CA2242060A1 - Cycloolefin-based adhesive - Google Patents
Cycloolefin-based adhesive Download PDFInfo
- Publication number
- CA2242060A1 CA2242060A1 CA 2242060 CA2242060A CA2242060A1 CA 2242060 A1 CA2242060 A1 CA 2242060A1 CA 2242060 CA2242060 CA 2242060 CA 2242060 A CA2242060 A CA 2242060A CA 2242060 A1 CA2242060 A1 CA 2242060A1
- Authority
- CA
- Canada
- Prior art keywords
- composition according
- substituted
- formula
- component
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 150000001925 cycloalkenes Chemical class 0.000 title claims abstract description 16
- 239000000853 adhesive Substances 0.000 title claims abstract description 14
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000077 silane Inorganic materials 0.000 claims abstract description 5
- 125000006734 (C2-C20) alkoxyalkyl group Chemical group 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052882 wollastonite Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 229910001679 gibbsite Inorganic materials 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims 1
- -1 polyethylene Polymers 0.000 description 135
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 21
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000003446 ligand Substances 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 13
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002367 halogens Chemical group 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 0.000 description 8
- 150000002390 heteroarenes Chemical class 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000001072 heteroaryl group Chemical group 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 5
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000001204 arachidyl group Chemical class [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 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000002704 decyl group Chemical class [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 5
- 125000003438 dodecyl group Chemical class [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 5
- 125000003187 heptyl group Chemical class [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 5
- 125000004051 hexyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000002960 margaryl group Chemical class [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 5
- 125000001421 myristyl group Chemical class [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 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001400 nonyl group Chemical class [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 5
- 125000002347 octyl group Chemical class [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 5
- 125000000913 palmityl group Chemical class [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 5
- 125000002958 pentadecyl group Chemical class [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 5
- 125000001147 pentyl group Chemical class C(CCCC)* 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 125000004079 stearyl group Chemical class [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 5
- 229930192474 thiophene Natural products 0.000 description 5
- 125000002889 tridecyl group Chemical class [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 5
- 125000002948 undecyl group Chemical class [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 5
- 229910001868 water Inorganic materials 0.000 description 5
- 241001120493 Arene Species 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000001196 nonadecyl group Chemical class [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 4
- 150000002848 norbornenes Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HNUALPPJLMYHDK-UHFFFAOYSA-N C[CH]C Chemical compound C[CH]C HNUALPPJLMYHDK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical class C1(=CC=CC1)* 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 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
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
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- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
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- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- GYQFZZIOJGPSSR-UHFFFAOYSA-N prop-2-ynylbenzene Chemical compound [C-]#CCC1=CC=CC=C1 GYQFZZIOJGPSSR-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 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
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical class [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- BUGOPWGPQGYYGR-UHFFFAOYSA-N thiane 1,1-dioxide Chemical compound O=S1(=O)CCCCC1 BUGOPWGPQGYYGR-UHFFFAOYSA-N 0.000 description 1
- NNLBRYQGMOYARS-UHFFFAOYSA-N thiane 1-oxide Chemical compound O=S1CCCCC1 NNLBRYQGMOYARS-UHFFFAOYSA-N 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical group CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the use, as an adhesive, of a composition comprising (a) at least one strained cycloolefin, (b) a catalyst for ring-opening metathesis polymerisation, (c) a filler and (d) a silane of formula I
(see fig. I) , wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may have been replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y1, Y2 and Y3 are each independently of the others C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C12cycloalkyl, C2-C20alkoxyalkyl or C1-C20acyl.
(see fig. I) , wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may have been replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y1, Y2 and Y3 are each independently of the others C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C12cycloalkyl, C2-C20alkoxyalkyl or C1-C20acyl.
Description
Cycloolefin-based adhesive The present invention relates to the use, as an adhesive, of a composition comprising a strained cycloolefin, a catalyst, a filler and a silane, and to a method of bonding substrates.
In WO 96/16100 and WO 96/20235 it is mentioned that the ROMP systems (ROMP = ring-opening metathesis polymerisation) described therein based on strained cycloolefins and specific ruthenium catalysts are suitable as adhesives for bonding Teflon, polyethylene and polypropylene. The adhesion to the substrate is inadequate for certain uses, however, owing to the low polarity of the cycloolefins.
Bonds made with reactive adhesives exhibit inner strains caused by reaction shrinkage when the relatively large intermolecular spacing between the monomers are replaced by the closer spacing of the covalent bonds between the polymer segments. The shrinkage can bereduced by the addition of suitable fillers, but the addition of fillers generally results in a breakdown of the cohesion.
Surprisingly, it has now been found that the ROMP systems described in EP-A-771 830, together with fillers, exhibit very good adhesion and can consequently be used as adhesives.
The present invention relates to the use, as an adhesive, of a composition comprising (a) at least one strained cycloolefin, (b) a catalyst for ring-opening metathesis polymerisation, (c) a filler and (d) a silane of formula I
OY, R--Si OY2 (I ), oy3 wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may be replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y" Y2 and Y3 are each independently of the others C,-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C,2cycloalkyl, C2-C20alkoxyalkyl or C,-C20acyl.
When fully cured, the ROMP system exhibits an especially high degree of adhesion to metals, for example iron or aluminium. Preference is accordingly given to the use of the above-specified composition as an adhesive for metals, especially for aluminium.
Within the scope of the present invention there is to be understood by "strained cycloolefin"
any cycloolefin, with the exception of cyclohexene and derivatives thereof, which cannot be polymerised by ring-opening metathesis.
Strained cycloolefins may be monocyclic or polycyclic fused or bridged ring systems, for example having from two to four rings, that are unsubstituted or substituted and may contain hetero atoms, for example oxygen, sulfur, nitrogen or silicon, in one or more rings and/or may contain fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthyl-ene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings may contain from 3 to 16, especially from 3 to 12, and more especially from 3 to 8, ring members. The strained cyclo-olefins may contain further non-aromatic double bonds, preference being given, depending on the ring size, to from 2 to 4 such additional double bonds. The ring substituents are inert, that is to say those substituents do not impair the chemical stability and the thermostability of the ROMP catalysts.
When the strained cycloolefins contain more than one double bond, for example from 2 to 4 double bonds, it is possible also for crosslinked polymers to be formed, depending on the reaction conditions, the monomer selected and the amount of catalyst.
There is preferably used as component (a) in the composition according to the invention a compound of formula ll \ / (Il), wherein Q, is a radical having at least one carbon atom, which radical, together with the -CH=CQ2 group, forms an alicyclic ring having a minimum of three members that may contain one or more hetero atoms selected from the group silicon, phosphorus, oxygen, nitrogen and sulfur and that is unsubstituted or substituted by halogen, =0, -CN, -NO2, R1R2R3Si-(O)u~, -COOM, -S03M, -PO3M, -COO(M,)1,2, -SO3(M,)"2, -PO3(M,)"2, C,-C20alkyl, C,-C20hydroxyalkyl, C,-C20haloalkyl, C1-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, C7-C,6-aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C,6heteroaralkyl or by R4-X-; or in which two adjacent carbon atoms are bonded by -CO-O-CO- or -CO-NR5-CO-; or in which there is fused to adjacent carbon atoms of the alicyclic ring an alicyclic, aromatic or heteroaromatic ring that is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-(O)U-, -COOM, -SO3M, -PO3M, -COO(M1)1,2, -S03(M1)"2, -PO3(M1)"2, C,-C20alkyl, C,-C20haloalkyl, C,-C20-hydroxyalkyl, C,-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, C7-C,6aralkyl, C3-C6heterocyclo-alkyl, C3-C,6heteroaryl, C4-C,6heteroaralkyl or by R,3-X,-; X and X1 are each independently of the other -O-, -S-, -CO-, -SO-, -SO2-, -O-CO-, -COO-, -CO-NR5-, -NR10-CO-, -SO2-O- or -O-SO2-; R1, R2 and R3 are each independently of the other C,-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl; R4 and R~3 are each independently of the other C,-C20alkyl, C,-C20-haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or C7-C,6aralkyl; R5 and R,O are each independently of the other hydrogen, C,-C,2alkyl, phenyl or benzyl, the alkyl groups in turn being unsubstituted or substituted by C,-C,2alkoxy or by C3-C8cycloalkyl; R6, R7 and R8 are each independently of the others C,-C,2alkyl, C,-C,2perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M, is an alkaline earth metal; and u is O or 1; it being possible for the alicyclic ring formed with Q, to contain further non-aromatic double bonds;
Q2 is hydrogen, C,-C20alkyl, C,-C20haloalkyl, C,-C,2alkoxy, halogen, -CN or R"-X2-; R" is C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or C7-C,6aralkyl; X2 is -COO- or -CO-NR,2-; and R,2 is hydrogen, C,-C,2alkyl, phenyl or benzyl;
wherein the above-mentioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups may be unsubstituted or substituted by C,-C,2alkyl, C,-C,2alkoxy, -NO2, -CN or by halogen, and wherein the hetero atoms of the above-mentioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group -O-, -S-, -NRg- and -N=, Rg being hydrogen, C,-C,2alkyl, phenyl or benzyl.
Fused-on alicyclic rings contain preferably from 3 to 8, especially from 4 to 7, and more especially 5 or 6, ring carbon atoms.
For the purpose of crosslinking or to control the molecular weight, the composition according to the invention may contain further olefins capable of metathesis, advantageously in amounts of up to 40 mol %, especially from 0.01 to 30 mol % and more especially from 0.1 to 20 mol %, based on the total amount of the cycloolefins and olefins present.
Suitable olefins capable of metathesis are, for example, cyclooctadiene, cyclooctatriene, norbornadiene and acetylnorbornene. Also suitable are compounds such as 2-butene-1,4-diol, as described in Feast, W.J., Harrison, B., J. Mol. Catal. 65, 63 (1991), or 1-hexene (rearrangements) .
The presence of an asymmetric centre in the compounds of formula ll means that those compounds may occur in optically isomeric forms. Some compounds of formula ll may occur in the form of tautomers (e.g. keto-enol tautomerism). If an aliphatic C=C double bond is present, then also geometric isomerism may occur (E-form or Z-form). In addition, exo/endo configurations are also possible. Formula ll hence includes all possible stereoisomers, which are in the form of enantiomers, tautomers, diastereoisomers, E/Z isomers or mixtures thereof.
The alkyl, alkenyl and alkynyl groups in the definitions of the substituents may be straight-chain or branched. The same applies also to the alkyl moiety or each of the alkyl moieties of alkoxy, alkylthio, alkoxycarbonyl and other alkyl-containing groups. The alkyl groups contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 4, carbon atoms. The alkenyl and alkynyl groups contain preferably from 2 to 12, especially from 2 to 8, and more especially from 2 to 4, carbon atoms.
Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomers of 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-hydroxyisobutyl, 1-hydroxy-sec-butyl, 1-hydroxy-tert-butyl and the various hydroxy-substituted isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-tri-chloroethyl and halogenated, especially fluorinated or chlorinated, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups and the various halogenated isomers of 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, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
Cycloalkyl is preferably C5-C8cycloalkyl, especially C5- or C6-cycloalkyl. Examples include cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Cyanoalkyl includes, for example, cyanomethyl (methylnitrile), cyanoethyl (ethylnitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyanoisobutyl, 1-cyano-sec-butyl, 1-cyano-tert-butyl and the various isomers of cyanopentyl and cyanohexyl.
