MXPA97003614A - Procedure for the polymerization of olephines ciclicas and composition photopolimeriza - Google Patents
Procedure for the polymerization of olephines ciclicas and composition photopolimerizaInfo
- Publication number
- MXPA97003614A MXPA97003614A MXPA/A/1997/003614A MX9703614A MXPA97003614A MX PA97003614 A MXPA97003614 A MX PA97003614A MX 9703614 A MX9703614 A MX 9703614A MX PA97003614 A MXPA97003614 A MX PA97003614A
- Authority
- MX
- Mexico
- Prior art keywords
- carbon atoms
- alkyl
- substituted
- unsubstituted
- alkoxy
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims description 36
- -1 cyclic olefin Chemical class 0.000 claims abstract description 102
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 125000001424 substituent group Chemical group 0.000 claims abstract description 21
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 20
- QUWPZPLTANKXAM-UHFFFAOYSA-N niobium(5+) Chemical compound [Nb+5] QUWPZPLTANKXAM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 230000003197 catalytic Effects 0.000 claims abstract description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 11
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 8
- 230000033458 reproduction Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 5
- 229920001169 thermoplastic Polymers 0.000 claims abstract 2
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract 2
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 456
- 125000000217 alkyl group Chemical group 0.000 claims description 158
- 125000003545 alkoxy group Chemical group 0.000 claims description 77
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 65
- 229910052736 halogen Inorganic materials 0.000 claims description 63
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 55
- 150000002367 halogens Chemical class 0.000 claims description 54
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 46
- 125000003118 aryl group Chemical group 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 35
- 125000001072 heteroaryl group Chemical group 0.000 claims description 30
- 125000001188 haloalkyl group Chemical group 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 22
- 125000002723 alicyclic group Chemical group 0.000 claims description 21
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 21
- 230000027455 binding Effects 0.000 claims description 20
- 150000001925 cycloalkenes Chemical class 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 20
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 19
- 125000004429 atoms Chemical group 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 125000005842 heteroatoms Chemical group 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 14
- 239000000969 carrier Substances 0.000 claims description 13
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 13
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 13
- 125000004848 alkoxyethyl group Chemical group 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- 150000002822 niobium compounds Chemical class 0.000 claims description 11
- 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 11
- 150000003482 tantalum compounds Chemical class 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 10
- 230000001264 neutralization Effects 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- WTKKCYNZRWIVKL-UHFFFAOYSA-N Tantalum Chemical class [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- 239000012442 inert solvent Substances 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 3
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 2
- 125000006619 (C1-C6) dialkylamino group Chemical group 0.000 claims description 2
- VCHQGHCBFOFZJK-UHFFFAOYSA-N 1-cyclopenta-1,3-dien-1-ylcyclopenta-1,3-diene Chemical group C1C=CC=C1C1=CC=CC1 VCHQGHCBFOFZJK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002619 bicyclic group Chemical group 0.000 claims description 2
- 125000005469 ethylenyl group Chemical group 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 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
- 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 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
- 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 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
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 150000002825 nitriles Chemical class 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
- 125000003367 polycyclic group Chemical group 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
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 125000002889 tridecyl 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])[H] 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
- POLCUAVZOMRGSN-UHFFFAOYSA-N Dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-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
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 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 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
- 239000011230 binding agent Substances 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000009750 centrifugal casting Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001681 protective Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
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- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003481 tantalum Chemical class 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- FCFMKFHUNDYKEG-UHFFFAOYSA-N thietane 1,1-dioxide Chemical compound O=S1(=O)CCC1 FCFMKFHUNDYKEG-UHFFFAOYSA-N 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
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, characterized in that a photochemical polymerization of ring opening by metathesis is carried out in the presence of a catalytic amount of at least one thermostable compound of niobium (V) or tantalum (V), which contains at least two methyl groups or two monosubstituted methyl groups, the substituent not containing any hydrogen atom in position (alpha). The process can also be carried out so that it is first irradiated and the polymerization is terminated by heating. The process is suitable, for example, for the manufacture of thermoplastic molded masses, coatings and reproductions of reliev
Description
PROCEDURE FOR THE POLYMERIZATION OF CYCLIC OLEFINS AND PHOTOPOLIMERIZABLE COMPOSITION
The present invention relates to a process for the polymerization of cyclic olefins by the photochemical polymerization of ring opening by metathesis, using catalytic amounts of a niobium or tantalum catalyst, which contains at least two methyl groups linked to the metal atom or two unsubstituted methyl groups, without hydrogen atoms a in the substituent, as well as compositions containing these olefins together with a catalytic amount of this catalyst. Ring-opening polymerization by metathesis, thermally induced using catalytic amounts of metal catalysts, has been known for a long time and is described in many places in the literature [see, for example, Ivin, K.J. Olefin Metathesis
1-12, Academic Press, London (1983)]. Said polymers are obtained industrially and can be obtained commercially. On the other hand, little has been known about ring-opening polymerization by metathesis, photochemically induced and commercial applications have not occurred until now. It is known from US Pat. No. 4,060,468 to perform an olefin metathesis polymerization in such a way that a mixture of two components is prepared from a metal salt, selected from the tungsten, olibdenum, rhenium and tantalum salts, and a substituted phenol or benzylalcohol, as cocatalysts, in a reaction vessel with the monomeric olefin and then the entire reaction mixture is irradiated with ultraviolet light. As olefins, only cyclic and acyclic hydrocarbons without functional groups or substituents are mentioned. The separate storage of the catalyst components directly before the reaction itself makes the process technically expensive and complicated. Tanielan and collaborators [Tanielan, C., Kieffer, R.,
Harfouch, A., Tetrahedron Letters 52: 4589-4592 (1977)] describe the catalytic system (C0) 6 / CC14, which can be used after irradiation with ultraviolet light for the polymerization by metathesis of cyclopentene and norborene. Metal carbonyls are volatile and toxic, so their use, for physiological reasons, makes costly protective measures necessary. In addition, a radical reaction of addition with the formation of monomeric l-chloro-2-trichlormethyl-cycloalkanes is observed as a competition reaction. By Thoi et al. [Thoi, H.H. , Ivin, K.J. , Rooney, J.J., J. Mol. Catal. 15: 245-270 (1982)] it is known that a complex of wolfra iopentacarbonilcarbeno of the formula Phenyl
it is a thermal catalyst for the ring opening polymerization by dimethylnorborene metathesis, and together with phenylacetylene as cocatalyst, it also represents a photocatalytic system for the same polymerization. This catalytic system has the great disadvantage that as a ready-to-use formulation it has only a low storage stability, the carbonyl compound has physiological objections and the tolerance with respect to functional groups in cycloolefins is too small. Feldman and Schroc [Feld an, J., Schrock, R.R. , in:
Lippard, S.J. (Editor), Progress in Inorganic Chemistry 39: 1-74 (1991)] describe complexes of molybdenum and wolframidealkyne, which alone are weak catalysts for the polymerization of cycloolefins, but together with Lewis acids are effective thermal catalysts. Therefore, photochemically known activatable catalysts always require a cocatalyst, so the quality of the processed polymers, due to the chosen type and sequence of the reactants, can vary greatly.
With the known processes only polymers from cyclic olefins can be obtained at great costs and in an unsatisfactory industrial manner, by photochemical polymerization of ring opening by metathesis. As essential disadvantages, poor storage stability is considered, which allows a mixture of the components just before the processing, the deficient tolerance with respect to functionalized cyclic olefins, as well as the need to use two components as catalyst system. Therefore, there is a requirement to make available a process for obtaining polymers from cyclic olefins by photochemical polymerization of ring opening by metathesis, improved from the technical, economic and ecological point of view and generally usable. In WO 93/13171 there are disclosed one and two component, air and water stable catalysts, based on molybdenum and tungsten compounds containing carbonyl groups, as well as ruthenium and osmium compounds with at least one polyene ligand for thermal polymerization by metathesis and polymerization by photoactivated metathesis of taut cycloolefins, in particular norborene and norborene derivatives. Other polycyclic cycloolefins, especially non-condensed polycyclics, are not mentioned. The one-component catalysts used for the ruthenium compounds, namely [(C6H6) Ru (CH3CN) 2C1] + PF6"and [Ru (cumen) Cl2] 2 can be activated by ultraviolet irradiation, however the storage stability of the compounds with norborene are completely inadequate.These catalysts can only supply insufficiently to the known two-component catalysts Petasis and Fu [Petasis, NA, Fu, D., J. Am. Chem.
