CA2035396A1 - Siloxane copolymers containing alkenyloxy groups, a process for preparing the same and their use - Google Patents
Siloxane copolymers containing alkenyloxy groups, a process for preparing the same and their useInfo
- Publication number
- CA2035396A1 CA2035396A1 CA 2035396 CA2035396A CA2035396A1 CA 2035396 A1 CA2035396 A1 CA 2035396A1 CA 2035396 CA2035396 CA 2035396 CA 2035396 A CA2035396 A CA 2035396A CA 2035396 A1 CA2035396 A1 CA 2035396A1
- Authority
- CA
- Canada
- Prior art keywords
- radical
- formula
- per
- group
- atom
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 55
- 125000003302 alkenyloxy group Chemical group 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- -1 siloxane units Chemical group 0.000 claims abstract description 126
- 150000003254 radicals Chemical class 0.000 claims abstract description 85
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 9
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract 5
- 125000004434 sulfur atom Chemical group 0.000 claims abstract 5
- 150000002894 organic compounds Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 229920001296 polysiloxane Polymers 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 229910052697 platinum Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920001843 polymethylhydrosiloxane Chemical group 0.000 description 5
- 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 5
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 4
- 238000010538 cationic polymerization reaction Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 3
- CGERYHYIVJQVLJ-UHFFFAOYSA-N 2-methylbutane Chemical compound CC[C](C)C CGERYHYIVJQVLJ-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005336 allyloxy group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical class CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 2
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 2
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- AENNXXRRACDJAY-UHFFFAOYSA-N bis(2-dodecylphenyl)iodanium Chemical class CCCCCCCCCCCCC1=CC=CC=C1[I+]C1=CC=CC=C1CCCCCCCCCCCC AENNXXRRACDJAY-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical compound C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 235000008247 Echinochloa frumentacea Nutrition 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- 101100237844 Mus musculus Mmp19 gene Proteins 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000004072 Panicum sumatrense Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 101100463797 Rattus norvegicus Pgrmc1 gene Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 101150010487 are gene Proteins 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- ZVENKBGRIGHMRG-UHFFFAOYSA-M carbon monoxide chloro(hydrido)ruthenium triphenylphosphane Chemical compound [C-]#[O+].[H][Ru]Cl.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 ZVENKBGRIGHMRG-UHFFFAOYSA-M 0.000 description 1
- MLIYPCQSOXNTLJ-UHFFFAOYSA-N carbon monoxide;ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MLIYPCQSOXNTLJ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HIGHHSNPFSMLCS-UHFFFAOYSA-M chloro(hydrido)ruthenium;triphenylphosphane Chemical compound [RuH]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HIGHHSNPFSMLCS-UHFFFAOYSA-M 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- JJCFRYNCJDLXIK-UHFFFAOYSA-N cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical class [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical class O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007775 late Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012758 reinforcing additive Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- RXFATFKBDIQXLS-UHFFFAOYSA-N ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RXFATFKBDIQXLS-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
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Abstract
SILOXANE COPOLYMERS CONTAINING
ALKENYLOXY GROUPS, A PROCESS FOR
PREPARING THE SAME AND THEIR USE
Abstract of the Disc1osure Novel siloxane copolymers containing alkenyloxy groups and containing (a) siloxane units of the formula (I) (b) at least one siloxane unit per molecule of the formula (II) and optionally (c) at least one unit per molecule selected from the group comprising units of the formula (III) ( IV), and (V) in which R represents the same or different hydrocarbon radicals having from 1 to 18. carbon atom(s) per radical or halogenated hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical, R1 represents the same or different alkyl radicals having from 1 to 4 carbon atom(s) per radical and can be substituted by an ether oxygen atom, Q represents a radical of the formula -CH2CHR2CHR2OY(OCR2=CR2CH3)X-1 in which R2 is the same or different and represents a hydrogen atom or a methyl radical, Y represents trivalent, tetravalent, pentavalent or hexava-valent hydrocarbon radical having from 2 to 20 carbon atoms per radical, which can be substituted by groups of the formula - OH, - OR3, - OSiR43, -X
or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula =P, =P=O or =SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X represents a halogen atom, and R5 is a monovalent hydrocarbon radical having from 1 to 8 carbon atom(s) per radical, or Y represents a tetravalent element, such as ?-C-? , -Si- and -Ti-.