Aralkyl contains especially from 7 to 12 carbon atoms and more especially from 7 to 10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, 4-phenylbutyl or a,a-dimethylbenzyl.
Aryl contains preferably from 6 to 10 carbon atoms. It may be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl or anthryl.
Heteroaryl contains preferably 4 or 5 carbon atoms and one or two hetero atoms from the group oxygen, sulfur and nitrogen. It may be, for example, pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, purinyl or quinolyl.
Heterocycloalkyl contains preferably 4 or 5 carbon atoms and one or two hetero atoms from the group oxygen, sulfur and nitrogen. It may be, for example, oxiranyl, azirinyl, 1,2-oxathiolanyl, pyrazolinyl, pyrrolidinyl, piperidyl, piperazinyl, morpholinyl, tetrahydrofuranyl or tetrahydrothiophenyl.
Alkoxy is, for example, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy or tert-butyloxy.
Within the scope of the present invention, alkali metal is to be understood as meaning lithium, sodium, potassium, rubidium or caesium, especially lithium, sodium or potassium.
Within the scope of the present invention, alkaline earth metal is to be understood as meaning beryllium, magnesium, calcium, strontium or barium, especially magnesium or calcium.
In the above definitions, halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Especially well-suited compounds of formula ll in the composition according to the invention are those wherein Q2 is hydrogen.
Preference is given also to compounds of formula ll wherein Q, is a radical having at least one carbon atom, which radical, together with the -CH=CQ2- group, forms a 3- to 10-membered alicyclic ring that may contain a hetero atom selected from the group silicon, oxygen, nitrogen and sulfur and that is unsubstituted or substituted by halogen, -CN, -NO2, R,R2R3Si-, -COOM, -SO3M, -PO3M, -COO(M,)"2, -S03(M,)"2, -PO3(M,)"2, C1-C6alkyl, C,-C6-haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or by R4-X-; or in which there may be fused to adjacent carbon atoms an aromatic or heteroaromatic or alicyclic ring that is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M,)1~2, -SO3(M1)1~2, -PO3(M1)1~2, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or by R13-X1-; R1, R2 and R3 are each independently of the others C1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M, is an alkaline earth metal; R4 and R13 are each independently of the other C1-C6alkyl, C1-C6haloalkyl, C,-C6hydroxyalkyl or C3-C6cycloalkyl; X and X1 are each independently of the other-O-, -S-, -CO-, -SO- or-S02- and R6, R7 and R8 are each independently of the others C,-C4alkyl, C,-C4perfluoroalkyl, phenyl or benzyl.
Norbornene and norbornene derivatives, especially dicyclopentadiene and dicyclopentadiene derivatives, are especially preferred as component (a).
Preferred norbornene derivatives are the compounds of formulae lll, IV, V and Vl ~14 ~ (IV), R.8 ~ (V), ~ (Vl), wherein X3 is -CHR16-, oxygen or sulfur, R14 and R15 are each independently of the other hydrogen, -CN, trifluoromethyl, (CH3)3SiO-, (CH3)3Si- or -COOR17, and R16 and R17 are each independently of the other hydrogen, C1-C12alkyl, phenyl or benzyl;
X4 is -CHR19-, oxygen or sulfur, R19 is hydrogen, C1-C12alkyl, phenyl or benzyl and R18 is hydrogen, C1-C6alkyl or halogen;
Xs is -CHR22-, oxygen or sulfur, R22 is hydrogen, C1-C12alkyl, phenyl or benzyl, R20 and R21 are each independently of the other hydrogen, CN, trifluoromethyl, (CH3)3SiO-, (CH3)3Si- or -COOR23 and R23 is hydrogen, C1-C12alkyl, phenyl or benzyl;
X6 is -CHR24-, oxygen or sulfur, R24 is hydrogen, C1-C12alkyl, phenyl or benzyl, Y is oxygen or \N--R and R25 is hydrogen, methyl, ethyl or phenyl.
Examples of suitable compounds of formula ll are the following cycloolefins:
~ (2)~ ~ (3).
CA 02242060 l998-06-30 COOH ~~ COOCH3 ~\~(4), ~ (5), / (6), o O o COOCH2phenyl ~_ COOCzHs /~~ COO(CH2)~CH3 ~ (7). ~ (8), ~ (9).
COOCH2phenyl COOCzHs coo(CH2)3cH3 O O
~_ COO(CH2)sCH3 ~ COO(CH2)9CH3 ~_ COO(CH2),lCH3 ~ (10). ~ (11), ~ (12 Coo(cH2)scH3coo(cH2)9cH3 coo(cH2)1~c~l3 O O
~f(,3). ~ f~(,4) ~ f~(1s) ~ O NH
O O O
O O O
f (16), f (17)' fo (18), N ' CH3 C2H5 ~ phenyl O O O
~(19)~ 3(20), (~)(21), (22), ~ (23), [3 (24), [~ (25), b (26), b (27), ~ (28), (29), ~ ~ (30)~ b CN (31), \CH2NHCH3 1~ .
~( (32), ~V Sl(CH3)3 (33), b P(C6H5)2 (34~ b~ CH2~(CH2)5~CH3 (35 P(C6H5)2 b 3 (36), ~ ~ (37), o_ _ ~ " (38), ~3 (39)' (40~ ,3(41)~
~1 ~3 (42), ~ 3 (43) In a preferred embodiment, the strained cycloolefins contain only carbon and hydrogen atoms, and are preferably 5- or 6-membered rings, or ring systems having from one to three 5- or 6-membered rings, for example norbornenes, alkylated norbornenes and dicyclopenta-diene.
Especially preferred as component (a) is dicyclopentadiene.
A large number of compounds of the transition metals titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium and osmium are known to the person skilled in the art as catalysts for ring-opening metathesis polymerisation (ROMP catalysts). Such compounds are, for example, complex metal halides, metallo-carbenes or co-ordination catalysts of the Ziegler-Natta type. In principle, any of those known ROMP catalysts may be used as component (b) in the compositions according to the invention.
Preferably, a ruthenium(+ll) complex salt or an osmium(+ll) complex salt, especially a ruthenium(+ll) complex salt, is used as component (b).
Since the fillers according to component (c) often contain small amounts of water, it is advisable to use ROMP catalysts that are not sensitive to moisture, such as, for example, the ruthenium(+ll) and osmium(+ll) complex salts described in WO 96/16100 and WO 96/20235.
The preferred component (b) is therefore a complex salt of formula lll (R2sR3oR31p)xLyMe2+z1-z2 (111), wherein R29, R30 and R3, are each independently of the others H, C,-C20alkyl, C,-C20alkoxy, unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C4-C,2cycloalkyl or cycloalkoxy, or unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C6-C,6aryl or C6-C,6aryloxy, or unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C7-C,6aralkyl or C7-C,6aralkyloxy; the radicals R30 and R3, together are unsub-stituted or C,-C6alkyl-, C,-G6haloalkyl- or C,-C6alkoxy-substituted tetra- or penta-methylene or tetra- or penta-methylenedioxy; or are tetra- or penta-methylene or tetra- or penta-methylenedioxy that is unsubstituted or substituted by C,-C6alkyl, C,-C6haloalkyl or C,-C6alkoxy and fused with one or two 1 ,2-phenylene radicals; or are tetramethylenedioxy that is unsubstituted or substituted by C,-C6alkyl, C1-C6haloalkyl or C,-C6alkoxy and fused in the 1,2- and 3,4-positions with 1,2-phenylene; and R3, is as defined hereinbefore;
L is a neutral ligand, Me is Ru or Os, Z,~ and Z2- are each a singly charged anion or Z,~ and Z2- together are a doubly charged anion, x is a number from 1 to 3 and y is a number from 0 to 3, such that 2 5 x+y < 4.
The ligands L in the compounds of formula lll may be identical or different.
The ruthenium and osmium compounds of formula lll are known or can be prepared according to known processes from the metal halides (for example MeX3 or [Me-areneX2]2) by reaction with phosphines of formula IV
R29R30R3, P (IV), wherein R29, R30 and R3, are as defined for formula (Ill), and ligand formers.
The radicals R29, R30 and R3, are preferably identical radicals. Also, sterically bulky radicals are preferred, for example branched, especially a-branched, alkyl or alkoxy, or cyclic radicals.
R29, R30 and R3, as alkyl may be linear or branched and contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 6, carbon atoms. Examples of alkyl are methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, CA 02242060 l998-06-30 heptadecyl, octadecyl and eicosyl. Preferred examples are methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl.
R29, R30 and R3, as alkoxy may be linear or branched and contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 6, carbon atoms. Examples of alkoxy are methoxy, ethoxy, n- and iso-propyloxy, n-, iso- and tert-butyloxy, and the isomers of pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy and eicosyloxy. Preferred examples are methoxy, ethoxy, n- and iso-propyloxy, n-, iso- and tert-butyloxy, 1-, 2- or 3-pentyloxy and 1-, 2-, 3- or 4-hexyloxy.
Where R29, R30 and R31 are substituted, the substituents are preferably C,-C4alkyl, C1-C4--haloalkyl or C,-C4alkoxy. Halogen is preferably chlorine and especially fluorine. Examples of preferred substituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl. R29, R30 and R3, are preferably substituted by from 1 to 3 substituents.
R29, R30 and R3, as cycloalkyl are preferably C5-C8cycloalkyl and especially C5- or C6-cycloalkyl. Examples include cyclobutyl, cycloheptyl and cyclooctyl, and especially cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-cyclopentyl and -cyclohexyl.
R29, R30 and R3, as cycloalkyloxy are preferably C5-C8cycloalkyloxy and especially C5- or C6-cycloalkyloxy. Examples include cyclobutyloxy, cycloheptyloxy and cyclooctyloxy, and especially cyclopentyloxy and cyclohexyloxy. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)-and tris(trifluoromethyl)-cyclopentyloxy and -cyclohexyloxy.
R29, R30 and R3, as aryl are preferably C6-C,2aryl and especially phenyl or naphthyl.
Examples of substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-phenyl.
R29, R30 and R3, as aryloxy are preferably C6-C,2aryloxy and especially unsubstituted or substituted phenyloxy or naphthyloxy. Examples of substituted aryloxy are methyl-, dimethyl-, trimethyl-, methylisopropyl-, isopropyl-, diisopropyl-, triisopropyl-, tert-butyl-, methyltert-butyl-, di(tert-butyl)-, tri(tert-butyl)-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-phenyloxy.
R29, R30 and R3, as aralkyl are preferably C7-C13aralkyl, the alkylene group in the aralkyl preferably being methylene. The aralkyl is especially benzyl. Examples of substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-benzyl.
R29, R30 and R3, as aralkyloxy are preferably unsubstituted or substituted C7-C13aralkyloxy, the alkylene group in the aralkyloxy preferably being methylene. The aralkyloxy is especially unsubstituted or substituted benzyloxy. Examples of substituted aralkyloxy are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)-and tris(trifluoromethyl)-benzyloxy.
Special preference is given to complex salts of formula lll wherein R29, R30 and R3, are C1-C6alkyl, C,-C6alkoxy, C4-C12cycloalkyl, C4-C12cycloalkoxy, C6-C16aryl or C6-C,6aryloxy.
Especially preferred are complex salts of formula lll wherein R29, R30 and R3, are phenyl, tolyl or cyclohexyl.