Soc. 115: 7208-7214 (1993)] describe the thermal polymerization of ring opening by metabolethesis of norborene using biscyclopentadienyl-bis (tri-ethylsilyl) methyl-titanium (IV) as a thermally active catalyst. No photochemical activity is mentioned. It was found that compositions from taut cycloolefins and a one-component catalyst are photochemically polymerizable, when the composition contains a niobium (V) or tantalum (V) compound, in which at least two alkyl groups, optionally substituted , are bound to the metal, the substituent not containing any hydrogen atom in position a. Surprisingly, these thermally stable compounds have proven to be effective catalysts for the photoinduced ring-opening polymerization by metathesis, where despite the photochemical reactivity, the storage stability of mixtures of cycloolefins and niobium or tantalum compounds is retained. . Furthermore, it was surprisingly found that the said catalysts, even after a short irradiation in the presence of cycloolefins, act 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 cycloolefin or at least two different cyclic olefins, in the presence of a metal compound as a catalyst, which is characterized in that a photochemical opening polymerization is carried out. ring by metathesis, in the presence of a catalytic amount of at least one thermostable niobium (V) or tantalum (V) compound, which contains at least two methyl groups or two monosubstituted methyl groups bound to the metal atom, not containing the substituent no hydrogen atom in position a. The other valencies of the niobium and tantalum atoms are preferably saturated with neutral thermostable ligands, which are known in large numbers. The number of neutral ligands can also exceed the stoichiometrically possible number (solvates). The cyclic olefins may be monocyclic or polycyclic ring systems, condensed and / or bridged, for example with two to four rings, which are unsubstituted or substituted and which may contain heteroatoms, such as O, S, N or Si, in one or various aromatic or heteroaromatic rings and / or rings, such as for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. Each cyclic ring may contain 3 to 16, preferably 3 to 12 and in particular preferred 3 to 8 ring members. The cyclic defines may contain other non-aromatic double bonds, according to the size of the ring of preference 2 to 4 of said additional double bonds. Annular substituents are those that are inert, that is, do not affect the chemical stability and thermostability of the niobium or tantalum compounds. Cycloolefins are rings, or ring systems tensed. In the context of the invention, thermostability means that the photocatalytically active niobium (V) or tantalum (V) compounds, when heated, do not form any active species for ring-opening polymerization by metathesis. For example, the catalyst, at room temperature to slightly elevated temperature as approximately + 40 ° C, in weeks, under the exclusion of light, may not initiate any ring opening polymerization by metathesis. During this time, only a negligible amount of monomer (less than 0.2% by weight) is transformed. The thermostability can be determined, for example, by storing in the dark for 96 hours at 50 ° C, a solution of toluene with 20% by weight of monomer and 0.33% by weight of niobium (V) or tantalum (V) catalyst and that the amount of polymer that eventually forms, which is recognized by the increase in viscosity and precipitation in a precipitating agent, for example quantitatively determinable with ethanol, filtration and drying, is not more than 0.5% by weight and preferably not more than 0.2% by weight. If the cyclic olefins contain more than one double bond, for example 2 to 4 double bonds, depending on the reaction conditions, the chosen monomer and the amount of catalyst, crosslinked polymerizers can also be formed. In a preferred embodiment of the process according to the invention, the cycloolefins correspond to the formula I
where Q? is a radical with at least one carbon atom, which forms together with the group -CH = CQ2 an alicyclic ring of at least three members, which, if appropriate, contains one or more heteroatoms chosen from the group consisting of silicon, phosphorus, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, = 0, -CN, -N02, R? R2R3Si- (0) u-, -C00M, -S03M, -PO3M, -C00 (M1) 1/2, -S03 (M1 ) 1 / 2f -P03 (M1) 1 /, alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, cyanoalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 16 carbon atoms, heteroaralkyl of 4 to 16 carbon atoms carbon or R4-X-; or are substituted on the two neighboring carbon atoms with -CO-O-CO- or -CO-NR5-CO-; or wherein, in the case of the neighboring carbon atoms of the alicyclic ring, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted by halogen -CN, -N02, R6R7R8SÍ- (0) u-, -C00M, -SO3M, -PO3M, -COO (M?)? 2, -S03 (M1)? / 2, ~ P03 (M1) 1/2, alkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cyanoalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 16 carbon atoms , heteroaralkyl of 4 to 16 carbon atoms or
R13-X1-; X and Xl, independently of each other, represent -O-, -S-, - CO-, -SO-, -S02-, -OC (O) -, -C (0) -0-, -C (0) -NR5-, -NR10- C (O) -, -S02-0- or -0-S02-; R 1, R 2 and R 3, independently of one another, mean alkyl of 1 to 12 carbon atoms, perfluoroalkyl of 1 to 12 carbon atoms, phenyl or benzyl; R4 and Ri3 independently represent alkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms; R5 and Rio "independently from each other, mean hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl, the alkyl groups being in turn unsubstituted or substituted by alkoxy of 1 to 12 carbon atoms or cycloalkyl of 3 to 8 atoms of carbon; R6 / R7 and R8 / independently of each other, mean alkyl of 1 to 12 carbon atoms, perfluoroalkyl of 1 to 12 carbon atoms, phenyl or benzyl; M represents an alkali metal and M an alkaline earth metal; and u represents 0 or 1; wherein the alicyclic ring formed with Qi contains, if appropriate, other non-aromatic double bonds; Q2 means hydrogen, alkyl of 1 to 20 carbon atoms, halogenalkyl of 1 to 20 carbon atoms, alkoxy of 1 to 12 carbon atoms, halogen, -CN, Rn ~
X2-; R n means alkyl of 1 to 20 carbon atoms, halogenalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms or aralkyl of 7 to 16 carbon atoms; X2 means -C (0) -0- or -C (0) -NR12; Ri2 means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; wherein the aforementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted with alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, -N02, -CN or halogen, and where the heteroatoms of the aforementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group -O-, -S-, -NRg- and -N =; and R9 means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl.
The fused alicyclic rings preferably contain 3 to 8, especially preferred 4 to 7 and particularly preferably 5 or 6 ring carbon atoms. If there is an asymmetric center in the compounds of formula IThis has the consequence that the compounds can be present in optically isomeric forms. Some compounds of the formula I can be present in tautomeric forms (for example, keto-enol tautomerism). If there is a double aliphatic bond C = C, geometric isomerism (form E or form Z) can also occur. In addition, exo-endo configurations are also possible. Formula I thus includes all possible stereoisomers which occur in the form of enantiomers, tautomers, diastereoisomers, E / Z isomers or their mixtures. In the definitions of the substituents, the alkyl, alkenyl and alkynyl groups may be straight or branched chain. The same applies to either or both alkyl groups of alkoxy, thioalkyl, alkoxycarbonyl groups and other alkyl-containing groups. These alkyl groups preferably contain 1 to 12, more preferably 1 to 8 and in particular preferred 1 to 4 carbon atoms. These alkenyl or alkynyl groups preferably contain 2 to 12, more preferably 2 to 8 and particularly preferably 2 to 4 carbon atoms. Alkyl includes, for example, methyl, ethyl, isopropyl, normal propyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, as well as the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-iso-butyl, 1-hydroxy-sec. -butyl, 1-hydroxy-ter. -butyl, as well as the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals. Halogenoalkyl includes, for example, fluomethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloethyl, as well as halogenated alkanes, in particular fluorinated or chlorinated, such as, for example, isopropyl, normal propyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Alkenyl includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-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 cycloalkyl is preferably cycloalkyl of 5 to 8 carbon atoms, particularly preferred cycloalkyl of 5 carbon atoms or 6 carbon atoms. Some examples are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cyanoalkyl includes, for example, cyanomethyl (methyl nitrile), cyanoethyl (ethyl nitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyano-iso-butyl, 1-cyano- sec. -butyl, 1-cyano-ter. -butyl, as well as the various cyanopentyl and cyanohexyl radicals. Aralkyl preferably contains 7 to 12 carbon atoms and particularly preferably 7 to 10 carbon atoms. It can be, for example, benzyl, phenethyl, 3-phenylpropyl, -ethylbenzene, phenylbutyl or a, a-dimethylbenzene. Aryl preferably contains 6 to 10 carbon atoms. It can be, for example, phenyl, pentalin, indene, naphthalene, bluish or anthracene. Heteroaryl preferably contains 4 or 5 carbon atoms and one or two heteroatoms of the group of O, S and N. It can be, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine or quinoline. Heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or two heteroatoms of the group of O, S and N. It can be, for example, oxirane, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or tetrahydrothiophene. Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, secondary butyloxy and t-butyloxy. In the context of the present invention, alkali metal is to be understood as meaning lithium, sodium, potassium, rubidium and cesium, in particular lithium, sodium and potassium. In the context of the present invention, alkaline earth metal should be understood as beryllium, magnesium, calcium, strontium and barium, in particular magnesium and calcium. In the above definitions, "halogen" is to be understood as meaning fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine. The compounds of formula I which are especially suitable for the process according to the invention are those in which Q2 is hydrogen. In addition, for the polymerization, compounds of the formula I are preferred in which the alicyclic ring, formed jointly by Q and the group -CH = CQ2-, has 3 to 16, preferably 3 to 12 and particularly preferred 3 to 8. ring atoms, and wherein it can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system. The process according to the invention can be carried out in a particularly advantageous manner with those compounds of the formula I, wherein: Q 1 is a radical with at least one carbon atom, which forms together with the group -CH = C 2 a alicyclic ring of 3 to 20 members, which, if appropriate, contains one or more heteroatoms chosen from the group consisting of silicon, oxygen, nitrogen and sulfur; and that is unsubstituted or substituted with halogen, = 0, -CN, -N02,
RlR2R3SÍ- (0) u-, -C00M, -S03M, -PO3M, -C00 (M1)? 2 S? 3 (M?)? 2, -P03 (M?)? / 2, alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 12 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 12 carbon atoms, heteroaralkyl of 4 to 12 carbon atoms carbon or
R4-X-; or wherein two neighboring carbon atoms in this Qi radical are substituted with -CO-O-CO- or -CO-NR5-CO-; or in which, if appropriate, in neighboring carbon atoms, an aromatic, alicyclic ring is condensed
Or heteroaromatic, which is unsubstituted or substituted with halogen -CN, -N0, RgR ^ sSi- (O) u-, -COOM, -SO3M, -P03M, -COO (M?)? / 2, -S03 (M) ?)? / 2, -P03 (!) 1/2, alkyl of 1 to 12 carbon atoms, halogenoalkyl of
1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 12 carbon atoms carbon, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 12 carbon atoms, heteroaralkyl of 4 to 12 carbon atoms or R 13 -X 1 -;
X and Xl, independently of each other, represent -O-, -S-, - CO-, -SO-, -S02-, -OC (O) -, -C (0) -0-, -C (0) -NR5-, -NR? 0- C (O) -, -S02-0- or -0-S02-; R 1, R 2 and R 3, independently of one another, mean alkyl of 1 to 6 carbon atoms, perfluoroalkyl of 1 to 6 carbon atoms, phenyl or benzyl; M represents an alkali metal and Mi an alkaline earth metal; and R4 and R13 independently represent alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 12 carbon atoms , aralkyl of 7 to 12 carbon atoms; R5 and R1? / Independently from each other, mean hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzyl, the alkyl groups being in turn unsubstituted or substituted with alkoxy of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; R6, R7 and Rβ, independently of each other, mean alkyl of 1 to 6 carbon atoms, perfluoroalkyl of 1 to 6 carbon atoms, phenyl or benzyl; u represents 0 or 1; wherein the alicyclic ring formed with Qi contains, if appropriate, other non-aromatic double bonds; Q2 means hydrogen, alkyl of 1 to 12 carbon atoms, halogenalkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, halogen, -CN, Ru-X2-; Ril means alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms or aralkyl of 7 to 12 carbon atoms; x2 means -C (?) - o- or -c (?) - NR? 2; and R 12 is hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzyl; wherein the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted with alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, -N02, -CN or halogen, and wherein the heteroatoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group -0-, -S-, -NR9- and -N =; and R9 means hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzyl. Of this group, those compounds of the formula I are preferred, in which Qi is a radical with at least one carbon atom, which together with the group -CH = CQ2 forms an alicyclic ring of 3 to 10 members, which , if appropriate, contains one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, -CN, -N02, RlR2R3SÍ-, -COOM, -S03M, -P03M, -COO (M?) 1 2, -S03 (M?) 1 2, -P03 (M? )? / 2, alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl, benzyl or R 4 -X-; or in which, if appropriate, in neighboring carbon atoms, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted by halogen -CN, -N02, R6R7R8SÍ- (0) U-, -COOM, -SO3M, -PO3M, -COO (M?)? / 2, "S03 (M?)? / 2, -P03 (M?)? / 2, alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl, benzyl or R 13-, R 1, R 2 and R 3, independently of each other, they mean alkyl of 1 to 4 carbon atoms, perfluoroalkyl of 1 to 4 carbon atoms, phenyl or benzyl, M represents an alkali metal and Mi an alkaline earth metal, and R4 and Rl3 independently represent alkyl of 1 to 6 carbon atoms, haloalkyl from 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; X and XI, independently of each other, mean -O-, -S-, -CO-, -SO- or -S02-; R5f R7 and R8, independently of each other, mean alkyl of 1 to 4 carbon atoms, perfluoroalkyl of 1 to 4 carbon atoms, phenyl or benzyl; and Q means hydrogen. In particular, the process according to the invention is suitable for the polymerization of norborene and norborene derivatives. Of these norborene derivatives, those corresponding to either formula II are particularly preferred.
