 3) 3 J [OCH (CH 3)] (CF 3 O) 2 Cl, W (= NC t H 5) [( OC (CH 3) 3] [CH 2 - Si (CH 3) 3 J Cl 2, (2,6-diisopropylphenyloxy) "Me [CH Si (CH)] Cl, Cp.Me [OC (CH 3) [(CH 2 Si ( CHJ Cl, CpMe [OC (CH 3) (CF 3) 2] 2 [(CH 2 Si (CH 3) 3 JCl, Mo 2, [(CH "- Si (CH or J) (CH or J 3) Cl] ,, Mo (= N-2, 6-diisopropylC HJ _ [CH -Si (CH 3) 3] Cl, OC (CH 3) 3J 2 [CH 2 -Si (CH 3) o JCl, Mo (= N-2, 6-diisopropylC.HJ [OCHoC (CH)], CH2-Si (CH) JCl 24. The process according to claim 1, characterized in that the compounds of titanium (IV), niobium ( V), tantalum (V), molybdenum (VI) and tungsten (VI) in an amount of 0.001% to 20% Molar with respect to the amount of the cycloolefin. 25. The process for the photocatalytically induced and thermally polarized polymerization of a cyclic olefin or at least two different cyclic olefins in the presence of a metal compound as catalyst according to claim 1, characterized in that a) cycloolefins are first irradiated in the presence of a catalytic amount of at least one thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen are attached to the metal; or a catalytic amount of at least one thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen are attached to the metal, optionally in an inert solvent and then this material is mixed with at least one cycloolefin; and b) the polymerization is then terminated by heating and without irradiation. 26. The composition containing (a) a cyclic olefin or at least two different cyclic olefins and (b) a catalytically active amount of at least one thermostable compound of titanium (IV), niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a silylmethyl group and at least one halogen are attached to the metal. 27. The coated carrier material characterized in that a layer of (a) a cyclic olefin or at least two different cyclic olefins and (b) a catalytically active amount of at least one thermostable titanium (IV) compound is applied above a carrier. , niobium (V), tantalum (V), molybdenum (VI) or tungsten (VI), in which a group of silylmethyl and at least one halogen are attached to the metal. 28. The carrier material that is coated with an oligomer or polymer made according to claim 1 and in that the material contains a crosslinking agent. 29. Coated carrier material characterized in that a layer consisting of a polymer made according to claim has been applied above a carrier. 30. The process for manufacturing coated materials or embossed configurations above carriers, in which a composition according to claim 26 is applied, and optionally the solvent is removed and the polymerization layer is irradiated and eventually hardened by the thermal path, or the layer is irradiated by means of a photographic mask, eventually hardens at a later time by the thermal path and then the non-irradiated portions are removed with the aid of a solvent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3460/94 | 1994-11-17 | ||
| CH346094 | 1994-11-17 | ||
| PCT/EP1995/004364 WO1996016105A1 (en) | 1994-11-17 | 1995-11-06 | Process for polymerizing cyclical olefins and photopolymerizable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MX9703318A MX9703318A (en) | 1997-07-31 |
| MXPA97003318A true MXPA97003318A (en) | 1997-12-01 |
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