Examples of suitable phosphines of formula IV are (C6Hs)3P, (C6H5CH2)3P, (C5H11)3P, (CH3)3P, (C2H5)3P, (n-C3H7)3P, (iso-C3H7)3P, (n-C4Hg)3P, (C6H5)2HP, (C6H5CH2)2HP, (C5H11)2HP, (CH3)2HP, (C2H5)2HP, (n-C3H7)2HP, (iso-C3H7)2HP, (n-C4Hg)2HP, (C6H5)H2P, (C6H5CH2)H2P, (C5H,1)H2P, (CH3)H2P, (C2H5)H2P, (n-C3H7)H2P, (iso-C3H7)H2P, (n-C4Hg)H2P, PH3, (2-CH3-C6H4)3P, (3-CH3-C6H4)3P, (4-CH3-C6H4)3P, (2,4-di-CH3-C6H3)3P, (2,6-di-CH3-C6H3)3P, (2-C2H5-C6H4)3P, (3-C2H5-C6H4)3P, (4-C2H5-C6H4)3P, (2-n-C3H7-C6H4)3P, (3-n-C3H7-C6H4)3P, (4-n-C3H7-C6H4)3P, (2-iso-C3H7-C6H4)3P, (3-iso-C3H7-C6H4)3P, (4-iso-C3H7-C6H4)3P, (2-n-C4Hg-C6H4)3P, (3-n-C4Hg-C6H4)3P, (4-n-C4Hg-C6H4)3P, (2-iso-C4Hg-C6H4)3P, (3-iso-C4Hg-C6H4)3P, (4-iso-C4Hg-C6H4)3P, (2-tert-C4Hg-C6H4)3P, (3-tert-C4Hg-C6H4)3P, (4-tert-C4Hg-C6H4)3P, (2-CH3-6-tert-C4Hg-C6H3)3P, (3-CH3-6-tert-C4Hg-C6H3)3P, (3-CH3-6-tert-C4Hg-C6H3)3P, (2,6-di-tert-C4Hg-C6H3)3P, (2,3-di-tert-C4Hg-C6H3)3P and (2,4-di-tert-C4Hg-C6H3)3P .
Especially preferred phosphines are triisopropylphosphine, tri-tert-butylphosphine and tricyclohexylphosphine.
CA 02242060 l998-06-30 The ligands L bonded to the metal atom in the compounds of formula lll may be photolabile or non-photolabile ligands.
In the case of compounds of formula lll having photolabile ligands the catalytic activity is achieved by the action of light, that is to say on irradiation of the catalyst with light in the visible or ultraviolet range the photolabile ligand is removed, and a species is formed which is catalytically active for the metathesis polymerisation.
The photolabile ligands may be, for example, nitrogen (N2), unsubstituted or OH-, C,-C4alkyl-, Cj-C4alkoxy-, C6-C12aryl- or halo-substituted monocyclic, polycyclic or fused arenes having from 6 to 24, especially from 6 to 18, and more especially from 6 to 12, carbon atoms, or unsubstituted or C,-C4alkyl-, C,-C4alkoxy- or halo-substituted monocyclic hetero-arenes, fused heteroarenes or fused arene-heteroarenes having from 3 to 22, especially from 4 to 16, and more especially from 4 to 10, carbon atoms and from 1 to 3 hetero atoms selected from the group oxygen, sulfur and nitrogen; or unsubstituted or C,-C4alkyl-, C,-C4alkoxy- or halo-substituted aliphatic, cycloaliphatic, aromatic or araliphatic nitriles having from 1 to 22, especially from 1 to 18, more especially from 1 to 12, and preferably from 1 to 7, carbon atoms. The preferred substituents are methyl, ethyl, methoxy, ethoxy, fluorine, chlorine and bromine. The arenes and heteroarenes are preferably substituted by from one to three radicals. The preferred heteroarenes are the electron-rich heteroarenes.
Examples of arenes and heteroarenes include benzene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoroanthrene, furan, thiophene, pyrrole, pyridine, ~-pyran, ~-thiopyran, pyrimidine, pyrazine, indole, cumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene and purine. Preferred arenes and heteroarenes are unsubstituted or substituted benzene, naphthalene, thiophene and benzthiophene. The arene is especially benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals and the heteroarene is preferably thiophene.
The nitriles may be substituted, for example, by methoxy, ethoxy, fluorine or chlorine;
preferably, the nitriles are unsubstituted. The alkylnitriles are preferably linear. Examples of CA 02242060 l998-06-30 nitriles include acetonitrile, propionitrile, butyronitrile, pentylnitrile, hexylnitrile, cyclopentyl-and cyclohexyl-nitrile, benzonitrile, methylbenzonitrile, benzylnitrile and naphthylnitrile. The nitriles are preferably linear C1-C4alkylnitriles or benzonitrile. Of the alkylnitriles, acetonitrile is especially preferred.
In a preferred sub-group, the photolabile ligands are N2, benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals, thiophene, benzonitrile or acetonitrile.
Within the scope of the present invention "non-photolabile ligand" (also called "strongly co-ordinating ligand") denotes that the ligand does not dissociate, or dissociates only to an insignificant extent, from the catalyst on irradiation of the catalyst in the visible or near ultraviolet spectral range.
The non-photolabile ligands may be, for example, solvating inorganic and organiccompounds containing the hetero atoms O, S or N, which are frequently also used as solvents. Examples of such compounds are H2O, H2S, NH3; unsubstituted or halogenated, especially fluorinated or chlorinated, aliphatic or cycloaliphatic alcohols or mercaptans having from 1 to 18, especially from 1 to 12, and more especially from 1 to 6, carbon atoms, aromatic alcohols or thiols having from 6 to 18, especially from 6 to 12, carbon atoms, araliphatic alcohols or thiols having from 7 to 18, especially from 7 to 12, carbon atoms;
open-chained or cyclic and aliphatic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones, carboxylic acid amides having from 2 to 20, especially from 2 to 12, and more especially from 2 to 6, carbon atoms which may be non-N-alkylated or N-C1-C4-mono- or -di-alkylated, and lactams which may be non-N-alkylated or N-C1-C4alkylated; and open-chained or cyclic and aliphatic, araliphatic or aromatic, primary, secondary and tertiary amines having from 1 to 20, especially from 1 to 12, and more especially from 1 to 6, carbon atoms.
Examples of such non-photolabile ligands are methanol, ethanol, n- and iso-propanol, n-, iso-and tert-butanol, 1,1,1-trifluoroethanol, bistrifluoromethylmethanol, tristrifluoromethyl-methanol, pentanol, hexanol, methyl- or ethyl-mercaptan, cyclopentanol, cyclohexanol, cyclohexylmercaptan, phenol, methylphenol, fluorophenol, phenylmercaptan, benzyl-mercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-tert-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, tetrahydrothiophene, dimethyl sulfoxide, diethyl sulfoxide, tetra- and penta-methylene sulfoxide, dimethylsulfone, CA 02242060 l998-06-30 diethylsulfone, tetra- and penta-methylenesulfone, acetone, methyl ethyl ketone, diethyl ketone, phenyl methyl ketone, methyl isobutyl ketone, benzyl methyl ketone, acetaldehyde, propionaldehyde, trifluoroacetaldehyde, benzaldehyde, ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide, pyrrolidone and N-methylpyrrolidone.
The primary amines may correspond to the formula R26NH2, the secondary amines to the formula R26R27NH and the tertiary amines to the formula R26R27R28N, wherein R26 is C1-C,8alkyl, unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C5- or C6-cycloalkyl, or unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C6-C18aryl or C7-C12aralkyl, R27 independently has the meaning given for R26, or R26 and R27 together are tetramethylene, pentamethylene, 3-oxa-1,5-penty!ene or-CH2-CH2-NH-CH2-CH2- or-CH2-CH2-N(C1-C4alkyl)-CH2-CH2-, and R28 independently has the meaning given for R26. The alkyl contains especially from 1 to 12, and more especially from 1 to 6, carbon atoms. The aryl contains preferably from 6 to 12 carbon atoms and the aralkyl contains preferably from 7 to 9 carbon atoms. Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methylethyl-, dimethylethyl-, n-propyl-, di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- and benzyl-amine, and also pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.
Preferably, the compositions according to the invention comprise as component (b) a complex salt of formula lll wherein L is an arene, a heteroarene, a nitrile, nitrogen (N2), an alcohol, an amine, CO, H20 or NH3.
Especially preferred as component (b) is a complex salt of formula lll wherein L is benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals, thiophene, benzonitrile, acetonitrile, nitrogen (N2), an unsubstituted or partially or fully fluorinated C1-C4alcohol, CO, H20 or NH3.
In the compounds of formula lll, Z1- and Z2- may each be a singly charged anion, it being possible for Z1- and Z2- to be identical or different, or Z1- and Z2- may together be a doubly charged anion.
Suitable anions are, for example, hydride (H-), halide (for example Cl-, Br~ and 1-), BF4-, PF6-, SbF6-, AsF6-, unsubstituted or C,-C4alkyl-, C1-C4alkoxy-, (C,-C4alkyl)3Si- or (C,-C4alkyl)3SiO-substituted cyclopentadienyl~, or indenyl~, and the anions of oxyacids.
CA 02242060 l998-06-30 Further suitable anions are C,-C,2-, especially C,-C6- and more especially C1-C4-alcoholates, which are especially branched and correspond, for example, to the formula RXRyRzC~O~~
wherein Rx is H or C1-C,0alkyl, Ry is C1-C10alkyl and Rz is C1-C10alkyl or phenyl. Examples are especially isopropyloxy and tert-butyloxy.
Other suitable anions are C3-C18-, especially C5-C14- and more especially C5-C12-acetylides, which may correspond to the formula RW-C-C-~ wherein Rw is C1-C16alkyl, preferably a-branched C3-C12alkyl, for example of the formula RXRyRzC~~ or is phenyl or benzyl unsubstituted or substituted by from one to three C1-C4alkyl or C1-C4alkoxy radicals.
Examples include isopropylacetylide, iso- and tert-butylacetylide, phenylacetylide, benzylacetylide, 2-methylphenylacetylide, 2-isopropylphenylacetylide, 2-isopropyl-6-methylphenylacetylide, 2-tert-butylphenylacetylide, 2,6-di-tert-butylphenylacetylide and 2-methyl-6-tert-butylphenylacetylide.
The anions of oxyacids may be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C1-C8carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or tri-chloro- or -fluoro-acetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate); phenylsulfonate or benzylsulfonate unsubstituted or substituted by C,-C4alkyl, C,-C4alkoxy or by halogen, especially fluorine, chlorine or bromine, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxy-phenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropyl-sulfonate; and phosphonates, for example methylphosphonate, ethylphosphonate, propylphoshonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate and benzylphosphonate.
Preferably, Z1- and Z2- in formula lll are H-, Cl-, Br~, BF4-, PF6-, SbF6-, AsF6-, CF3SO3-, C6H5-SO3-, p-toluenesulfonate (tosylate), 3,5-dimethylphenylsulfonate, 2,4,6-trimethylphenyl-sulfonate, 4-trifluoromethylphenylsulfonate or cyclopentadienyl.
Especially preferred ROMP catalysts of formula lll are [(cyclohexyl)3P]2RuCI2, [(C6H5)3P]3RuC12, [(C6H5)3P]3(CO)RuH2, [(C6H5)3P]3RuCl(cyclopentadienyl), CA 02242060 l998-06-30 [(cyclohexyl)3P]2(CH3OH)Ru(tosylate)2, [(o-tolyl)3P]3RuCI2, [(CH3)2CH]3P(p-cymene)RuCI2 and especially (cyclohexyl)3P(p-cymene)RuCI2.