wherein X3 means -CHR16-, oxygen or sulfur; 14 and R15 independently of each other, mean hydrogen,
-CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3-Si or -C00R17; and R16 and R17 'independently from each other, denote hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; or to formula III
wherein X 4 means -CHR 19, oxygen or sulfur; R19 means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; and Ri3 means hydrogen, alkyl of 1 to 6 carbon atoms or halogen; or to formula IV
where? 5 means -CHR2-, oxygen or sulfur; R22 denotes hydro-cene, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; R2? and R2if independently of each other, they mean hydrogen,
CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3Si- or -COOR23; and R23 means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; or to formula V
wherein X6 means -CHR24-, oxygen or sulfur; R2 means hydroquinone, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; And it means oxygen or > N-R25; and R25 means hydrogen, methyl, ethyl or phenyl. The following compounds of the formula I are especially suitable for the polymerization process according to the invention, with bi-and polycyclic systems being accessible through Diels-Alder reactions:
or
or O
O (23),
The niobium (V) and tantalum (V) compounds to be used according to the invention contain a metal atom. The methyl group or monosubstituted methyl group bonded to the metal is bound as a ligand at least two, particularly preferably two to five times and especially preferred two or three times. This ligand corresponds preferably to formula VII,
-CH2-R (VII) wherein R represents H, -CF3, -CR26R2 R28 -SiR29R3oR3 ?, aryl with 6 to 16 carbon atoms or heteroaryl with 4 to 15 carbon atoms unsubstituted or substituted with alkyl with 1 to 6 atoms carbon or alkoxy with 1 to 6 carbon atoms, with 1 to 3 heteroatoms of group 0, S and N; and R26 R27 and R28"independently from each other, mean alkyl having 1 to 10 carbon atoms, which is unsubstituted or substituted by alkoxy with 1 to 10 carbon atoms, or R26 and R27 have this meaning and R2s means aryl with 6 to 10 carbon atoms or heteroaryl with 4 to 9 carbon atoms, which is unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms; and R29 R30 and R31I independently of each other, mean alkyl having 1 to 6 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, or phenyl or benzyl unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms. If R26 to R3 mean alkyl, it may be linear or branched and preferably contain 1 to 8, particularly preferably 1 to 4, carbon atoms. If R28 to R3l mean aryl, it is preferably phenyl or naphthyl. If in formula VII R means aryl, it is preferably phenyl or naphthyl. If in the formula VII R means heteroaryl, it is preferably pyridinyl, furanyl, thiophenyl or pyrrolyl. Within the framework of the definitions, preferred substituents for R26 to R3i are methyl, ethyl, methoxy and ethoxy. Examples of the radicals R6 to R31 were indicated above under the compounds of the formula I. In a preferred embodiment, the group R in the formula VII means H, -C (CH3) 3, -C (CH3) 2C6H5, unsubstituted phenyl or substituted with methyl, ethyl, methoxy or ethoxy, -CF3 or -Si (CH3) 3. The other valences of niobium and tantalum are preferably saturated with neutral thermostable ligands, the definition of thermostability having been indicated at the beginning. Preferably, ligands are the same or different from the group consisting of = 0, = N-R33, secondary amines with 2 to 18 carbon atoms, R320-, R32S-, halogen, cyclopentadienyl, bridged bicyclopentadienyl, tridentate monoanionic neutral ligands and ligands , such as ethers, nitriles CO and phosphines and tertiary amines, wherein R32, independently of each other, represents linear or branched alkyl with 1 to 18 carbon atoms, unsubstituted or substituted with alkoxy with 1 to 6 carbon atoms or halogen, cycloalkyl with 5 or 6 carbon atoms, unsubstituted or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms or halogen, unsubstituted or substituted phenyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms carbon, C 1 -C 6 -alkoxymethyl, C 1 -C 6 -alkoxyethyl or halogen, or benzyl or unsubstituted phenylethyl or substituted with C 1 -C 6 -alkyl, C 1-6 -alkoxy, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms or halogen; and R33 means linear or branched alkyl having 1 to 18 carbon atoms, unsubstituted or substituted by alkoxy with 1 to 6 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, unsubstituted or substituted with alkyl having 1 to 6 carbon atoms , C 1 -C 6 alkoxy or halogen, unsubstituted or substituted phenyl with 1 to 6 carbon atoms, C 1 -C 6 alkoxy, C 1 -C 6 alkoxymethyl, alkoxyethyl with 1 6 carbon or halogen atoms, di (C 1 -C 6 -alkyl) amino, di (C 1 -C 6 -alkyl) to unsubstituted alkyl with 1 to 3 carbon atoms or halogen, or unsubstituted benzyl or phenylethyl or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms or halogen. The secondary amines are preferably those of the formula R34R35N-, wherein R3 and R35, independently of one another, mean linear or branched alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, benzyl or phenylethyl or (alkyl having 1 to 6 carbon atoms) 3 Si unsubstituted or substituted by alkoxy with 1 to 6 carbon atoms or halogen; or together they mean tetramethylene, pentamethylene or 3-oxapentan-l, 5-diyl. The alkyl preferably contains 1 to 12, particularly preferably 1 to 6 carbon atoms. Some examples are dimethylamino, diethylamino, di-n-propylamino, di-i-propylamino, di-n-butylamino, ethyl -ethyl-amino, dibenzyl-amino, benzyl-methyl-amino, diphenyl-amino, phenyl-methylamino and di (trimethylsilyl) amino. Halogen as another ligand in the metal atoms or as a substituent is preferably fluorine or chlorine and particularly preferred chlorine. The cyclopentadienyl can be unsubstituted or substituted by one to five alkyls with 1 to 4 carbon atoms, in particular methyl or -Si (alkyl with 1 to 4 carbon atoms), in particular -Si (CH 3) 3. Bridged cyclopentadienyl are in particular those of the formula R36-A-R36, wherein R36 means cyclopentadienyl unsubstituted or substituted by one to five alkyls with 1 to 4 carbon atoms, in particular methyl, or -Si (alkyl with 1 to 4 carbon atoms), in particular -Si (CH3) 3 and A represents -CH2-, -CH2-CH2-, -Si (CH3) 2, -YES (CH3) 2-Si (CH3) 2 or -Si (CH3) ) 2-0-Si (CH3) 2-. In the case of the ethers as neutral ligands, it can be a dialkyl ether with 2 to 8 carbon atoms or a cyclic ether with 5 or 6 ring members. Some examples are diethyl ether, methylethyl ether, diethyl ether, di-n-propyl ether, di-1-propyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane. In the case of nitriles as neutral ligands, it may be aliphatic or aromatic nitriles with 1 to 12, 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 ligands, it may be those with 3 to 24, preferably 3 to 18, carbon atoms. Some examples are trimethylamine and -phosphine, triethylamine and -phosphine, tri-n-propylamine and -phosphine, tri-n-butyl-amine and -phosphine, triphenylamine and -phosphine, tricyclohexylamine and -phosphine, phenyldimethylamine and -phosphine, benzyldimethylamine and -phosphine, 3, 5-dimethyl-phenyl-dimethylamine and -phosphine. In the case of tridentate monoanionic ligands, it can be, for example, hydro (tris-pyrazol-1-yl) borates or alkyl borates (trispyrazol-1-yl), which are unsubstituted or substituted by one to three C1 to C4 alkyls [see Trofimenko, S., Chem. Rev., 93: 943-980 (1993)], or of [C5 (R15) Co (R37R38P = 0) 3] ~, where R 'means H or methyl and R37 as well as R38 > independently of one another, they mean alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or phenyl [see Klaui, W., Angew. Chem. 102: 661-670 (1990)]. In the case of halogen as a substituent of the radicals R32 and R33, it is preferably fluorine and particularly preferred chlorine. The alkyl, alkoxy or alkoxy substituents in alkoxymethyl or -ethyl preferably contain 1 to 4, particularly preferably 1 or 2 carbon atoms. Examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy. R32 and R33 contain as alkyl preferably 1 to 12, particularly preferably 1 to 8, and especially preferred 1 to 4 carbon atoms. It is preferably branched alkyl. Some examples of R32 are methoxy, ethoxy, n- and i-propyloxy, n-, i- and t-butyloxy, hexafluoro-i-propyloxy and hexa-fluorbutyloxy as well as perfluorobutyloxy. Some examples for phenyl and substituted benzyl for R32 and R33 are p-methyl-phenyl or benzyl, p-fluor- or p-chlorphenyl or -benzyl, p-ethylphenyl or -benzyl, p-, n- or i-propylphenyl or - benzyl, pi-butylphenyl or -benzyl, 3-methyl-phenyl or -benzyl, 3-i-propylphenyl or -benzyl, 3,5-dimethylphenyl or -benzyl, 3,5-i-propylphenyl or -benzyl, 3,5 - n- or -t-butylphenyl and -benzyl. R33 represents particularly preferred phenyl unsubstituted or substituted by alkyl having 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms. In a preferred embodiment, the niobium and tantalum compounds correspond in particular to formula VIII,