Q1 is a radical of the formula Q2 represents a radical of the formula and Q3 represents a radical of the formula
ALKENYLOXY GROUPS, A PROCESS FOR
PREPARING THE SAME AND THEIR USE
Abstract of the Disc1osure Novel siloxane copolymers containing alkenyloxy groups and containing (a) siloxane units of the formula (I) (b) at least one siloxane unit per molecule of the formula (II) and optionally (c) at least one unit per molecule selected from the group comprising units of the formula (III) ( IV), and (V) in which R represents the same or different hydrocarbon radicals having from 1 to 18. carbon atom(s) per radical or halogenated hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical, R1 represents the same or different alkyl radicals having from 1 to 4 carbon atom(s) per radical and can be substituted by an ether oxygen atom, Q represents a radical of the formula -CH2CHR2CHR2OY(OCR2=CR2CH3)X-1 in which R2 is the same or different and represents a hydrogen atom or a methyl radical, Y represents trivalent, tetravalent, pentavalent or hexava-valent hydrocarbon radical having from 2 to 20 carbon atoms per radical, which can be substituted by groups of the formula - OH, - OR3, - OSiR43, -X
or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula =P, =P=O or =SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X represents a halogen atom, and R5 is a monovalent hydrocarbon radical having from 1 to 8 carbon atom(s) per radical, or Y represents a tetravalent element, such as ?-C-? , -Si- and -Ti-.
Q1 is a radical of the formula Q2 represents a radical of the formula and Q3 represents a radical of the formula
Description
2~3~$
Docket No. WA 8~29 S
Paper No. 1 SILOXANE COPOLYMERS CONTAINING
ALXENYLOXY GROUPS, A PROCESS FOR PREPARING THE SAME
AND THEIR USE
The present invention relates to siloxane copolymers and more particularly to siloxane copolymers containing alkenyloxy groups and to a process for preparing the same. The invention furthermore relates to the use of the siloxane copolymers containing alkenyloxy groups in compositions which can be crosslinked by means of light.
Backqround of the Invention Organopolysiloxanes which contain at least one Si-bonded vinyloxy-functional group per-molecule o~:the formula H2C=CH-O-G-in which G is an alkylene radical or represents an alkylene radical which is interrupted by a divalent hetero atom or a combination of hetero atoms, are known from U.S. Patent No.
4,617,238 (published 14th October 1986, J.V. Crivello et al., General Electric Company). Compositions which can be cross-linked by means of light and which contain ~he organopoly- ~:
siloxanes mentioned above, and onium salts which catalyze the cationic polymerization of these organopolysiloxanes are described in U.S. Patent No. 4,617,238. ~ ::
2~ The reaction of an organic compound containing four aliphatic double bonds, such as,:for example, tetraallyloxy-ethane,:with a silane containing Si bonded hydxogen in the ~ :
presence of a catalyst which promotes the addition of the Si- ~ :
bonded hydrogen atom to an al~iphatic double bond is described in U.S. Patent No. 4,208,319 (published 18~h June 1980, P. August et al, Wacker-Chemie GmbH). Yields of organosilane containing 3 aliphatic double bonds~of practically 100~ of ~ . . .
: . . : .......... . ~:: : . . , . :
. , . ~ ; .
5~
theory are obtained in this reaction. The organosilanes thus obtained are us~d as reinforcing additives in compositions which are ~ased on organic polymers and fillers and can be crosslinked by means of sulfur or free radicals.
It is an object of the present invention to pro-vide siloxane copolymers which contain alkenyloxy groups.
Another ob~ect of the present invention is to provide a process for preparing siloxane copolymers containing alkeny-loxy groups which allows for the introduction of more than 10 one alkenyloxy group to a silicon atom. A further object of the present invention is to provide siloxane copolymers containing alkenyloxy groups which crosslink rapidly in the presence of light, especially ultraviolet light, ko undergo cationic polymerization.
Summ~ry of the Invention The foregoing objects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing alkenyloxy containing siloxane copolymers having 20 (a) siloxane units of the formula RaSi(ORl)bo4~
in which R represents the same or different hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical or halogenated hydrocarbon radicals having from 1 to 18 carbon atom(s) p ~ radical, Ri represents the same or different alkyl r ~icals which have from 1 to 4 carbon atom(s) per radical and can be substituted by an ether oxygen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3 and the sum of a+b is not greater than 3, (b) at least one siloxane unit per molecule of the formula QRcSiO4-(c+1) (II) in which R is the same as above, c is 0, 1 or 2 and Q
represents a radical of the ~rmula ': :
, ~ ~ .. ` . . . .
~3~3~
-CH2CHR2CHR20Y(OCR~=CR2CH3)X_l in which R~ is the same or different and represents a hydrogen atom or a methyl radical, Y represents a triva-lent, tetra~alent, pentavalent or hexavalent hydrocarbon radical which has from 2 to 20 carbon atoms per radical and can be substituted by groups of the ~ormula - OH, -oR3, - oSiR43, 1 0 - ocR3, o -- X, or can be interrupted by at least one oxygen atom or sulfur tom or one carhonyl group, or Y represents a i5 trivalent radical of th~ formula 5p ~ ap=O or asiR5 in which R3 represents an alkyl radical having from 1 to 6 carbon atom~s) per radical, R4 represents a methyl, ethyl, isopropyl, tert~butyl or phenyl radical, X
represents a halogen atom,and Rs represents a monovalent hydrocarbon radical having from 1 to ~ carbon atom(s) per radical, or Y represents a tetra-valent element, such as -C- , -Si- or -and x is 3, 4, 5 or 6, and optionally ~ :
(c) at least one unit per molecule selected from the yroup : -of units of:the formula : . ~ . . . : : " j .