Suitable fillers which may be used as component (c) in the compositions according to the invention are, for example, metal powders, wood dust, glass powder, glass beads, semi-metal and metal oxides, for example SiO2 (Aerosils, quartz, quartz powder, vitreous fused silica), corundum and titanium oxide, semi-metal and metal nitrides, for example silicon nitride, boron nitride and aluminium nitride, semi-metal and metal carbides (SiC), metal carbonates (dolomite, chalk, CaCO3), metal sulfates (barite, gypsum), and powdered rock and natural or synthetic minerals, mainly from the silicate series, for example talcum, mica, kaolin, wollastonite, bentonite and others.
Preferably, a metal oxide, carbonate, sulfate or silicate or SiO2 is used as component (c).
Preferred fillers are Al2O3, Al(OH)3, CaCO3, CaSiO3, SiO2, woven glass fibres, woven carbon fibres and woven aramid fibres.
Especially preferred as component (c) are Al2O3, Al(OH)3, wollastonite, quartz powder, dolomite, lime, chalk, woven glass fibres, woven carbon fibres and woven aramid fibres.
The silanes of formula I are known and can be prepared according to known methods. Some of those silanes are available commercially.
Preference is given to silanes of formula I wherein R as a monovalent organic group having from 2 to 100 carbon atoms is C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C,2cycloalkyl, C2-C20-alkoxyalkyl, C2-C20alkenyl, C4-C25acryloxyalkyl, C4-C25methacryloxyalkyl, C2-C20aminoalkyl, C4-C25glycidyloxyalkyl, C7-C25epoxycyclohexylalkyl or the radical of a polysiloxane.
Alkyl as R, Y1, Y2 or Y3 includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Aryl as R, Y1, Y2 or Y3 contains preferably from 6 to 10 carbon atoms. It may be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl or anthryl.
Aralkyl as R, Y" Y2 or Y3 contains especially from 7 to 12 carbon atoms and more especially from 7 to 10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, 4-phenylbutyl or a,a-dimethylbenzyl.
Cycloalkyl as R, Y1, Y2 or Y3iS preferably C5-C8cycloalkyl, especially C5- or C6-cycloalkyl.
Examples include cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclo-pentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Examples of alkoxyalkyl as R, Y" Y2 or Y3 are 2-methoxyethyl, 2-ethoxyethyl, 2-methoxy-propyl, 3-methoxypropyl, 2-ethoxypropyl and 3-ethoxypropyl.
Alkenyl as R includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
Examples of acryloxyalkyl and methacryloxyalkyl are 2-acryloxyethyl, 2-methacryloxyethyl, 3-acryloxypropyl and 3-methacryloxypropyl.
Suitable aminoalkyl groups are, for example, 2-aminoethyl, 3-aminopropyl, 3-aminobutyl and 4-aminobutyl.
Suitable glycidyloxyalkyl groups are, for example, 2-glycidyloxyethyl, 3-glycidyloxypropyl, 3-glycidyloxybutyl and 4-glycidyloxybutyl.
Epoxycyclohexylalkyl is preferably ~-(3,4-epoxycyclohexyl)ethyl.
R in formula I is preferably methyl, ethyl, n-octyl, vinyl, 3-mercaptopropyl, 3-aminopropyl, 3-glycidyloxypropyl, 3-acryloxypropyl, 3-methacryloxypropyl, ~-(3,4-epoxycyclohexyl)ethyl, N-(,B-aminoethyl)-3-aminopropyl, 3-ureidopropyl, 3-isocyanatopropyl, H2N-CH2CH2NH-CH2CH2NH-CH2CH2CH2-, (CH30)3Si-CH2CH2CH2NH-CH2CH2CH2- or a group of formula (CH30)3siCH2CH2CH2~N ~N ,cH2cH2cH2si(ocH3)3 O N ~O
Preference is given to silanes of formula I wherein R is methyl, vinyl, 3-mercaptopropyl or 3-aminopropyl.
Y" Y2 and Y3 in formula I are preferably methyl, ethyl, acetyl or 2-methoxyethyl.
Examples of suitable silanes of formula I are octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris(2-methoxyethoxy)silane, ~-methacryloxypropyltrimethoxy-silane, ~-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, y-glycidyloxypropyltrimethoxysilane, y-mercaptopropyltrimethoxysilane, ~-aminopropyltriethoxysilane, y-aminopropyltrimethoxy-silane, N-(,~-aminoethyl)-~-aminopropyltrimethoxysilane, H2NCH2CH2NHCH2CH2NHCH2CH2CH2Si(OCH3)3, bis[~-(trimethoxysilyl)propyl]amine, organically modified polydimethylsiloxane of formula (CH3)3SiO- E(CH3)2SiO~E(CH3)2 ISiO~E(CH3)2 ISi~~Si(CH3)3 wherein R and R' = alkyl or aryl, NR2 NHR'Si(OR)3 ~-ureidopropyltrimethoxysilane, ~-isocyanatopropyltriethoxysilane, 3-chloropropyltrimethoxy-silane, 3-triethoxysilylpropylsuccinic acid anhydride, 3-methacryloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane and 3-(2-aminoethylamino)propylmethyldimethoxysilane.
Vinyltrimethoxysilane is especially preferred as component (d).
It should be mentioned that when using quartz powder as filler, it is also possible to use, instead of a mixture of components (c) and (d), a quartz powder pre-treated with a silane of formula 1. Such quartz powders pre-treated with epoxysilane, alkylsilane or vinylsilane are available commercially, for example under the names Silbond~ W12 EST, Vp W12 VST and Vp W12 SST.
The amounts of components (a) to (d) in the compositions according to the invention may vary within wide limits.
Preferably, the compositions according to the invention contain from 15 to 75 % by weight of component (a), from 0.001 to 10.0 % by weight of component (b), from 20 to 80 % by weight of component (c) and from 0.01 to 20.0 % by weight of component (d), the sum of components (a), (b), (c) and (d) being 100 % by weight.
Especially preferred are compositions according to the invention containing from 25 to 65 %
by weight, especially from 30 to 50 % by weight, of component (a), from 0.01 to 2.0 % by weight, especially from 0.1 to 1.0 % by weight, of component (b), from 30 to 75 % by weight, especially from 50 to 70 % by weight, of component (c) and from 0.05 to 10.0 % by weight, especially from 0.1 to 2.0 % by weight, of component (d).
The substance mixtures according to the invention can be prepared in customary manner by mixing the components using known mixing equipment (e.g. stirrers, rollers).
In addition to components (a) to (d), the composition according to the invention may comprise further customary additives, for example anti-oxidants, light stabilisers, plasticisers, colourants, pigments, thixotropic agents, viscosity improvers, anti-foams, antistatics, lubricants and mould release agents.
The composition according to the invention may be prepared directly before polymerisation, or may be used in the form of a preformulated mixture. Before polymerisation, the mixture can be stored in the form of a ready-to-use formulation for a prolonged period, which is advantageous for use on an industrial scale. Storage with the exclusion of light is recommended, however, when the catalyst contains photolabile ligands.
The present invention relates also to a method of bonding two or more substrates, which comprises applying a curable composition comprising the above-mentioned components (a) to (d) to at least one of the substrates to be bonded, bringing the substrates to be bonded CA 02242060 l998-06-30 into contact with one another, and curing the composition by heating to a temperature , 40~C.
Advantageously, the method according to the invention is carried out at a temperature of at least 60~C. The method according to the invention is especially carried out at temperatures of from 60 to 300~C, more especially from 60 to 250~C, preferably from 60 to 200~C and especially preferably from 70 to 1 60~C. After polymerisation, it may be advantageous to temper the mixture at elevated temperatures, for example at from 80 to 200~C.
The adhesive mixture is applied to the substrate in known manner. The layer thickness of the adhesive films is generally not more than 500 ~m, and is preferably from 40 to 120,um. It is, however, possible for substantially thicker layers to be fully cured thermally.
Before being coated with the adhesive mixture, the surfaces to be bonded may, ifappropriate, be degreased and roughened.
After they have been brought together, the coated surfaces are pressed together or clamped, if appropriate.
Suitable surfaces for bonding are especially those made of metals, such as iron, steel, or especially aluminium and its alloys, for example with magnesium or silicon. The adhesive can also be used to bond two different materials, for example to bond metals to polymeric materials.
The bonds produced in accordance with the method according to the invention are distinguished especially by a high bond strength and minimal water absorption.
Example 1:
0.39 9 of Norsorex NS (thermoplastic polynorbornene, Nippon Zeon) is dissolved at 80~C in 38.91 g of dicyclopentadiene. After cooling to 60~C, 0.5 g of vinyltrimethoxysilane (Silquest~
A-171, Osi Specialties) and 0.2 g of (cyclohexyl)3P(p-cymene)RuCI2 are added, and the mixture is stirred for 20 minutes at 60~C. After the addition, in portions, of 60 g of wollastonite FW 200 (Partek Minerals), the mixture is stirred for a further 15 minutes. The mixture is then degassed for from 3 to 5 minutes in vacuo (3 mbar).
The mixture so obtained is poured into a 4 mm-thick plate mould of aluminium and then fully cured (2 h/80~C, 4 h/1 00~C, 1 h/1 50~C). It is established that the cured moulding has very good adhesion to aluminium and cannot be removed from the mould either at -180~C or at 200~C.
In WO 96/16100 and WO 96/20235 it is mentioned that the ROMP systems (ROMP = ring-opening metathesis polymerisation) described therein based on strained cycloolefins and specific ruthenium catalysts are suitable as adhesives for bonding Teflon, polyethylene and polypropylene. The adhesion to the substrate is inadequate for certain uses, however, owing to the low polarity of the cycloolefins.
Bonds made with reactive adhesives exhibit inner strains caused by reaction shrinkage when the relatively large intermolecular spacing between the monomers are replaced by the closer spacing of the covalent bonds between the polymer segments. The shrinkage can bereduced by the addition of suitable fillers, but the addition of fillers generally results in a breakdown of the cohesion.
Surprisingly, it has now been found that the ROMP systems described in EP-A-771 830, together with fillers, exhibit very good adhesion and can consequently be used as adhesives.
The present invention relates to the use, as an adhesive, of a composition comprising (a) at least one strained cycloolefin, (b) a catalyst for ring-opening metathesis polymerisation, (c) a filler and (d) a silane of formula I
OY, R--Si OY2 (I ), oy3 wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may be replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y" Y2 and Y3 are each independently of the others C,-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C,2cycloalkyl, C2-C20alkoxyalkyl or C,-C20acyl.
When fully cured, the ROMP system exhibits an especially high degree of adhesion to metals, for example iron or aluminium. Preference is accordingly given to the use of the above-specified composition as an adhesive for metals, especially for aluminium.
Within the scope of the present invention there is to be understood by "strained cycloolefin"
any cycloolefin, with the exception of cyclohexene and derivatives thereof, which cannot be polymerised by ring-opening metathesis.
Strained cycloolefins may be monocyclic or polycyclic fused or bridged ring systems, for example having from two to four rings, that are unsubstituted or substituted and may contain hetero atoms, for example oxygen, sulfur, nitrogen or silicon, in one or more rings and/or may contain fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthyl-ene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings may contain from 3 to 16, especially from 3 to 12, and more especially from 3 to 8, ring members. The strained cyclo-olefins may contain further non-aromatic double bonds, preference being given, depending on the ring size, to from 2 to 4 such additional double bonds. The ring substituents are inert, that is to say those substituents do not impair the chemical stability and the thermostability of the ROMP catalysts.