where Me represents Nb (V) or Ta (V), at least two, preferably two or three of the radicals R39 to R43 mean a radical -CH2-R of the formula VII, where R means H, -CF3, -CR26R27 28, ~ SiR29R3? R3i, aryl with 6 to 16 carbon atoms or heteroaryl with 4 to 15 carbon atoms unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms, with 1 to 3 heteroatoms of group O, S and N; R26 / R27 and R28, independently of each other, mean alkyl having 1 to 10 carbon atoms, which is unsubstituted or substituted by alkoxy with 1 to 10 carbon atoms, or R26 and R27 have this meaning and R28 means aryl with 6 to 10 carbon atoms or heteroaryl with 4 to 9 carbon atoms, which is unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms; and 29 / R3? and R3i > independently from each other, they mean alkyl having 1 to 6 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, or phenyl or benzyl unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms; two of the other radicals from R39 to R3 mean together = 0 or = N-R33, and R33 means linear or branched alkyl with 1 to 18 carbon atoms, unsubstituted or substituted by alkoxy with 1 to 6 carbon atoms, cycloalkyl with 5 or with 6 carbon atoms, unsubstituted or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms or halogen, phenyl unsubstituted or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms, di (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino- alkyl having 1 to 3 carbon atoms or halogen, or benzyl or unsubstituted phenylethyl or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms, di (C 1-6 alkyl) amino, di (alkyl with 1 to 6 carbon atoms) amino-alkyl with 1 to 3 carbon atoms or halogen; and / or the other radicals from R39 to R43, independently of one another, mean secondary amino with 2 to 18 carbon atoms, R320- or R32S-, halogen, cyclopentadienyl or biscyclopentadienyl or a neutral ligand, wherein R2, independently of each other, means linear or branched alkyl with 18 carbon atoms, unsubstituted or substituted by alkoxy with 1 to 6 carbon atoms or halogen, cycloalkyl with 5 or 6 carbon atoms, unsubstituted or substituted with alkyl having 1 to 6 carbon atoms, C 1 -C 6 alkoxy or halogen, unsubstituted or substituted phenyl with 1 to 6 carbon atoms, C 1 -C 6 alkoxy, C 1 -C 6 alkoxymethyl, C 1 -C 6 alkoxyethyl carbon or halogen atoms, or benzyl or unsubstituted or substituted phenylethyl with 1 to 6 carbon atoms, 1 to 6 carbon atoms, 1 to 6 carbon atoms, 1 to 6 carbon atoms, day C 1 -C 6 -alkyl) amino, di (C 1 -C 6 -alkyl) amino-C 1 -C 3 -alkyl, or halogen, or benzyl or unsubstituted phenylethyl or substituted with alkyl with 1 to 6 atoms of carbon, C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxymethyl, C 1 -C 6 -alkoxyethyl, C 1 -C 6 -alkyl amino, di (alkyl with 1 to 6) carbon atoms) amino-alkyl having 1 to 3 carbon atoms or halogen. For the radicals R and R26 to R33 the preferences indicated above are valid. In a preferred embodiment, in the process according to the invention, niobium and tantalum compounds of the formula VIII are used, wherein a) R39 to R3 respectively represent a radical of the formula VII -CH2-R, or b) R39 and R4? represent respectively a radical of the formula VII -CH2-R, R4i and R42 together represent the radical = N-R33 and R43 means unsubstituted or substituted cyclopentadienyl, R2-0- or halogen, or c) R39, Ro and R4? respectively represent a radical of the formula VII -CH2-R and R42 and R43 together represent the radical = N-R33, or R39f R4? f R41 and R42 represent respectively a radical of the formula VII -CH-R and R43 means unsubstituted cyclopentadienyl or substituted, R32-O- or halogen, wherein R, R32 and R33 have the above meaning. Stop,
R32 and R33 are valid previous preferences. Very particularly preferred are niobium and tantalum compounds of the formulas IX, IXa or IXb in the process according to the invention,
where Me represents Nb (V) or Ta (V), R represents H, -C (CH3) 3, -C (CH3) 2-C6H5, -C6H5 or Si (alkyl having 1 to 4 carbon atoms), R33 means phenyl or phenyl substituted with one to three alkyls with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, R43 in the formula IX, represents the group -CH2-R or F, Cl,
Br, C 1 -C 4 -alkoxy, linear or in particular branched, unsubstituted or substituted by fluorine, unsubstituted phenyloxy or substituted by C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy or unsubstituted or substituted cyclopentadienyl with alkyl having 1 to 4 carbon atoms; R4i R42 and R43 in the formula IXa, independently of each other, mean F, Cl, Br, alkoxy with 1 to 4 carbon atoms, linear or in particular branched, unsubstituted or substituted with fluorine, unsubstituted phenyloxy or substituted with alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or cyclopentadienyl unsubstituted or substituted with alkyl having 1 to 4 carbon atoms; and R41 and R42 in formula IXb, independently of each other, mean F, Cl, Br, alkoxy with 1 to 4 carbon atoms, linear or in particular branched, unsubstituted or substituted with fluorine, unsubstituted phenyloxy or substituted with alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or cyclopentadienyl unsubstituted or substituted with alkyl having 1 to 4 carbon atoms. Alkoxy is particularly preferably branched alkoxy which, if appropriate, is totally or partially substituted with F, for example i-propyloxy, i- and t-butyloxy, hexafluoropropyloxy and nonafluoropropyloxy. Some examples of niobium (V) and tantalum (V) compounds are [Cp means cyclopentadienyl and
means Nb (V) or Ta (V)]:
Me [CH2SÍ (CH3) 3] 5, CpMe [(CH2C (CH3) 2-C6H5)] 3, Me (= N-2,6-dimethylC6H3) (CH3) 3, Me (= N-C5H5) [OC ( CH3) 3] [(CH2Si (CH3) 3] 2, Me (= N-
2,6-diisopropylC6H3) [(CH2-C6H5)] 3, Me (= N-C6H5) [0CCH3 (CF3) 2] [(CH2Si (CH3) 3] 2, CpMe [0CCH3 (CF3) 2] 2 [( CH2-C6H5)] 2,
Me (= N-2, 6-diisopropylC5H3) [(CH2C (CH3) 2-C6H5)] 2C1,
Cp2Me (CH3) 2 [OCH (CH3) 2], Me (= N-2, 6-dimethylC6H3 [(CH2-C6H5)] 3,
CpMe [0CH (CH3) 2] 2 [(CH2SÍ (CH3) 3] 2, Cp2Me [(CH2-C6H5)] 3,
Me [CH2Si (CH3) 3] 3Cl2, Me [CH2Si (CH3) 3] 3 [0CH2C (CH3) 3] 2, Cp2Me [3, 5-dimethyI6C30] [(CH2Si (CH3) 3)] 2 Me (2, 6-diisopropylphenyloxy) 2 (CH 3) 3, Cp 2 Me (CH 3) 3, Me (2,6-dimethyl-phenyloxy) 2 (CH 3) 3, Me [CH 2 Si (CH 3) 3] 3 [0CH (CH 3)] 2,
CpMe [0C (CH3) 3] 2 [(CH2-C6H5)] 2, Cp2Me [(CH2SY (CH3) 3] 3. The niobium and tantalum compounds to be used according to the invention are known or can be obtained according to known and the like, starting from the metal halides, if any substituted, by way of Grignard reactions and / or substitution reactions
[Schrock, R.R. , Murdzeck, J.S., Bazan, G.C., Robbins, J., DiMare, 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 using a solvent. Inert means that the choice of solvent is governed by the reactivity of the niobium and tantalum compounds, for example, that protic polar solvents are not used, when substitution reactions such as the exchange of halogen by alkoxy can be expected. Suitable inert solvents are, for example, protic-polar and aprotic solvents, which can be used individually or in mixtures of at least two solvents. Examples are: ether (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol, onomethyl ether or ethylene glycol dimethyl ether, ethylene glycol methyl ether or ethylene glycol diethyl ether, diethylene glycol diethyl ether), triethylene glycol ethyl ether), halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, 1,1-trichloroethane, 1,1,2,2-tetrachloroethane), esters of carboxylic acid and lactones (ethyl ester of acid acetic, propionic acid methyl ester, benzoic acid ethyl ester, 2-methoxyethyl acetate,? -butyrolactone, d-valerolactone, pivalolactone), carboxylic acid amides and lactams (N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, tetra ethylurea, hexamethyl triamide of phosphoric acid, β-butyrolactam, e-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam), sulfoxides (dimethyl sulfoxide), sulfones (dimethyl sulfone, diethyl sulfone, trimethylene sulfone, tetramethylene sulfone), tertiary amines (N-ethylpiperidine, N-methylmorpholine), aliphatic and aromatic hydrocarbons, such as petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene or substituted groups (chlorbenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene) and nitriles (acetonitrile, propionitrile, benzonitrile, phenylacetonitrile). Preferred solvents are polar and non-polar aprotic solvents. Preferred solvents are aliphatic and aromatic hydrocarbons, as well as mixtures of said solvents. It should be noted in particular that the compositions used according to the invention in the process, starting from a substituted cycloolefin and a catalyst, are often insensitive to oxygen, which makes it possible to keep them stored, as well as carrying out the reactions without gas protective. However, the exclusion of humidity is recommended, that is, the use of dry reaction and storage conditions.