~33~3~
04_(C+l)Rcsi-Ql-siRco4-(c~l) (III), 04_(C+l)Rcsi-Q2-siRco4-(c+l) SiR~04-(c~1) (IV), and SiRC04- (c+l) 04-(c+l)RcSi-Q3-SiRc04_(c+l~ (V) SiRC04- (c+l) in which R and c are the same as above, Ql represents a radical of the formula 15(OCR2=CR2CH33X-2 -CH2CHR2CElR20-Y-OCHR2CHR2CH2-Q2 represents a radical of the formula (fCR2-CR2CH3)X_ -CH2C~R2CHR20-Y-OCHR2CHR2CH2- and I
20OCNR~CHR2CH2~
Q3 represents a radical of the formula :
Docket No. WA 8~29 S
Paper No. 1 SILOXANE COPOLYMERS CONTAINING
ALXENYLOXY GROUPS, A PROCESS FOR PREPARING THE SAME
AND THEIR USE
The present invention relates to siloxane copolymers and more particularly to siloxane copolymers containing alkenyloxy groups and to a process for preparing the same. The invention furthermore relates to the use of the siloxane copolymers containing alkenyloxy groups in compositions which can be crosslinked by means of light.
Backqround of the Invention Organopolysiloxanes which contain at least one Si-bonded vinyloxy-functional group per-molecule o~:the formula H2C=CH-O-G-in which G is an alkylene radical or represents an alkylene radical which is interrupted by a divalent hetero atom or a combination of hetero atoms, are known from U.S. Patent No.
4,617,238 (published 14th October 1986, J.V. Crivello et al., General Electric Company). Compositions which can be cross-linked by means of light and which contain ~he organopoly- ~:
siloxanes mentioned above, and onium salts which catalyze the cationic polymerization of these organopolysiloxanes are described in U.S. Patent No. 4,617,238. ~ ::
2~ The reaction of an organic compound containing four aliphatic double bonds, such as,:for example, tetraallyloxy-ethane,:with a silane containing Si bonded hydxogen in the ~ :
presence of a catalyst which promotes the addition of the Si- ~ :
bonded hydrogen atom to an al~iphatic double bond is described in U.S. Patent No. 4,208,319 (published 18~h June 1980, P. August et al, Wacker-Chemie GmbH). Yields of organosilane containing 3 aliphatic double bonds~of practically 100~ of ~ . . .
: . . : .......... . ~:: : . . , . :
. , . ~ ; .
5~
theory are obtained in this reaction. The organosilanes thus obtained are us~d as reinforcing additives in compositions which are ~ased on organic polymers and fillers and can be crosslinked by means of sulfur or free radicals.
It is an object of the present invention to pro-vide siloxane copolymers which contain alkenyloxy groups.
Another ob~ect of the present invention is to provide a process for preparing siloxane copolymers containing alkeny-loxy groups which allows for the introduction of more than 10 one alkenyloxy group to a silicon atom. A further object of the present invention is to provide siloxane copolymers containing alkenyloxy groups which crosslink rapidly in the presence of light, especially ultraviolet light, ko undergo cationic polymerization.
Summ~ry of the Invention The foregoing objects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing alkenyloxy containing siloxane copolymers having 20 (a) siloxane units of the formula RaSi(ORl)bo4~
in which R represents the same or different hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical or halogenated hydrocarbon radicals having from 1 to 18 carbon atom(s) p ~ radical, Ri represents the same or different alkyl r ~icals which have from 1 to 4 carbon atom(s) per radical and can be substituted by an ether oxygen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3 and the sum of a+b is not greater than 3, (b) at least one siloxane unit per molecule of the formula QRcSiO4-(c+1) (II) in which R is the same as above, c is 0, 1 or 2 and Q
represents a radical of the ~rmula ': :
, ~ ~ .. ` . . . .