When the strained cycloolefins contain more than one double bond, for example from 2 to 4 double bonds, it is possible also for crosslinked polymers to be formed, depending on the reaction conditions, the monomer selected and the amount of catalyst.
There is preferably used as component (a) in the composition according to the invention a compound of formula ll \ / (Il), wherein Q, is a radical having at least one carbon atom, which radical, together with the -CH=CQ2 group, forms an alicyclic ring having a minimum of three members that may contain one or more hetero atoms selected from the group silicon, phosphorus, oxygen, nitrogen and sulfur and that is unsubstituted or substituted by halogen, =0, -CN, -NO2, R1R2R3Si-(O)u~, -COOM, -S03M, -PO3M, -COO(M,)1,2, -SO3(M,)"2, -PO3(M,)"2, C,-C20alkyl, C,-C20hydroxyalkyl, C,-C20haloalkyl, C1-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, C7-C,6-aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C,6heteroaralkyl or by R4-X-; or in which two adjacent carbon atoms are bonded by -CO-O-CO- or -CO-NR5-CO-; or in which there is fused to adjacent carbon atoms of the alicyclic ring an alicyclic, aromatic or heteroaromatic ring that is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-(O)U-, -COOM, -SO3M, -PO3M, -COO(M1)1,2, -S03(M1)"2, -PO3(M1)"2, C,-C20alkyl, C,-C20haloalkyl, C,-C20-hydroxyalkyl, C,-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, C7-C,6aralkyl, C3-C6heterocyclo-alkyl, C3-C,6heteroaryl, C4-C,6heteroaralkyl or by R,3-X,-; X and X1 are each independently of the other -O-, -S-, -CO-, -SO-, -SO2-, -O-CO-, -COO-, -CO-NR5-, -NR10-CO-, -SO2-O- or -O-SO2-; R1, R2 and R3 are each independently of the other C,-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl; R4 and R~3 are each independently of the other C,-C20alkyl, C,-C20-haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or C7-C,6aralkyl; R5 and R,O are each independently of the other hydrogen, C,-C,2alkyl, phenyl or benzyl, the alkyl groups in turn being unsubstituted or substituted by C,-C,2alkoxy or by C3-C8cycloalkyl; R6, R7 and R8 are each independently of the others C,-C,2alkyl, C,-C,2perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M, is an alkaline earth metal; and u is O or 1; it being possible for the alicyclic ring formed with Q, to contain further non-aromatic double bonds;
Q2 is hydrogen, C,-C20alkyl, C,-C20haloalkyl, C,-C,2alkoxy, halogen, -CN or R"-X2-; R" is C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or C7-C,6aralkyl; X2 is -COO- or -CO-NR,2-; and R,2 is hydrogen, C,-C,2alkyl, phenyl or benzyl;
wherein the above-mentioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups may be unsubstituted or substituted by C,-C,2alkyl, C,-C,2alkoxy, -NO2, -CN or by halogen, and wherein the hetero atoms of the above-mentioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group -O-, -S-, -NRg- and -N=, Rg being hydrogen, C,-C,2alkyl, phenyl or benzyl.
Fused-on alicyclic rings contain preferably from 3 to 8, especially from 4 to 7, and more especially 5 or 6, ring carbon atoms.
For the purpose of crosslinking or to control the molecular weight, the composition according to the invention may contain further olefins capable of metathesis, advantageously in amounts of up to 40 mol %, especially from 0.01 to 30 mol % and more especially from 0.1 to 20 mol %, based on the total amount of the cycloolefins and olefins present.
Suitable olefins capable of metathesis are, for example, cyclooctadiene, cyclooctatriene, norbornadiene and acetylnorbornene. Also suitable are compounds such as 2-butene-1,4-diol, as described in Feast, W.J., Harrison, B., J. Mol. Catal. 65, 63 (1991), or 1-hexene (rearrangements) .
The presence of an asymmetric centre in the compounds of formula ll means that those compounds may occur in optically isomeric forms. Some compounds of formula ll may occur in the form of tautomers (e.g. keto-enol tautomerism). If an aliphatic C=C double bond is present, then also geometric isomerism may occur (E-form or Z-form). In addition, exo/endo configurations are also possible. Formula ll hence includes all possible stereoisomers, which are in the form of enantiomers, tautomers, diastereoisomers, E/Z isomers or mixtures thereof.
The alkyl, alkenyl and alkynyl groups in the definitions of the substituents may be straight-chain or branched. The same applies also to the alkyl moiety or each of the alkyl moieties of alkoxy, alkylthio, alkoxycarbonyl and other alkyl-containing groups. The alkyl groups contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 4, carbon atoms. The alkenyl and alkynyl groups contain preferably from 2 to 12, especially from 2 to 8, and more especially from 2 to 4, carbon atoms.
Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomers of 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-hydroxyisobutyl, 1-hydroxy-sec-butyl, 1-hydroxy-tert-butyl and the various hydroxy-substituted isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-tri-chloroethyl and halogenated, especially fluorinated or chlorinated, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups and the various halogenated isomers of 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, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
Cycloalkyl is preferably C5-C8cycloalkyl, especially C5- or C6-cycloalkyl. Examples include cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Cyanoalkyl includes, for example, cyanomethyl (methylnitrile), cyanoethyl (ethylnitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyanoisobutyl, 1-cyano-sec-butyl, 1-cyano-tert-butyl and the various isomers of cyanopentyl and cyanohexyl.
Aralkyl contains especially from 7 to 12 carbon atoms and more especially from 7 to 10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, 4-phenylbutyl or a,a-dimethylbenzyl.
Aryl contains preferably from 6 to 10 carbon atoms. It may be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl or anthryl.
Heteroaryl contains preferably 4 or 5 carbon atoms and one or two hetero atoms from the group oxygen, sulfur and nitrogen. It may be, for example, pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, purinyl or quinolyl.
Heterocycloalkyl contains preferably 4 or 5 carbon atoms and one or two hetero atoms from the group oxygen, sulfur and nitrogen. It may be, for example, oxiranyl, azirinyl, 1,2-oxathiolanyl, pyrazolinyl, pyrrolidinyl, piperidyl, piperazinyl, morpholinyl, tetrahydrofuranyl or tetrahydrothiophenyl.
Alkoxy is, for example, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy or tert-butyloxy.
Within the scope of the present invention, alkali metal is to be understood as meaning lithium, sodium, potassium, rubidium or caesium, especially lithium, sodium or potassium.
Within the scope of the present invention, alkaline earth metal is to be understood as meaning beryllium, magnesium, calcium, strontium or barium, especially magnesium or calcium.
In the above definitions, halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Especially well-suited compounds of formula ll in the composition according to the invention are those wherein Q2 is hydrogen.
Preference is given also to compounds of formula ll wherein Q, is a radical having at least one carbon atom, which radical, together with the -CH=CQ2- group, forms a 3- to 10-membered alicyclic ring that may contain a hetero atom selected from the group silicon, oxygen, nitrogen and sulfur and that is unsubstituted or substituted by halogen, -CN, -NO2, R,R2R3Si-, -COOM, -SO3M, -PO3M, -COO(M,)"2, -S03(M,)"2, -PO3(M,)"2, C1-C6alkyl, C,-C6-haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or by R4-X-; or in which there may be fused to adjacent carbon atoms an aromatic or heteroaromatic or alicyclic ring that is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M,)1~2, -SO3(M1)1~2, -PO3(M1)1~2, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or by R13-X1-; R1, R2 and R3 are each independently of the others C1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M, is an alkaline earth metal; R4 and R13 are each independently of the other C1-C6alkyl, C1-C6haloalkyl, C,-C6hydroxyalkyl or C3-C6cycloalkyl; X and X1 are each independently of the other-O-, -S-, -CO-, -SO- or-S02- and R6, R7 and R8 are each independently of the others C,-C4alkyl, C,-C4perfluoroalkyl, phenyl or benzyl.
Norbornene and norbornene derivatives, especially dicyclopentadiene and dicyclopentadiene derivatives, are especially preferred as component (a).
Preferred norbornene derivatives are the compounds of formulae lll, IV, V and Vl ~14 ~ (IV), R.8 ~ (V), ~ (Vl), wherein X3 is -CHR16-, oxygen or sulfur, R14 and R15 are each independently of the other hydrogen, -CN, trifluoromethyl, (CH3)3SiO-, (CH3)3Si- or -COOR17, and R16 and R17 are each independently of the other hydrogen, C1-C12alkyl, phenyl or benzyl;
X4 is -CHR19-, oxygen or sulfur, R19 is hydrogen, C1-C12alkyl, phenyl or benzyl and R18 is hydrogen, C1-C6alkyl or halogen;
Xs is -CHR22-, oxygen or sulfur, R22 is hydrogen, C1-C12alkyl, phenyl or benzyl, R20 and R21 are each independently of the other hydrogen, CN, trifluoromethyl, (CH3)3SiO-, (CH3)3Si- or -COOR23 and R23 is hydrogen, C1-C12alkyl, phenyl or benzyl;
X6 is -CHR24-, oxygen or sulfur, R24 is hydrogen, C1-C12alkyl, phenyl or benzyl, Y is oxygen or \N--R and R25 is hydrogen, methyl, ethyl or phenyl.
Examples of suitable compounds of formula ll are the following cycloolefins:
~ (2)~ ~ (3).
CA 02242060 l998-06-30 COOH ~~ COOCH3 ~\~(4), ~ (5), / (6), o O o COOCH2phenyl ~_ COOCzHs /~~ COO(CH2)~CH3 ~ (7). ~ (8), ~ (9).
COOCH2phenyl COOCzHs coo(CH2)3cH3 O O
~_ COO(CH2)sCH3 ~ COO(CH2)9CH3 ~_ COO(CH2),lCH3 ~ (10). ~ (11), ~ (12 Coo(cH2)scH3coo(cH2)9cH3 coo(cH2)1~c~l3 O O
~f(,3). ~ f~(,4) ~ f~(1s) ~ O NH
O O O
O O O
f (16), f (17)' fo (18), N ' CH3 C2H5 ~ phenyl O O O
~(19)~ 3(20), (~)(21), (22), ~ (23), [3 (24), [~ (25), b (26), b (27), ~ (28), (29), ~ ~ (30)~ b CN (31), \CH2NHCH3 1~ .
~( (32), ~V Sl(CH3)3 (33), b P(C6H5)2 (34~ b~ CH2~(CH2)5~CH3 (35 P(C6H5)2 b 3 (36), ~ ~ (37), o_ _ ~ " (38), ~3 (39)' (40~ ,3(41)~
~1 ~3 (42), ~ 3 (43) In a preferred embodiment, the strained cycloolefins contain only carbon and hydrogen atoms, and are preferably 5- or 6-membered rings, or ring systems having from one to three 5- or 6-membered rings, for example norbornenes, alkylated norbornenes and dicyclopenta-diene.
Especially preferred as component (a) is dicyclopentadiene.
A large number of compounds of the transition metals titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium and osmium are known to the person skilled in the art as catalysts for ring-opening metathesis polymerisation (ROMP catalysts). Such compounds are, for example, complex metal halides, metallo-carbenes or co-ordination catalysts of the Ziegler-Natta type. In principle, any of those known ROMP catalysts may be used as component (b) in the compositions according to the invention.