The monomers of the formula I and the catalysts used for the process according to the invention can be stored either separately or together as a mixture, since the catalyst used has particularly high stability. The mixture can be stored before the photochemical polymerization as a ready-to-use formulation, which is an advantage for the large-scale technical application of the process according to the invention. Due to the high photosensitivity, in particular to ultraviolet light, the storage is carried out outside the 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 niobium (V) or tantalum (V) compound, containing minus two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position a. The composition according to the invention can additionally contain other non-volatile open-chain comonomers, which form copolymers with the cycloolefins which are tensed. In the case of using, for example, dienes, crosslinked polymerisates can be formed. Some examples of such comonomers are mono- or di-unsaturated olefinic compounds, such as olefins and dienes from the group of pentene, hexene, heptene, octene, decene, dodecylene, acrylic and methacrylic acid, their esters and amides, vinyl ether, styrene, butadiene, isoprene and chlorbutadiene. The other olefins suitable for metathesis polymerization are contained in the composition according to the invention, for example, in an amount of up to 80% by weight, preferably from 0.1 to 80% by weight, more preferably from 0.5 to 60% by weight and particularly preferred from 5 to 40% by weight, based on the total amount of the compound of the formula I and other olefins suitable for the metathesis polymerization. The composition according to the invention may contain auxiliaries of the formulation. The known auxiliaries are antistatic agents, antioxidants, light-protecting agents, softeners, dyes, pigments, fillers, fortifying fillers, lubricants, binders, viscosity-increasing agents and deformation aids. The fillers can be added in surprisingly high proportions without negatively influencing the polymerization, for example in amounts of up to 70% by weight, preferably from 1 to 70% by weight, more preferably from 5 to 60% by weight, particularly preferred from 10 to 50% by weight, and especially preferred from 10 to 40% by weight, based on the composition. Fillers and fortifying fillers to improve the optical, physical, mechanical and electrical characteristics are known in a large number. Some examples are glass and quartz in the form of powder, spheres and fibers, oxides of metals and semimetals, carbonates such as MgC03 / CaC03 dolomite, metal sulfates such as gypsum and heavy spar, natural and synthetic silicates such as talc, zeolite, volastonite, plagioclase, clays such as white clay, rock flours, whisker, carbon fibers, fibers or plastic powders and carbon black. The agents for increasing the viscosity are in particular polymerized by metathesis which have olefinically unsaturated groups and can be incorporated with the polymerization in the polymer. Such polymerizations by metathesis are known and can be purchased, for example, under the trade name Vestenamere ~. Other additives for increasing the viscosity are polybutadiene, polyisoprene or polychlorbutadiene, as well as copolymers of butadiene, isoprene and chloroprene with olefins. The agents for increasing the viscosity can be contained in an amount of 0.1 to 50, preferably 1 to 30, and particularly preferred 1 to 20% by weight, based on the composition. In the case of using fillers, it is advisable to preserve the 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 during the entire duration of the same. Once polymerization has been initiated photochemically, the rest of the development of the reaction takes place independently, even in the dark. Advantageously, the irradiation is carried out with light of the wavelength in the range of 50 nm to 1000 nm, preferably 200 nm to 500 nm and very particularly preferred in the ultraviolet range. The duration of irradiation depends on the type of light source. Preferably ultraviolet lasers or ultraviolet lamps are used. The irradiation of the catalyst can take place both before, during, and after addition of the monomers. Suitable irradiation times are from one minute to 8 hours, in particular 5 minutes to 4 hours. The sequence of monomer and catalyst addition is not critical. The monomer can be pre-arranged or added after adding the catalyst. Likewise, the catalyst can be previously irradiated and then the monomer can be added. In addition, the solution containing the catalyst and the monomer can be irradiated. The process according to the invention is preferably carried out at room temperature to a slightly elevated temperature. An increase in temperature serves to increase the reaction rate. The catalysts used only initiate thermal polymerization in exceptional cases. For this reason, photopolymerization takes place in particular at the temperatures chosen to accelerate the reaction. However, it should be mentioned that the catalysts can be transformed into thermoactive catalysts by sufficient irradiation. In particular, the process according to the invention is carried out at temperatures of -20sc to + ll? Sc. A very particular and surprising advantage of the process according to the invention is that the niobium (V) and tantalum (V) compounds used serve as thermal catalysts after irradiation. This results in the possibility of continuing and finishing the polymerization after a short time of irradiation by means of heat supply, which offers economic and technical advantages in different areas of the manufacture of molded bodies or coatings. In particular, the combined process is suitable for the manufacture of ter oplasts. Another object of the invention is a process for the photocatalytically induced and then thermally induced 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 cycloolefin in the presence of a catalytic amount of at least one thermostable compound of niobium (V) or tantalum (V), containing at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position to; or a catalytic amount of at least one thermostable compound of niobium (V) or tantalum (V), which contains at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position optionally in an inert solvent and then mixed with at least one cycloolefin; and b) the polymerization is then terminated by heating and without irradiation. For procedure stage a) the preferences indicated above are valid. The duration of the irradiation depends basically on the control of the desired reaction. A short irradiation is chosen, for example, when the polymerization is initiated only by irradiation and it is desired to terminate by heating. Short may mean an irradiation time of up to 60 seconds, preferably 5 to 60 seconds and particularly preferred 10 to 40 seconds. A longer irradiation time is chosen, for example, when it is desired to carry out the polymerization, especially under irradiation, and it is desired to terminate the final polymerization only by annealing. Heating in process step b) can mean a reaction temperature of 50 to 2002C, preferably 50 to 1502C and particularly preferred 70 to 1202C. In the context of the present invention, catalytic amounts preferably mean an amount of 0.001 to
% in mol, particularly preferred 0.01 to 15% in mol and very particularly preferred 0.01 to 10% in mol, based on the amount of the monomer. Another object of the invention is a process for producing thermal catalysts for ring-opening metathesis polymerization of cyclic olefins, which is characterized in that it is irradiated in substance or in a solvent, a thermosetting niobium or tantalum compound, containing minus two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position a. The cycloolefins used according to the invention are tensioned rings. Cyclohexane, as an exception, usually can not be homopolymerized with olefin metathesis. This exception is known to the person skilled in the art and is described, for example, in Ivin [Ivin, K.J. in: Ivin, K.J.,
Saegusa, T. (editor), Ring-Opening Poly erisation 1: 139-144 Elsevier Applied Science Publishers, London and New York
(1984) With the process according to the invention, it is possible to obtain oligomers and polymers cured by irradiation with the same or different structural units of the formula XI,
where Qi and Q2 have the indicated meanings for the formula I. For these polymers the preferences indicated above are valid. They can be homopolymers or copolymers with statistical distribution of the structural units, graft polymers or block polymers. They may have an average molecular weight (Mw) of, for example, 500 to 2 million Daltons, preferably 1000 to 1 million Daltons (determined according to GPC by comparison with narrowly distributed polystyrene standards). With the process according to the invention, thermoplastically deformable materials can be produced for the production of moldings of all kinds, coatings and the reproduction of reliefs. Depending on the monomer used, the polymers according to the invention can have very different characteristics.
Some are characterized by a very high oxygen permeability, low dielectric constant, good thermal stability and low water absorption. Others have excellent optical characteristics, such as high transparency or low refractive index. In addition, low shrinkage should be especially emphasized. For these reasons, they can be used in the most diverse technical fields. The compositions according to the invention are characterized as layers on the surfaces of carrier materials, by a high adhesive force. In addition, the coated materials are characterized by a very high surface smoothness and gloss. Under the good mechanical characteristics should be emphasized especially the low shrinkage and high resistance to shock, but also the thermal resistance. It should also mention the easy moldability and high resistance to solvents. These polymers are suitable for the manufacture of medical devices, implants or contact lenses; for the manufacture of electronic components; as binders for lacquers; as photo-hardening compositions for the construction of models or as glues for the bonding of substrates with low surface energies (for example, Teflon, polyethylene and polypropylene), also as a photopolymerizable composition in stereolithography. The compliant compositions; The invention can also be used for the production of lacquers by photopolymerization, it being possible to use clear (transparent) and even pigmented compositions on the one hand. Both white pigment and colored pigment can be used. Mention should also be made of the manufacture of molded bodies according to thermoplastic molding processes for objects of all kinds. The photo-curable or photo-curing compositions according to the invention are particularly suitable for the production of protective layers and relief reproductions. Another object of the invention is a variant of the method according to the invention for the manufacture of coated materials or reproduction of reliefs on substrates, in which a cyclic olefin composition, catalyst and, if appropriate, solvent is applied as a layer on the carrier, for example by means of immersion, brush application, casting, rolling, raking or centrifugal casting processes, if necessary The solvent is removed and the layer is irradiated for polymerization, or the layer is irradiated by a photomask and then the non-irradiated parts are removed with a solvent. With this method, the substrates surfaces can be modified or protected, or for example, printed switches, pressed plates or pressed cylinders can be manufactured. In the manufacture of printed switches, the compositions according to the invention can also be used as a weld stop plate. other possibilities of application are the manufacture of screenprinting sheets, the use as curable printing colors by irradiation for offset printing, silk 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, which is coated with an oligomer or polymer according to the invention. These materials are suitable for the production of protective layers or the reproduction of reliefs by irradiation (optionally under a photomask) and subsequent development with a solvent. Suitable crosslinking agents, which may be contained, for example, in an amount of 0.01 to 20% by weight, are especially organic bisazides, in particular 2,6-bis (4-azidobenzilidene) -4-methyl-cyclohexanone. what can I buy. Another object of the present invention is furthermore a coated carrier material, which is characterized in that, in a carrier, a layer of (a) a cyclic olefin or at least two different cyclic olefins and (b) a catalytically effective amount of at least one thermostable compound of niobium (V) or tantalum (V), containing at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position a. Suitable carrier materials are, for example, those of glass, minerals, ceramics, plastics, woods, semimetals, metals, metal oxides and metal nitrides. The layer thicknesses are basically governed by the desired application and can be, for example, from 0.1 to 1000 μm, preferably from 0.5 to 500 μm, particularly preferred from 1 to 100 μm. The coated materials are characterized by a high bond strengthsion and good thermal and mechanical characteristics. The preparation of the coated materials according to the invention can be carried out according to known methods, such as brush application, raking, casting processes such as screen casting or centrifugal casting. In coatings, good results are often achieved when cycloolefins, which additionally contain one to three and, preferably, one further double bond and which, in the context of the invention, represent ring systems, are used for polymerization by photometatesis. condensed polycyclic The following examples illustrate the invention in more detail.