Preferably, a ruthenium(+ll) complex salt or an osmium(+ll) complex salt, especially a ruthenium(+ll) complex salt, is used as component (b).
Since the fillers according to component (c) often contain small amounts of water, it is advisable to use ROMP catalysts that are not sensitive to moisture, such as, for example, the ruthenium(+ll) and osmium(+ll) complex salts described in WO 96/16100 and WO 96/20235.
The preferred component (b) is therefore a complex salt of formula lll (R2sR3oR31p)xLyMe2+z1-z2 (111), wherein R29, R30 and R3, are each independently of the others H, C,-C20alkyl, C,-C20alkoxy, unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C4-C,2cycloalkyl or cycloalkoxy, or unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C6-C,6aryl or C6-C,6aryloxy, or unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C7-C,6aralkyl or C7-C,6aralkyloxy; the radicals R30 and R3, together are unsub-stituted or C,-C6alkyl-, C,-G6haloalkyl- or C,-C6alkoxy-substituted tetra- or penta-methylene or tetra- or penta-methylenedioxy; or are tetra- or penta-methylene or tetra- or penta-methylenedioxy that is unsubstituted or substituted by C,-C6alkyl, C,-C6haloalkyl or C,-C6alkoxy and fused with one or two 1 ,2-phenylene radicals; or are tetramethylenedioxy that is unsubstituted or substituted by C,-C6alkyl, C1-C6haloalkyl or C,-C6alkoxy and fused in the 1,2- and 3,4-positions with 1,2-phenylene; and R3, is as defined hereinbefore;
L is a neutral ligand, Me is Ru or Os, Z,~ and Z2- are each a singly charged anion or Z,~ and Z2- together are a doubly charged anion, x is a number from 1 to 3 and y is a number from 0 to 3, such that 2 5 x+y < 4.
The ligands L in the compounds of formula lll may be identical or different.
The ruthenium and osmium compounds of formula lll are known or can be prepared according to known processes from the metal halides (for example MeX3 or [Me-areneX2]2) by reaction with phosphines of formula IV
R29R30R3, P (IV), wherein R29, R30 and R3, are as defined for formula (Ill), and ligand formers.
The radicals R29, R30 and R3, are preferably identical radicals. Also, sterically bulky radicals are preferred, for example branched, especially a-branched, alkyl or alkoxy, or cyclic radicals.
R29, R30 and R3, as alkyl may be linear or branched and contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 6, carbon atoms. Examples of alkyl are methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, CA 02242060 l998-06-30 heptadecyl, octadecyl and eicosyl. Preferred examples are methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl.
R29, R30 and R3, as alkoxy may be linear or branched and contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 6, carbon atoms. Examples of alkoxy are methoxy, ethoxy, n- and iso-propyloxy, n-, iso- and tert-butyloxy, and the isomers of pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy and eicosyloxy. Preferred examples are methoxy, ethoxy, n- and iso-propyloxy, n-, iso- and tert-butyloxy, 1-, 2- or 3-pentyloxy and 1-, 2-, 3- or 4-hexyloxy.
Where R29, R30 and R31 are substituted, the substituents are preferably C,-C4alkyl, C1-C4--haloalkyl or C,-C4alkoxy. Halogen is preferably chlorine and especially fluorine. Examples of preferred substituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl. R29, R30 and R3, are preferably substituted by from 1 to 3 substituents.
R29, R30 and R3, as cycloalkyl are preferably C5-C8cycloalkyl and especially C5- or C6-cycloalkyl. Examples include cyclobutyl, cycloheptyl and cyclooctyl, and especially cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-cyclopentyl and -cyclohexyl.
R29, R30 and R3, as cycloalkyloxy are preferably C5-C8cycloalkyloxy and especially C5- or C6-cycloalkyloxy. Examples include cyclobutyloxy, cycloheptyloxy and cyclooctyloxy, and especially cyclopentyloxy and cyclohexyloxy. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)-and tris(trifluoromethyl)-cyclopentyloxy and -cyclohexyloxy.
R29, R30 and R3, as aryl are preferably C6-C,2aryl and especially phenyl or naphthyl.
Examples of substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-phenyl.
R29, R30 and R3, as aryloxy are preferably C6-C,2aryloxy and especially unsubstituted or substituted phenyloxy or naphthyloxy. Examples of substituted aryloxy are methyl-, dimethyl-, trimethyl-, methylisopropyl-, isopropyl-, diisopropyl-, triisopropyl-, tert-butyl-, methyltert-butyl-, di(tert-butyl)-, tri(tert-butyl)-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-phenyloxy.
R29, R30 and R3, as aralkyl are preferably C7-C13aralkyl, the alkylene group in the aralkyl preferably being methylene. The aralkyl is especially benzyl. Examples of substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-benzyl.
R29, R30 and R3, as aralkyloxy are preferably unsubstituted or substituted C7-C13aralkyloxy, the alkylene group in the aralkyloxy preferably being methylene. The aralkyloxy is especially unsubstituted or substituted benzyloxy. Examples of substituted aralkyloxy are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)-and tris(trifluoromethyl)-benzyloxy.
Special preference is given to complex salts of formula lll wherein R29, R30 and R3, are C1-C6alkyl, C,-C6alkoxy, C4-C12cycloalkyl, C4-C12cycloalkoxy, C6-C16aryl or C6-C,6aryloxy.
Especially preferred are complex salts of formula lll wherein R29, R30 and R3, are phenyl, tolyl or cyclohexyl.
Examples of suitable phosphines of formula IV are (C6Hs)3P, (C6H5CH2)3P, (C5H11)3P, (CH3)3P, (C2H5)3P, (n-C3H7)3P, (iso-C3H7)3P, (n-C4Hg)3P, (C6H5)2HP, (C6H5CH2)2HP, (C5H11)2HP, (CH3)2HP, (C2H5)2HP, (n-C3H7)2HP, (iso-C3H7)2HP, (n-C4Hg)2HP, (C6H5)H2P, (C6H5CH2)H2P, (C5H,1)H2P, (CH3)H2P, (C2H5)H2P, (n-C3H7)H2P, (iso-C3H7)H2P, (n-C4Hg)H2P, PH3, (2-CH3-C6H4)3P, (3-CH3-C6H4)3P, (4-CH3-C6H4)3P, (2,4-di-CH3-C6H3)3P, (2,6-di-CH3-C6H3)3P, (2-C2H5-C6H4)3P, (3-C2H5-C6H4)3P, (4-C2H5-C6H4)3P, (2-n-C3H7-C6H4)3P, (3-n-C3H7-C6H4)3P, (4-n-C3H7-C6H4)3P, (2-iso-C3H7-C6H4)3P, (3-iso-C3H7-C6H4)3P, (4-iso-C3H7-C6H4)3P, (2-n-C4Hg-C6H4)3P, (3-n-C4Hg-C6H4)3P, (4-n-C4Hg-C6H4)3P, (2-iso-C4Hg-C6H4)3P, (3-iso-C4Hg-C6H4)3P, (4-iso-C4Hg-C6H4)3P, (2-tert-C4Hg-C6H4)3P, (3-tert-C4Hg-C6H4)3P, (4-tert-C4Hg-C6H4)3P, (2-CH3-6-tert-C4Hg-C6H3)3P, (3-CH3-6-tert-C4Hg-C6H3)3P, (3-CH3-6-tert-C4Hg-C6H3)3P, (2,6-di-tert-C4Hg-C6H3)3P, (2,3-di-tert-C4Hg-C6H3)3P and (2,4-di-tert-C4Hg-C6H3)3P .
Especially preferred phosphines are triisopropylphosphine, tri-tert-butylphosphine and tricyclohexylphosphine.
CA 02242060 l998-06-30 The ligands L bonded to the metal atom in the compounds of formula lll may be photolabile or non-photolabile ligands.
In the case of compounds of formula lll having photolabile ligands the catalytic activity is achieved by the action of light, that is to say on irradiation of the catalyst with light in the visible or ultraviolet range the photolabile ligand is removed, and a species is formed which is catalytically active for the metathesis polymerisation.
The photolabile ligands may be, for example, nitrogen (N2), unsubstituted or OH-, C,-C4alkyl-, Cj-C4alkoxy-, C6-C12aryl- or halo-substituted monocyclic, polycyclic or fused arenes having from 6 to 24, especially from 6 to 18, and more especially from 6 to 12, carbon atoms, or unsubstituted or C,-C4alkyl-, C,-C4alkoxy- or halo-substituted monocyclic hetero-arenes, fused heteroarenes or fused arene-heteroarenes having from 3 to 22, especially from 4 to 16, and more especially from 4 to 10, carbon atoms and from 1 to 3 hetero atoms selected from the group oxygen, sulfur and nitrogen; or unsubstituted or C,-C4alkyl-, C,-C4alkoxy- or halo-substituted aliphatic, cycloaliphatic, aromatic or araliphatic nitriles having from 1 to 22, especially from 1 to 18, more especially from 1 to 12, and preferably from 1 to 7, carbon atoms. The preferred substituents are methyl, ethyl, methoxy, ethoxy, fluorine, chlorine and bromine. The arenes and heteroarenes are preferably substituted by from one to three radicals. The preferred heteroarenes are the electron-rich heteroarenes.
Examples of arenes and heteroarenes include benzene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoroanthrene, furan, thiophene, pyrrole, pyridine, ~-pyran, ~-thiopyran, pyrimidine, pyrazine, indole, cumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene and purine. Preferred arenes and heteroarenes are unsubstituted or substituted benzene, naphthalene, thiophene and benzthiophene. The arene is especially benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals and the heteroarene is preferably thiophene.
The nitriles may be substituted, for example, by methoxy, ethoxy, fluorine or chlorine;
preferably, the nitriles are unsubstituted. The alkylnitriles are preferably linear. Examples of CA 02242060 l998-06-30 nitriles include acetonitrile, propionitrile, butyronitrile, pentylnitrile, hexylnitrile, cyclopentyl-and cyclohexyl-nitrile, benzonitrile, methylbenzonitrile, benzylnitrile and naphthylnitrile. The nitriles are preferably linear C1-C4alkylnitriles or benzonitrile. Of the alkylnitriles, acetonitrile is especially preferred.
In a preferred sub-group, the photolabile ligands are N2, benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals, thiophene, benzonitrile or acetonitrile.
Within the scope of the present invention "non-photolabile ligand" (also called "strongly co-ordinating ligand") denotes that the ligand does not dissociate, or dissociates only to an insignificant extent, from the catalyst on irradiation of the catalyst in the visible or near ultraviolet spectral range.
The non-photolabile ligands may be, for example, solvating inorganic and organiccompounds containing the hetero atoms O, S or N, which are frequently also used as solvents. Examples of such compounds are H2O, H2S, NH3; unsubstituted or halogenated, especially fluorinated or chlorinated, aliphatic or cycloaliphatic alcohols or mercaptans having from 1 to 18, especially from 1 to 12, and more especially from 1 to 6, carbon atoms, aromatic alcohols or thiols having from 6 to 18, especially from 6 to 12, carbon atoms, araliphatic alcohols or thiols having from 7 to 18, especially from 7 to 12, carbon atoms;
open-chained or cyclic and aliphatic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones, carboxylic acid amides having from 2 to 20, especially from 2 to 12, and more especially from 2 to 6, carbon atoms which may be non-N-alkylated or N-C1-C4-mono- or -di-alkylated, and lactams which may be non-N-alkylated or N-C1-C4alkylated; and open-chained or cyclic and aliphatic, araliphatic or aromatic, primary, secondary and tertiary amines having from 1 to 20, especially from 1 to 12, and more especially from 1 to 6, carbon atoms.