Examples 1 to 7: Polymerization of cycloolefins.
The catalyst in toluene is placed in a stirring vessel. The cycloolefin in toluene is then 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 filtered, washed with ethanol and dried under vacuum. The polymer is characterized by gel permeation chromatography [GPC; solvent: tetrahydrofuran, the numerical averages (Mn) and weight (Mw) of the molecular weight relative to the polystyrene calibration standard] and 1H-NMR (Bruker 300 MHz, solvent CDCL3) are determined. An identical experiment without irradiation at 15 = C does not result in any increase in viscosity and after adding ethanol no polymer is precipitated. The following catalysts are used: A = Ta [CH2Si (CH3) 3] 3Cl2
B = Ta [2.6- (CH3) 2C6H30] 2 (CH3) 3
C = Ta [CH2SÍ (CH3) 3] [0CH (CH3) 2] 2 D = Nb [2.6- (CH3) 2C6H30] 2 (CH3) 3 E = Ta [2.6- (CH3) 2CHC6H30] ( CH3) 3 Compounds (1) and (20) are used as monomers. The following sources of irradiation are used: (a) Mercury vapor ultraviolet lamp of medium pressure of 200 W (Osrim HBO 200 W / 2, manufacturer: Spindler &Hoyer, Göttingen). (b) Self-built ultraviolet irradiation device with TL 40W / 10R 4 X 40 W R-UVA and 2 X 20W TL 20W / 05 lamps from Philips. Distance approximately 25 cm. The results are shown in Table 1:
Table 1:
Example Catalyst Irradiation Time Yield MG 1 10 mg A 3 min (a) 100% Mn = 16 k 2 10 mg C 10 min (a) 14 h 502C 4% crosslinked 3 10 mg B 10 min (a) 14 h 502C 35% Mn = 25 k 4 10 mg E 10 min (a) 14 h 50sc 90% Mn = 165 k 5 10 mg D 3 min (a) 80% Mn = 2320k 6 250 mg A 2 h (b) 1 h 802C 100% reticulated 7 250 mg B 14 h (b) 14 h 502C 100% crosslinked
Monomer: 500 mg (20) in examples 1 to 5 (solvent: 5 ml of toluene); 25 g (1) in examples 6 and 7 (substance) Irradiation: light source (a) or (b) at 25 c Time: before treating MG: molecular weight (GPC, g / mol)
Claims (28)
1. 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, characterized in that a photochemical polymerization of ring opening by metathesis is carried out in the presence of a catalytic amount of at least a thermostable compound of niobium (V) or tantalum (V), which contains at least two methyl groups or two monosubstituted methyl groups, the substituent not containing any hydrogen atom in position a.
2. A 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 contain, if necessary, one or more heteroatoms of group 0, S, N and Si in one or more rings and, if appropriate, contain aromatic or heteroaromatic rings.
3. A method according to claim 2, characterized in that the cyclic rings contain 3 to 16 ring members.
4. A method according to claim 3, characterized in that the cyclic rings contain 3 to 12 ring members.
5. A process according to claim 2, characterized in that the cyclic olefins contain other non-aromatic double bonds.
6. A process according to claim 1, characterized in that the cycloolefins correspond to the formula I wherein Qx is a radical with at least one carbon atom, which forms together with the group -CH = CQ an alicyclic ring of at least three members, which, if appropriate, contains one or more heteroatoms chosen from the group consisting of by silicon, phosphorus, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, = 0, -CN, -N02, R? R2R3SÍ- (0) u-, -COOM, -S03M, -P03M, -COO (M?)? / 2, "S03 ( M?)? / 2, -3 (M!)? / 2, alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, cyanoalkyl of 1 to 6 atoms of carbon, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 16 carbon atoms, heteroaralkyl of 4 to 16 carbon atoms or R4-X-, or are substituted on the two neighboring carbon atoms with -CO-O-CO- or -CO-NR5-CO-, or in which, if appropriate, on the atoms of carbon adjacent to the alicyclic ring, an alicyclic, aromatic or heteroaryl atomic ring is condensed, which is unsubstituted or substituted with halogen -CN, -N02, R6R7R8SÍ- (0) u-, -COOM, -S03M, -P03M, - COO (M?)? 2, - S03 (M?)? / 2, -P03 (M?)? / 2, alkyl of 1 to 20 carbon atoms rbonone, halogenalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cyanoalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 16 carbon atoms, heteroaralkyl of 4 to 16 carbon atoms or i3 - *? -; X and Xi, independently of each other, represent -O-, -S-, - CO-, -SO-, -S02-, -OC (O) -, -C (0) -0-, -C (0) -NR5-, -NR10- C (O) -, -S02-0- or -0-S02-; R 1, R 2 and R 3, independently of one another, mean alkyl of 1 to 12 carbon atoms, perfluoroalkyl of 1 to 12 carbon atoms, phenyl or benzyl; R 4 and R 3 represent independently alkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms; R5 and R ?? independently of one another, they mean hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl, the alkyl groups for their part being unsubstituted or substituted by alkoxy of 1 to 12 carbon atoms or cycloalkyl of 3 to 8 carbon atoms; R6, R7 and Rs, independently of each other, mean alkyl of 1 to 12 carbon atoms, perfluoroalkyl of 1 to 12 carbon atoms, phenyl or benzyl; M represents an alkali metal and Mi an alkaline earth metal; and u represents 0 or 1; wherein the alicyclic ring formed with Qi contains, if appropriate, other non-aromatic double bonds; Q2 means hydrogen, alkyl of 1 to 20 carbon atoms, halogenalkyl of 1 to 20 carbon atoms, alkoxy of 1 to 12 carbon atoms, halogen, -CN, Rn ~ X2-; R n means alkyl of 1 to 20 carbon atoms, halogenalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms or aralkyl of 7 to 16 carbon atoms; X2 means -C (0) -0- or -C (0) -NR12; R 12 denotes hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; wherein the aforementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted with alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, -N02, -CN or halogen, and wherein the heteroatoms of the aforementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group -0-, -S-, -NR9- and -N =; and R9 means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl.
7. A process according to claim 6, characterized in that the alicyclic ring forming Qi together with the group -CH = CQ, has 3 to 16 ring atoms, and wherein it is a monocyclic, bicyclic, tricyclic or tetracyclic ring system .
8. A process according to claim 6, characterized in that Q2 in formula I represents hydrogen.
9. A process according to claim 6, characterized in that in the formula I Q1 is a radical with at least one carbon atom, which forms together with the group -CH = CQ2 an alicyclic ring of 3 to 20 members, which , if appropriate, contains one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and that is unsubstituted or substituted by halogen, = 0, -CN, -N02, RlR2R3SÍ- (0) u-, -C00M, -S03M, -P03M, -COO (M?)? / 2, S03 (M?) ? / 2, -P03 (M?)? / 2 alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl from 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 12 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 12 carbon atoms, heteroaralkyl of 4 to 12 atoms of carbon or R4-X-; or wherein two neighboring carbon atoms in this Q radical are substituted with -CO-O-CO- or -C0-NR5-C0-; or in which, if appropriate, in neighboring carbon atoms, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted with halogen -CN, -N02, R6R7R8SÍ- (O) u-, -COOM, -S03M, -P03M, -COO (M?)? / 2, -S03 (M?)? 2, -P03 (M?) 1/2, alkyl of 1 to 12 carbon atoms, halogenalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 12 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 12 carbon atoms, heteroaralkyl of 4 to 12 carbon atoms carbon or R13-X1-; X and XI, independently of each other, represent -0-, -S-, - CO-, -SO-, -S02-, -0-C (0) -, -C (0) -0-, -C ( 0) -NR5-, -NR? Or ~ C (O) -, -S02-0- or -0-S02-; R 1, R 2 and R 3, independently of one another, mean alkyl of 1 to 6 carbon atoms, perfluoroalkyl of 1 to 6 carbon atoms, phenyl or benzyl; M represents an alkali metal and Mi an alkaline earth metal; and R4 and R13 independently represent alkyl of 1 to 12 carbon atoms, halogenalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 12 carbon atoms. carbon, aralkyl of 7 to 12 carbon atoms; R5 and Rio, independently of one another, mean hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzyl, the alkyl groups for their part being unsubstituted or substituted by alkoxy of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 atoms of carbon; R6, R7 and Rs, independently of each other, mean alkyl of 1 to 6 carbon atoms, perfluoroalkyl of 1 to 6 carbon atoms, phenyl or benzyl; u represents 0 or 1; wherein the alicyclic ring formed with Q contains, if appropriate, other non-aromatic double bonds; Q2 means hydrogen, alkyl of 1 to 12 carbon atoms, halogenalkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, halogen, -CN, Rn- 2-; R n means alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms or aralkyl of 7 to 12 carbon atoms; X2 means -C (0) -0- or -C (0) -NRi2; and R 12 is hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzyl; wherein the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted with alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, -N02, -CN or halogen, and wherein the heteroatoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group -O-, -S-, -NR9- and -N =; and R9 means hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzyl.