Examples of such non-photolabile ligands are methanol, ethanol, n- and iso-propanol, n-, iso-and tert-butanol, 1,1,1-trifluoroethanol, bistrifluoromethylmethanol, tristrifluoromethyl-methanol, pentanol, hexanol, methyl- or ethyl-mercaptan, cyclopentanol, cyclohexanol, cyclohexylmercaptan, phenol, methylphenol, fluorophenol, phenylmercaptan, benzyl-mercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-tert-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, tetrahydrothiophene, dimethyl sulfoxide, diethyl sulfoxide, tetra- and penta-methylene sulfoxide, dimethylsulfone, CA 02242060 l998-06-30 diethylsulfone, tetra- and penta-methylenesulfone, acetone, methyl ethyl ketone, diethyl ketone, phenyl methyl ketone, methyl isobutyl ketone, benzyl methyl ketone, acetaldehyde, propionaldehyde, trifluoroacetaldehyde, benzaldehyde, ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide, pyrrolidone and N-methylpyrrolidone.
The primary amines may correspond to the formula R26NH2, the secondary amines to the formula R26R27NH and the tertiary amines to the formula R26R27R28N, wherein R26 is C1-C,8alkyl, unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C5- or C6-cycloalkyl, or unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C6-C18aryl or C7-C12aralkyl, R27 independently has the meaning given for R26, or R26 and R27 together are tetramethylene, pentamethylene, 3-oxa-1,5-penty!ene or-CH2-CH2-NH-CH2-CH2- or-CH2-CH2-N(C1-C4alkyl)-CH2-CH2-, and R28 independently has the meaning given for R26. The alkyl contains especially from 1 to 12, and more especially from 1 to 6, carbon atoms. The aryl contains preferably from 6 to 12 carbon atoms and the aralkyl contains preferably from 7 to 9 carbon atoms. Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methylethyl-, dimethylethyl-, n-propyl-, di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- and benzyl-amine, and also pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.
Preferably, the compositions according to the invention comprise as component (b) a complex salt of formula lll wherein L is an arene, a heteroarene, a nitrile, nitrogen (N2), an alcohol, an amine, CO, H20 or NH3.
Especially preferred as component (b) is a complex salt of formula lll wherein L is benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals, thiophene, benzonitrile, acetonitrile, nitrogen (N2), an unsubstituted or partially or fully fluorinated C1-C4alcohol, CO, H20 or NH3.
In the compounds of formula lll, Z1- and Z2- may each be a singly charged anion, it being possible for Z1- and Z2- to be identical or different, or Z1- and Z2- may together be a doubly charged anion.
Suitable anions are, for example, hydride (H-), halide (for example Cl-, Br~ and 1-), BF4-, PF6-, SbF6-, AsF6-, unsubstituted or C,-C4alkyl-, C1-C4alkoxy-, (C,-C4alkyl)3Si- or (C,-C4alkyl)3SiO-substituted cyclopentadienyl~, or indenyl~, and the anions of oxyacids.
CA 02242060 l998-06-30 Further suitable anions are C,-C,2-, especially C,-C6- and more especially C1-C4-alcoholates, which are especially branched and correspond, for example, to the formula RXRyRzC~O~~
wherein Rx is H or C1-C,0alkyl, Ry is C1-C10alkyl and Rz is C1-C10alkyl or phenyl. Examples are especially isopropyloxy and tert-butyloxy.
Other suitable anions are C3-C18-, especially C5-C14- and more especially C5-C12-acetylides, which may correspond to the formula RW-C-C-~ wherein Rw is C1-C16alkyl, preferably a-branched C3-C12alkyl, for example of the formula RXRyRzC~~ or is phenyl or benzyl unsubstituted or substituted by from one to three C1-C4alkyl or C1-C4alkoxy radicals.
Examples include isopropylacetylide, iso- and tert-butylacetylide, phenylacetylide, benzylacetylide, 2-methylphenylacetylide, 2-isopropylphenylacetylide, 2-isopropyl-6-methylphenylacetylide, 2-tert-butylphenylacetylide, 2,6-di-tert-butylphenylacetylide and 2-methyl-6-tert-butylphenylacetylide.
The anions of oxyacids may be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C1-C8carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or tri-chloro- or -fluoro-acetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate); phenylsulfonate or benzylsulfonate unsubstituted or substituted by C,-C4alkyl, C,-C4alkoxy or by halogen, especially fluorine, chlorine or bromine, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxy-phenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropyl-sulfonate; and phosphonates, for example methylphosphonate, ethylphosphonate, propylphoshonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate and benzylphosphonate.
Preferably, Z1- and Z2- in formula lll are H-, Cl-, Br~, BF4-, PF6-, SbF6-, AsF6-, CF3SO3-, C6H5-SO3-, p-toluenesulfonate (tosylate), 3,5-dimethylphenylsulfonate, 2,4,6-trimethylphenyl-sulfonate, 4-trifluoromethylphenylsulfonate or cyclopentadienyl.
Especially preferred ROMP catalysts of formula lll are [(cyclohexyl)3P]2RuCI2, [(C6H5)3P]3RuC12, [(C6H5)3P]3(CO)RuH2, [(C6H5)3P]3RuCl(cyclopentadienyl), CA 02242060 l998-06-30 [(cyclohexyl)3P]2(CH3OH)Ru(tosylate)2, [(o-tolyl)3P]3RuCI2, [(CH3)2CH]3P(p-cymene)RuCI2 and especially (cyclohexyl)3P(p-cymene)RuCI2.
Suitable fillers which may be used as component (c) in the compositions according to the invention are, for example, metal powders, wood dust, glass powder, glass beads, semi-metal and metal oxides, for example SiO2 (Aerosils, quartz, quartz powder, vitreous fused silica), corundum and titanium oxide, semi-metal and metal nitrides, for example silicon nitride, boron nitride and aluminium nitride, semi-metal and metal carbides (SiC), metal carbonates (dolomite, chalk, CaCO3), metal sulfates (barite, gypsum), and powdered rock and natural or synthetic minerals, mainly from the silicate series, for example talcum, mica, kaolin, wollastonite, bentonite and others.
Preferably, a metal oxide, carbonate, sulfate or silicate or SiO2 is used as component (c).
Preferred fillers are Al2O3, Al(OH)3, CaCO3, CaSiO3, SiO2, woven glass fibres, woven carbon fibres and woven aramid fibres.
Especially preferred as component (c) are Al2O3, Al(OH)3, wollastonite, quartz powder, dolomite, lime, chalk, woven glass fibres, woven carbon fibres and woven aramid fibres.
The silanes of formula I are known and can be prepared according to known methods. Some of those silanes are available commercially.
Preference is given to silanes of formula I wherein R as a monovalent organic group having from 2 to 100 carbon atoms is C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C,2cycloalkyl, C2-C20-alkoxyalkyl, C2-C20alkenyl, C4-C25acryloxyalkyl, C4-C25methacryloxyalkyl, C2-C20aminoalkyl, C4-C25glycidyloxyalkyl, C7-C25epoxycyclohexylalkyl or the radical of a polysiloxane.
Alkyl as R, Y1, Y2 or Y3 includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Aryl as R, Y1, Y2 or Y3 contains preferably from 6 to 10 carbon atoms. It may be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl or anthryl.
Aralkyl as R, Y" Y2 or Y3 contains especially from 7 to 12 carbon atoms and more especially from 7 to 10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, 4-phenylbutyl or a,a-dimethylbenzyl.
Cycloalkyl as R, Y1, Y2 or Y3iS preferably C5-C8cycloalkyl, especially C5- or C6-cycloalkyl.
Examples include cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclo-pentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Examples of alkoxyalkyl as R, Y" Y2 or Y3 are 2-methoxyethyl, 2-ethoxyethyl, 2-methoxy-propyl, 3-methoxypropyl, 2-ethoxypropyl and 3-ethoxypropyl.
Alkenyl as R includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
Examples of acryloxyalkyl and methacryloxyalkyl are 2-acryloxyethyl, 2-methacryloxyethyl, 3-acryloxypropyl and 3-methacryloxypropyl.
Suitable aminoalkyl groups are, for example, 2-aminoethyl, 3-aminopropyl, 3-aminobutyl and 4-aminobutyl.
Suitable glycidyloxyalkyl groups are, for example, 2-glycidyloxyethyl, 3-glycidyloxypropyl, 3-glycidyloxybutyl and 4-glycidyloxybutyl.
Epoxycyclohexylalkyl is preferably ~-(3,4-epoxycyclohexyl)ethyl.
R in formula I is preferably methyl, ethyl, n-octyl, vinyl, 3-mercaptopropyl, 3-aminopropyl, 3-glycidyloxypropyl, 3-acryloxypropyl, 3-methacryloxypropyl, ~-(3,4-epoxycyclohexyl)ethyl, N-(,B-aminoethyl)-3-aminopropyl, 3-ureidopropyl, 3-isocyanatopropyl, H2N-CH2CH2NH-CH2CH2NH-CH2CH2CH2-, (CH30)3Si-CH2CH2CH2NH-CH2CH2CH2- or a group of formula (CH30)3siCH2CH2CH2~N ~N ,cH2cH2cH2si(ocH3)3 O N ~O
Preference is given to silanes of formula I wherein R is methyl, vinyl, 3-mercaptopropyl or 3-aminopropyl.
Y" Y2 and Y3 in formula I are preferably methyl, ethyl, acetyl or 2-methoxyethyl.
Examples of suitable silanes of formula I are octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris(2-methoxyethoxy)silane, ~-methacryloxypropyltrimethoxy-silane, ~-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, y-glycidyloxypropyltrimethoxysilane, y-mercaptopropyltrimethoxysilane, ~-aminopropyltriethoxysilane, y-aminopropyltrimethoxy-silane, N-(,~-aminoethyl)-~-aminopropyltrimethoxysilane, H2NCH2CH2NHCH2CH2NHCH2CH2CH2Si(OCH3)3, bis[~-(trimethoxysilyl)propyl]amine, organically modified polydimethylsiloxane of formula (CH3)3SiO- E(CH3)2SiO~E(CH3)2 ISiO~E(CH3)2 ISi~~Si(CH3)3 wherein R and R' = alkyl or aryl, NR2 NHR'Si(OR)3 ~-ureidopropyltrimethoxysilane, ~-isocyanatopropyltriethoxysilane, 3-chloropropyltrimethoxy-silane, 3-triethoxysilylpropylsuccinic acid anhydride, 3-methacryloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane and 3-(2-aminoethylamino)propylmethyldimethoxysilane.
Vinyltrimethoxysilane is especially preferred as component (d).
It should be mentioned that when using quartz powder as filler, it is also possible to use, instead of a mixture of components (c) and (d), a quartz powder pre-treated with a silane of formula 1. Such quartz powders pre-treated with epoxysilane, alkylsilane or vinylsilane are available commercially, for example under the names Silbond~ W12 EST, Vp W12 VST and Vp W12 SST.
The amounts of components (a) to (d) in the compositions according to the invention may vary within wide limits.
Preferably, the compositions according to the invention contain from 15 to 75 % by weight of component (a), from 0.001 to 10.0 % by weight of component (b), from 20 to 80 % by weight of component (c) and from 0.01 to 20.0 % by weight of component (d), the sum of components (a), (b), (c) and (d) being 100 % by weight.
Especially preferred are compositions according to the invention containing from 25 to 65 %
by weight, especially from 30 to 50 % by weight, of component (a), from 0.01 to 2.0 % by weight, especially from 0.1 to 1.0 % by weight, of component (b), from 30 to 75 % by weight, especially from 50 to 70 % by weight, of component (c) and from 0.05 to 10.0 % by weight, especially from 0.1 to 2.0 % by weight, of component (d).
The substance mixtures according to the invention can be prepared in customary manner by mixing the components using known mixing equipment (e.g. stirrers, rollers).
In addition to components (a) to (d), the composition according to the invention may comprise further customary additives, for example anti-oxidants, light stabilisers, plasticisers, colourants, pigments, thixotropic agents, viscosity improvers, anti-foams, antistatics, lubricants and mould release agents.
The composition according to the invention may be prepared directly before polymerisation, or may be used in the form of a preformulated mixture. Before polymerisation, the mixture can be stored in the form of a ready-to-use formulation for a prolonged period, which is advantageous for use on an industrial scale. Storage with the exclusion of light is recommended, however, when the catalyst contains photolabile ligands.
The present invention relates also to a method of bonding two or more substrates, which comprises applying a curable composition comprising the above-mentioned components (a) to (d) to at least one of the substrates to be bonded, bringing the substrates to be bonded CA 02242060 l998-06-30 into contact with one another, and curing the composition by heating to a temperature , 40~C.
Advantageously, the method according to the invention is carried out at a temperature of at least 60~C. The method according to the invention is especially carried out at temperatures of from 60 to 300~C, more especially from 60 to 250~C, preferably from 60 to 200~C and especially preferably from 70 to 1 60~C. After polymerisation, it may be advantageous to temper the mixture at elevated temperatures, for example at from 80 to 200~C.
The adhesive mixture is applied to the substrate in known manner. The layer thickness of the adhesive films is generally not more than 500 ~m, and is preferably from 40 to 120,um. It is, however, possible for substantially thicker layers to be fully cured thermally.
Before being coated with the adhesive mixture, the surfaces to be bonded may, ifappropriate, be degreased and roughened.
After they have been brought together, the coated surfaces are pressed together or clamped, if appropriate.
Suitable surfaces for bonding are especially those made of metals, such as iron, steel, or especially aluminium and its alloys, for example with magnesium or silicon. The adhesive can also be used to bond two different materials, for example to bond metals to polymeric materials.
The bonds produced in accordance with the method according to the invention are distinguished especially by a high bond strength and minimal water absorption.
Example 1:
0.39 9 of Norsorex NS (thermoplastic polynorbornene, Nippon Zeon) is dissolved at 80~C in 38.91 g of dicyclopentadiene. After cooling to 60~C, 0.5 g of vinyltrimethoxysilane (Silquest~
A-171, Osi Specialties) and 0.2 g of (cyclohexyl)3P(p-cymene)RuCI2 are added, and the mixture is stirred for 20 minutes at 60~C. After the addition, in portions, of 60 g of wollastonite FW 200 (Partek Minerals), the mixture is stirred for a further 15 minutes. The mixture is then degassed for from 3 to 5 minutes in vacuo (3 mbar).
The mixture so obtained is poured into a 4 mm-thick plate mould of aluminium and then fully cured (2 h/80~C, 4 h/1 00~C, 1 h/1 50~C). It is established that the cured moulding has very good adhesion to aluminium and cannot be removed from the mould either at -180~C or at 200~C.
Claims (9)
1. Use, as an adhesive, of a composition comprising (a) at least one strained cycloolefin, (b) a catalyst for ring-opening metathesis polymerisation, (c) a filler and (d) a silane of formula I
wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may have been replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y1, Y2 and Y3 are each independently of the others C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C12cycloalkyl, C2-C20alkoxyalkyl or C1-C20acyl.
wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may have been replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y1, Y2 and Y3 are each independently of the others C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C12cycloalkyl, C2-C20alkoxyalkyl or C1-C20acyl.
2. The use of a composition according to claim 1 as an adhesive for metals.
3. The use of a composition according to claim 1 as an adhesive for aluminium.
4. The use of a composition according to claim 1 comprising dicyclopentadiene ascomponent (a).
5. The use of a composition according to claim 1 comprising (cyclohexyl)3P(p-cymene)RuCl2 as component (b).
6. The use of a composition according to claim 1 comprising as component (c) Al2O3, Al(OH)3, CaCO3, CaSiO3, SiO2, woven glass fibres, woven carbon fibres or woven aramid fibres.
7. The use of a composition according to claim 1 comprising as component (c) Al2O3, Al(OH)3, wollastonite, quartz powder, dolomite, lime, chalk, woven glass fibres, woven carbon fibres or woven aramid fibres.
8. The use of a composition according to claim 1 comprising vinyltrimethoxysilane as component (d).
9. A method of bonding two or more substrates, which comprises applying a curable composition comprising components (a) to (d) according to claim 1 to at least one of the substrates to be bonded, bringing the substrates to be bonded into contact with one another, and curing the composition by heating to a temperature > 40°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1619/97 | 1997-07-03 | ||
| CH161997 | 1997-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2242060A1 true CA2242060A1 (en) | 1999-01-03 |
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ID=4214678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2242060 Abandoned CA2242060A1 (en) | 1997-07-03 | 1998-06-30 | Cycloolefin-based adhesive |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0889107A3 (en) |
| JP (1) | JPH1180698A (en) |
| CA (1) | CA2242060A1 (en) |
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| US8597794B2 (en) | 1999-02-05 | 2013-12-03 | Materia, Inc. | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| WO2015011404A1 (en) | 2013-07-23 | 2015-01-29 | Bostik Sa | Hydrocarbon polymers with two alkoxysilane end groups |
| WO2015011405A1 (en) | 2013-07-23 | 2015-01-29 | Bostik Sa | Hydrocarbon polymers having an alkoxysilane end group |
| WO2016110653A1 (en) | 2015-01-08 | 2016-07-14 | Bostik Sa | Hydrocarbon polymers with two alcoxysilane end groups |
| WO2016116680A1 (en) | 2015-01-22 | 2016-07-28 | Bostik Sa | Hydrocarbonated polymers with two alcoxysilane end groups |
| US20170218131A1 (en) * | 2014-08-01 | 2017-08-03 | Kolon Industries, Inc. | Curable petroleum resin and method for preparing same |
| US9796889B2 (en) | 1999-02-05 | 2017-10-24 | Materia, Inc. | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| WO2017198935A1 (en) | 2016-05-17 | 2017-11-23 | Bostik Sa | Hydrocarbon polymers with two alkoxysilane end groups and processes for preparing same |
| WO2018002473A1 (en) | 2016-06-29 | 2018-01-04 | Bostik Sa | New hydrocarbon polymers comprising two alkoxysilane end groups, and methods for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6962729B2 (en) | 1998-12-11 | 2005-11-08 | Lord Corporation | Contact metathesis polymerization |
| US7025851B2 (en) | 1998-12-11 | 2006-04-11 | Lord Corporation | Contact metathesis polymerization |
| CA2318711A1 (en) * | 2000-09-13 | 2002-03-13 | Lord Corporation | Contact metathesis polymerization |
| EP1320566B1 (en) * | 2000-09-25 | 2005-12-14 | Lord Corporation | Contact metathesis polymerization |
| EP1241196A3 (en) * | 2001-03-12 | 2002-11-20 | Ciba SC Holding AG | ROMP with alkoxy ether groups |
| WO2016018131A1 (en) * | 2014-08-01 | 2016-02-04 | 코오롱인더스트리 주식회사 | Curable petroleum resin and method for preparing same |
| KR102003451B1 (en) | 2016-06-30 | 2019-07-24 | 코오롱인더스트리 주식회사 | Curable petroleum resin, preparation method thereof, and the use comprising of the same |
| KR102291384B1 (en) * | 2016-09-27 | 2021-08-20 | 코오롱인더스트리 주식회사 | Curable modified petroleum resin, preparation method thereof, and the use comprising the same |
| WO2021124156A1 (en) * | 2019-12-20 | 2021-06-24 | 3M Innovative Properties Company | Method of pattern coating adhesive composition comprising unpolymerized cyclic olefin and latent catalyst, adhesive compositions and articles |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0349855A3 (en) * | 1988-06-27 | 1991-01-23 | Hercules Incorporated | Molded article of metathesis polymerized polymer containing fillers and process for its preparation |
| US4910077A (en) * | 1988-08-04 | 1990-03-20 | B.F. Goodrich Company | Polynorbornene laminates and method of making the same |
| US5071701A (en) * | 1989-11-22 | 1991-12-10 | B. F. Goodrich Corporation | Copolymer for use in preparing prepregs, printed circuit wiring boards prepared from such prepregs and processes for preparing such printed circuit wiring boards |
| CN1166176A (en) * | 1994-11-17 | 1997-11-26 | 希巴特殊化学控股公司 | Thermal metathesis polymerisation process and a polymerisable compsn. |
| CN1096480C (en) * | 1994-12-23 | 2002-12-18 | 希巴特殊化学控股公司 | Polymerisable compound and polymerisation method |
| EP0771830B1 (en) * | 1995-11-02 | 2003-01-29 | Ciba Specialty Chemicals Holding Inc. | Curable composition containing cycloolefins, silane and filler |
-
1998
- 1998-06-24 EP EP98810579A patent/EP0889107A3/en not_active Ceased
- 1998-06-30 CA CA 2242060 patent/CA2242060A1/en not_active Abandoned
- 1998-07-03 JP JP10204424A patent/JPH1180698A/en active Pending
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| US7160969B2 (en) | 2001-03-12 | 2007-01-09 | Ciba Specialty Chemicals Corp. | ROMP with alkoxy ether groups |
| AU2014294874B2 (en) * | 2013-07-23 | 2018-06-28 | Bostik Sa | Hydrocarbon polymers with two alkoxysilane end groups |
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| US10662265B2 (en) | 2013-07-23 | 2020-05-26 | Bostik Sa | Hydrocarbon-based polymers bearing an alkoxysilane end group |
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| EP3176191A4 (en) * | 2014-08-01 | 2018-02-28 | Kolon Industries, Inc. | Curable petroleum resin and method for preparing same |
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| FR3031517A1 (en) * | 2015-01-08 | 2016-07-15 | Bostik Sa | HYDROCARBON POLYMERS WITH TWO ALCOXYSILANE TERMINAL GROUPS |
| WO2016110653A1 (en) | 2015-01-08 | 2016-07-14 | Bostik Sa | Hydrocarbon polymers with two alcoxysilane end groups |
| WO2016116680A1 (en) | 2015-01-22 | 2016-07-28 | Bostik Sa | Hydrocarbonated polymers with two alcoxysilane end groups |
| WO2017198935A1 (en) | 2016-05-17 | 2017-11-23 | Bostik Sa | Hydrocarbon polymers with two alkoxysilane end groups and processes for preparing same |
| WO2018002473A1 (en) | 2016-06-29 | 2018-01-04 | Bostik Sa | New hydrocarbon polymers comprising two alkoxysilane end groups, and methods for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1180698A (en) | 1999-03-26 |
| EP0889107A3 (en) | 1999-03-24 |
| EP0889107A2 (en) | 1999-01-07 |
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