10. A process according to claim 6, characterized in that in the compounds of the formula I Q1 is a radical with at least one carbon atom, which forms together with the group -CH = CQ2 an alicyclic ring of 3 to 10 members , which, if appropriate, contains one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, -CN, -N02, R? R2R3SÍ-, -COOM, -S03M, -P03M, -COO (M?)? / 2, -S03 M1) 1/2, -P03 ( M?)? / 2 / alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms carbon, phenyl, benzyl or RX-; or in which, if appropriate, in neighboring carbon atoms, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted by halogen -CN, -N02, R6R7R8Si- (0) u-, -COOM, -S03M, -P03M, -COO (M?) 1 2, -S03 (M1)? / 2, -P03 (M1)? / 2, alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms , hydroxyalkyl of 1 to 6 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl, benzyl or R 13 -X 1 -; Ri, R2 and R3, independently of each other, mean alkyl of 1 to 4 carbon atoms, perfluoroalkyl of 1 to 4 carbon atoms, phenyl or benzyl; M represents an alkali metal and Mi an alkaline earth metal; and R4 and R13 independently represent alkyl of 1 to 6 carbon atoms, halogenalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; X and XI, independently of each other, mean -O-, -S-, - CO-, -SO- or -S02-; R6, R7 and Rβ, independently of each other, mean alkyl of 1 to 4 carbon atoms, perfluoroalkyl of 1 to 4 carbon atoms, phenyl or benzyl; and Q2 means hydrogen.
11. A procedure according to the claim I, characterized in that the cyclic olefins are norborene or norborene derivatives ..
12. A process according to the claim II, characterized in that the norborene derivatives are those of the formula II where? 3 means -CHR15-, oxygen or sulfur; R14 and R15 / independently of each other, mean hydrogen, -CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3-Si or -C00R? 7; and R16 and R17? independently of one another, they mean hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; or of formula III wherein X 4 means -CHR 19, oxygen or sulfur; R19 means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; and R 8 represents hydrogen, alkyl of 1 to 6 carbon atoms or halogen; or of formula IV wherein X5 means -CHR22-, oxygen or sulfur; R22 means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; 2? and R21 independently of each other, mean hydrogen, CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3Si- or -C00R23; and R23 means hydroquinone, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; or of the formula V wherein X6 means -CHR24-, oxygen or sulfur; R 24 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzyl; And it means oxygen or > N-R25; and R25 means hydrogen, methyl, ethyl or phenyl.
13. A process according to claim 1, characterized in that the methyl group or the monosubstituted methyl group bonded to the metal atom is bonded two or three times as a ligand.
14. A process according to claim 1, characterized in that the methyl group or monosubstituted methyl group bonded to the metal atom corresponds to formula VII -CH2-R (VII), where R represents H, -CF3, -CR 5R27R28 / -SiR29R3oR3? , aryl with 6 to 16 carbon atoms or heteroaryl with 4 to 15 carbon atoms unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms, with 1 to 3 heteroatoms of group O, S and N; and R26Í R27 and R28 > independently from each other, they mean alkyl having 1 to 10 carbon atoms, which is unsubstituted or substituted by alkoxy with 1 to 10 carbon atoms, or R26 and R27 have this meaning and R28 means aryl having 6 to 10 carbon atoms or heteroaryl with 4 to 9 carbon atoms, which is unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms; and 29r R3? and R3i, independently of one another, mean alkyl having 1 to 6 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, or phenyl or benzyl unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 atoms of carbon.
15. A process according to claim 14, characterized in that the group R in the formula VII represents H, -C (CH3) 3, -C (CH3) 2C6H5, phenyl unsubstituted or substituted with methyl, ethyl, methoxy or ethoxy, - CF3 or Si (CH3) 3.
16. A process according to claim 1, characterized in that the remaining valences 1 to 3 of the atoms of Nb (V) and Ta (V) are saturated with ligands equal to or different from the group consisting of = 0, = N-R33, secondary amines with 2 to 18 carbon atoms, R3 0-, R32S-, halogen, cyclopentadienyl, bridged bicyclopentadienyl, tridentate monoanionic neutral ligands and ligands, wherein R32, independently of one another, represents linear or branched alkyl with 1 to 18 carbon atoms. carbon, unsubstituted or substituted by alkoxy with 1 to 6 carbon atoms or halogen, cycloalkyl with 5 or 6 carbon atoms, unsubstituted or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms or halogen , phenyl unsubstituted or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms, di (alkyl with 1 to 6 carbon atoms no) amino, di (C1-C6-alkyl) amino-C1-C3 alkyl or halogen, or benzyl or unsubstituted phenylethyl or substituted with C1-C6 alkyl, C1-6 alkoxy carbon atoms, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms, di (alkyl with 1 to 6 carbon atoms) amino, di (alkyl with 1 to 6 carbon atoms) amino-alkyl with 1 to 3 carbon atoms or halogen; and R33 means linear or branched alkyl with 1 to 18 carbon atoms, unsubstituted or substituted by alkoxy with 1 to 6 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, unsubstituted or substituted with alkyl having 1 to 6 carbon atoms , C 1 -C 6 alkoxy or halogen, unsubstituted or substituted phenyl with 1 to 6 carbon atoms, C 1 -C 6 alkoxy, C 1 -C 6 alkoxymethyl, alkoxyethyl with 1 6 carbon or halogen atoms, di (C 1 -C 6 -alkyl) amino, di (C 1 -C 6 -alkyl) amino-C 1 -C 3 -alkyl or halogen, or benzyl or unsubstituted phenylethyl or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms or halogen.
17. A process according to claim 1, characterized in that the niobium and tantalum compounds correspond to formula VIII wherein Me represents Nb (V) or Ta (V), at least two, preferably two or three of the radicals R39 to R3 mean a radical -CH2-R of the formula VII, wherein R means H, -CF3 , -CR26R27R28, -SiR29R30R3? , aril with 6 to 16 carbon atoms or heteroaryl with 4 to 15 carbon atoms unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms, with 1 to 3 heteroatoms of group O, S and N; R26 / R27 and 28 independently of one another, mean alkyl having 1 to 10 carbon atoms, which is unsubstituted or substituted by alkoxy with 1 to 10 carbon atoms, or R26 and R27 have this meaning and R28 means aryl with 6 to 10. carbon atoms or heteroaryl with 4 to 9 carbon atoms, which is unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms; and R29, R30 and R3i, independently of one another, mean alkyl having 1 to 6 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, or phenyl or benzyl unsubstituted or substituted with alkyl having 1 to 6 carbon atoms or alkoxy with 1 to 6 carbon atoms; two of the other radicals from R39 to R43 together denote = 0 or = N-R33, and R33 means linear or branched alkyl with 1 to 18 carbon atoms, unsubstituted or substituted by alkoxy with 1 to 6 carbon atoms, cycloalkyl with 5 or with 6 carbon atoms, unsubstituted or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms or halogen, phenyl unsubstituted or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms, di (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino- alkyl having 1 to 3 carbon atoms or halogen, or benzyl or unsubstituted phenylethyl or substituted with alkyl having 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkoxymethyl with 1 to 6 carbon atoms, alkoxyethyl with 1 to 6 carbon atoms, di (C 1-6 alkyl) amino, di (alkyl with 1 to 6 carbon atoms) to ino-alkyl having 1 to 3 carbon atoms or halogen; and / or the other radicals from R39 to R3, independently of each other, mean secondary amino with 2 to 18 carbon atoms, R320- or R2S-, halogen, cyclopentadienyl or biscyclopentadienyl or a neutral ligand, wherein R32, independently of each other, means linear or branched alkyl having 1 to 18 carbon atoms, unsubstituted or substituted by alkoxy with 1 to 6 carbon atoms or halogen, cycloalkyl with 5 or 6 carbon atoms, unsubstituted or substituted with alkyl having 1 to 6 carbon atoms , C 1 -C 6 alkoxy or halogen, unsubstituted or substituted phenyl with 1 to 6 carbon atoms, C 1 -C 6 alkoxy, C 1 -C 6 alkoxymethyl, alkoxyethyl with 1 6 carbon or halogen atoms, or benzyl or unsubstituted or substituted phenylethyl with 1 to 6 carbon atoms, 1 to 6 carbon atoms, 1 to 6 carbon atoms, 1 to 6 carbon atoms , di (al C 1 -C 6 -alkyl) amino, di (C 1 -C 6 -alkyl) amino-C 1 -C 3 -alkyl, or halogen, or benzyl or unsubstituted phenylethyl or substituted with alkyl with 1 to 6 atoms of carbon, C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxymethyl, C 1 -C 6 -alkoxyethyl, C 1 -C 6 -alkyl amino, di (alkyl with 1 to 6) carbon atoms) amino-alkyl having 1 to 3 carbon atoms or halogen.
18. A process according to claim 17, characterized in that two or three of the radicals R39 to R3 mean a radical -CH2R of the formula VII.
19. A process according to claim 1, characterized in that niobium and tantalum compounds of the formula VIII are used, wherein a) R 9 to R43 respectively represent a radical of the formula VII -CH2-R, or b) R39 and R40 represent respectively a radical of the formula VII -CH2-R, R? and R42 together represent the radical = N-R33 and R43 means unsubstituted or substituted cyclopentadienyl, R32-0- or halogen, or c) R3g, R o and R4? respectively represent a radical of the formula VII -CH2-R and R42 and R43 together represent the radical = N-R33, or R39f R4? / R4i and R42 represent respectively a radical of the formula VII -CH2 ~ R and R43 means unsubstituted cyclopentadienyl or substituted, R 32 -O- or halogen, wherein R, R 2 and R 33 have the meaning indicated in claim 17.
20. A process according to claim 1, characterized in that niobium (V) and tantalum compounds are used ( V) of formulas IX, IXa or IXb CH2-R wherein Me represents Nb (V) or Ta (V), R represents H, -C (CH3) 3, -C (CH3) 2-C6H5, -C6H5 or -Si (alkyl having 1 to 4 carbon atoms), R33 means phenyl or phenyl substituted with one to three C 1 -C 4 alkyls or C 1 -C 4 alkoxy, R 43 in formula IX, represents the group -CH 2 -R or F, Cl, Br, alkoxy with 1 to 4 carbon atoms, linear or in particular branched, unsubstituted or substituted with fluorine, phenyloxy unsubstituted or substituted with alkyl having 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or unsubstituted cyclopentadienyl or substituted with alkyl with 1 to 4 carbon atoms; R4 ?, R 2 and R43 in the formula IXa, independently of each other, mean F, Cl, Br, alkoxy with 1 to 4 carbon atoms, linear or in particular branched, unsubstituted or substituted with fluorine, phenyloxy unsubstituted or substituted with alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or cyclopentadienyl unsubstituted or substituted with alkyl having 1 to 4 carbon atoms; and R41 and R42 in formula IXb, independently of each other, mean F, Cl, Br, alkoxy with 1 to 4 carbon atoms, linear or in particular branched, unsubstituted or substituted with fluorine, unsubstituted phenyloxy or substituted with alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms 0 cyclopentadienyl unsubstituted or substituted with alkyl with 1 to 4 carbon atoms.
21. A process according to claim 1, characterized in that niobium (V) and tantalum (V) compounds of the formulas Me [CH2Si (CH3) 3] 5, CpMe [(CH2C (CH3) 2-C6H5)] are used] 3, Me (= N-2,6-dimethylC6H3) (CH3) 3, Me (= N-C6H5) [0C (CH3) 3] [(CH2SÍ (CH3) 3] 2, Me (= N- 2,6-diisopropylC6H3) [(CH2-C6H5)] 3 / Me (= N-C6H5) [0CCH3 (CF3) 2] [(CH2Si (CH3) 3] 2 / CpMe [0CCH3 (CF3) 2] 2 [( CH2-COH5)] 2, Me (= N-2, 6-diisopropylC6H3) [(CH2C (CH3) 2-C6H5)] 2C1, Cp2Me (CH3) 2 [0CH (CH3) 2], Me (= N-2, 6-di-methylC6H3 [(CH2-C6H5)] 3, CpMe [0CH (CH3) 2] 2 [(CH2Si (CH3) 3] 2, Cp2Me [(CH2-C6H5)] 3, Me [CH2SÍ (CH3) 3] 3 Cl2, Me [CH2SÍ (CH3) 3] 3 [0CH2C (CH3) 3] 2, Cp2Me [3, 5-dimethylC6H30] [(CH2Si (CH3) 3)] 2, Me (2 , 6-diisopropylphenyloxy) 2 (CH) 3, Cp Me (CH 3) 3, Me (2,6-dimethylphenyloxy) 2 (CH 3) 3, Me [CH 2 Si (CH 3) 3] 3 [0CH (CH 3)] 2, CpMe [OC (CH3) 3] 2 [(CH2-C6H5)] 2, Cp2Me [(CH2Si (CH3) 3] 3, where Cp means cyclopentadienyl and Me means Nb (V) or Ta (V). A process for the photocatalytically induced and then thermally induced polymerization of a cyclic cycloolefin or at least two cyclic cycloolefins in the presence of a metal compound as a catalyst according to claim 1, characterized in that a) the cycloolefin is first irradiated in the presence of a catalytic amount of at least one thermostable compound of niobium (V) or tantalum (V), containing at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position a; or a catalytic amount of at least one thermostable compound of niobium (V) or tantalum (V), which contains at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position optionally in an inert solvent and then mixed with at least one cycloolefin; and b) the polymerization is then terminated by heating and without irradiation. 23. A procedure according to the claim 1, characterized in that the niobium (V) and tantalum (V) compounds are used in an amount of 0.001 to 20% mol based on the amount of cycloolefin. 24. A composition containing a) a cyclic olefin or at least two different cyclic olefins and b) a catalytically effective amount of at least one thermostable niobium (V) or tantalum (V) compound, containing at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position a. 25. A coated carrier material, characterized in that a layer of (a) a cyclic olefin or at least two different cyclic olefins and (b) a catalytically effective amount of at least one thermostable niobium compound (V) is applied on a carrier. or tantalum (V), which contains at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent not containing any hydrogen atom in position a. 26. A carrier material that is coated with an oligomer or polymer obtained according to claim 1 and containing a crosslinking agent. 27. A coated carrier material, characterized in that a layer of a polymer obtained according to claim 1 is applied on a carrier. 28. A process for the manufacture of materials or reproductions of reliefs coated on carriers, in which a composition is applied According to claim 24, if appropriate, the solvent is removed, and the polymerization layer is irradiated and, if necessary, thermally annealed, or the layer is irradiated through a photomask, optionally thermally annealed, and then the non-irradiated parts are removed with a solvent. Process for the polymerization of cyclic olefins and photo-polymerizable composition Summary 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, characterized in that a photochemical polymerization of ring opening by metathesis is carried out in the presence of a catalytic amount of at least one thermostable compound of niobium (V) or tantalum (V), which contains at least two methyl groups or two monosubstituted methyl groups, the substituent not containing any hydrogen atom in position a. The process can also be carried out so that it is first irradiated and the polymerization is terminated by heating. The process is suitable, for example, for the manufacture of thermoplastic molded masses, coatings and reproductions of reliefs.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH346194 | 1994-11-17 | ||
| CH3461/94 | 1994-11-17 | ||
| PCT/EP1995/004363 WO1996016104A1 (en) | 1994-11-17 | 1995-11-06 | Process for polymerising cyclic olefins and a photopolymerisable composition |
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| Publication Number | Publication Date |
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| MXPA97003614A true MXPA97003614A (en) | 1997-08-01 |
| MX9703614A MX9703614A (en) | 1997-08-30 |
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| MX9703614A MX9703614A (en) | 1994-11-17 | 1995-11-06 | Process for polymerising cyclic olefins and a photopolymerisable composition. |
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| Country | Link |
|---|---|
| US (1) | US5821278A (en) |
| EP (1) | EP0792308B1 (en) |
| JP (1) | JPH10508893A (en) |
| KR (1) | KR970707204A (en) |
| AU (1) | AU3982295A (en) |
| BR (1) | BR9509661A (en) |
| DE (1) | DE59504518D1 (en) |
| ES (1) | ES2126948T3 (en) |
| MX (1) | MX9703614A (en) |
| TW (1) | TW355712B (en) |
| WO (1) | WO1996016104A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69814991T2 (en) | 1997-01-31 | 2004-02-26 | Teijin Ltd. | ALPHA OLEFIN AND CYCLOOLEFIN COPOLYMERS AND METHOD FOR THE PRODUCTION THEREOF |
| US5851945A (en) * | 1997-02-07 | 1998-12-22 | Exxon Chemical Patents Inc. | Olefin polymerization catalyst compositions comprising group 5 transition metal compounds stabilized in their highest metal oxidation state |
| US6040363A (en) | 1997-09-05 | 2000-03-21 | A. O. Smith Corporation | Metathesis polymerizered olefin composites including sized reinforcement material |
| US6872792B2 (en) | 2001-06-25 | 2005-03-29 | Lord Corporation | Metathesis polymerization adhesives and coatings |
| US20080200011A1 (en) * | 2006-10-06 | 2008-08-21 | Pillalamarri Sunil K | High-temperature, spin-on, bonding compositions for temporary wafer bonding using sliding approach |
| US9169334B2 (en) | 2013-01-30 | 2015-10-27 | Exxonmobil Chemical Patents Inc. | Preparation of bottlebrush polymers via ring-opening metathesis polymerization |
| WO2014120433A1 (en) * | 2013-01-30 | 2014-08-07 | Exxonmobil Chemical Patents Inc. | Preparation of bottlebrush polymers via ring-opening metathesis polymerization |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4060468A (en) * | 1976-10-04 | 1977-11-29 | The Goodyear Tire & Rubber Company | Olefin metathesis process and catalyst therefor |
| DE3922546A1 (en) * | 1989-07-08 | 1991-01-17 | Hoechst Ag | METHOD FOR THE PRODUCTION OF CYCLOOLEFINPOLYMERS |
| US5371158A (en) * | 1990-07-05 | 1994-12-06 | Hoechst Aktiengesellschaft | Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers |
| US5198511A (en) * | 1991-12-20 | 1993-03-30 | Minnesota Mining And Manufacturing Company | Polymerizable compositions containing olefin metathesis catalysts and cocatalysts, and methods of use therefor |
| EP0719294A1 (en) * | 1993-06-30 | 1996-07-03 | Exxon Chemical Patents Inc. | A new catalyst for ring-opening metathesis polymerization |
| JP3423378B2 (en) * | 1993-11-12 | 2003-07-07 | 三井化学株式会社 | Novel transition metal compound, olefin polymerization catalyst component comprising the transition metal compound, olefin polymerization catalyst containing the olefin polymerization catalyst component, and olefin polymerization method |
-
1995
- 1995-11-06 MX MX9703614A patent/MX9703614A/en unknown
- 1995-11-06 BR BR9509661A patent/BR9509661A/pt not_active Application Discontinuation
- 1995-11-06 US US08/836,227 patent/US5821278A/en not_active Expired - Fee Related
- 1995-11-06 KR KR1019970703294A patent/KR970707204A/en active IP Right Grant
- 1995-11-06 AU AU39822/95A patent/AU3982295A/en not_active Abandoned
- 1995-11-06 DE DE59504518T patent/DE59504518D1/en not_active Expired - Fee Related
- 1995-11-06 ES ES95938426T patent/ES2126948T3/en not_active Expired - Lifetime
- 1995-11-06 JP JP8516498A patent/JPH10508893A/en not_active Ceased
- 1995-11-06 EP EP95938426A patent/EP0792308B1/en not_active Expired - Lifetime
- 1995-11-06 WO PCT/EP1995/004363 patent/WO1996016104A1/en active IP Right Grant
- 1995-11-16 TW TW084112121A patent/TW355712B/en active
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