~3~3~
-CH2CHR2CHR20Y(OCR~=CR2CH3)X_l in which R~ is the same or different and represents a hydrogen atom or a methyl radical, Y represents a triva-lent, tetra~alent, pentavalent or hexavalent hydrocarbon radical which has from 2 to 20 carbon atoms per radical and can be substituted by groups of the ~ormula - OH, -oR3, - oSiR43, 1 0 - ocR3, o -- X, or can be interrupted by at least one oxygen atom or sulfur tom or one carhonyl group, or Y represents a i5 trivalent radical of th~ formula 5p ~ ap=O or asiR5 in which R3 represents an alkyl radical having from 1 to 6 carbon atom~s) per radical, R4 represents a methyl, ethyl, isopropyl, tert~butyl or phenyl radical, X
represents a halogen atom,and Rs represents a monovalent hydrocarbon radical having from 1 to ~ carbon atom(s) per radical, or Y represents a tetra-valent element, such as -C- , -Si- or -and x is 3, 4, 5 or 6, and optionally ~ :
(c) at least one unit per molecule selected from the yroup : -of units of:the formula : . ~ . . . : : " j .
~33~3~
04_(C+l)Rcsi-Ql-siRco4-(c~l) (III), 04_(C+l)Rcsi-Q2-siRco4-(c+l) SiR~04-(c~1) (IV), and SiRC04- (c+l) 04-(c+l)RcSi-Q3-SiRc04_(c+l~ (V) SiRC04- (c+l) in which R and c are the same as above, Ql represents a radical of the formula 15(OCR2=CR2CH33X-2 -CH2CHR2CElR20-Y-OCHR2CHR2CH2-Q2 represents a radical of the formula (fCR2-CR2CH3)X_ -CH2C~R2CHR20-Y-OCHR2CHR2CH2- and I
20OCNR~CHR2CH2~
Q3 represents a radical of the formula :
3 ~ ~
(ocR2-cR2cH3)x-4 -CH2CHR2C~R2O-Y-OCHR2CHR2CH2- (X-4~0) (1C~R2CHR~CH2-~ 2, in which R2, Y and x are the same as above.
Description of the Invention The siloxane copolymers containing alkenyloxy groups preferably contain siloxane units of formula (I), at least one siloxane unit per molecule of formula (II) and at least one unit per molecule selected from the group comprising units of formula (III), (IV) and ~V).
The invention also relates to a process for pre-paring siloxane copolymers containing alkenyloxy groups, which comprises, in a 1st stage, reacting an organic compound (1) containing more than two aliphatic double bonds, of the general formula Y(OCHR2CR2=C~I2)X
in which R2, Y and x are the same as above, with~an organo-polysiloxane (2) having at least one Si-bonded hydrogen atom per molecule in the presence of a catalyst (3) which promotes zo the addition of Si-bonded hydrogen to an aliphatic double bond, the ratio employed for the aliphatic double bond in the organic compound (l) to the Si-bonded hydrogen in the organo-polysiloxane (2) being a ratio such that siloxane copolymers which contain alkenyl groups and have an average of more than two alkenyl groups A of the formula ~ OC~IR2CR2=CEI2 in which R2 is the same as above, are obtained, and then, ln a 2nd stage, transferring the double bond in the alkenyl groups A to the carbon atom adjacent to the ether oxygen atom by heating the siloxane copolymer containing alkenyl groups obtained in the 1st stage in the presence of a catlyst (4) which promotes such a transfer of the double bond, siloxane ::
: ~
, :.
2 ')S~3:~
copolymers which contain alkenyloxy groups and have an average of more than two alkenyloxy groups B of the formula -OCR~=CR2CH3 in which R2 is the same as above, are obtained.
Preferably, x is 3 or 4 and Y is a trivalent or tetravalent radical.
The organopolysiloxanes o~ this invention con-taining alkenyloxy groups preferably have a visoosity of from 5 to 5x105 mPa.s at 25C, and more preferably ~rom 50 to 50,000 mPa.s at 25C.
Examples of radicals represented by R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, l~n-butyl, 2-n butyl, iso-butyl, tert-butyl, n-pentyl, iso pentyl, neo-pentyl and tert-pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl'radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl - radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical; cycloalkyl radicals, ~uch as cyclo-pentyl, cyclohexyl and cycloheptyl radicals and methylcyclo-hexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the ~- and ~-phenethyl rad'ical. The methyl radical is an example of the preferred radical.
Examples of halogenated radicals represented by R
are halogenoalkyl radicals, such as the 3,3,3-trifluoro-n- -propyl radical, the 2,2,2,2',2',2'-hexa~luoroisopropyl radical and the heptafluoroisopropyl radical, and halogenaryl radicals, such as the o-, m- and p-chlorophenyl radical.
Examples of alkyl radicals represented by R1 are the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl and tert-butyl radical. The methyl and ; ethyl radicals are the pre~erred radicals. Examples of alkyl ' , , .
, ~
.
, .
.
' ' ~ ~ ~ ~ 3 ~ ~
radicals represented by Rl which are substituted by an ether oxygen atom are the methoxyethyl and ethoxyethyl radicals.
The radical represented by R2 is preferably a hydrogen atom.
Examples of alkyl radicals represented by R3 are the methyl, ethyl, n-propyl, iso-pxopyl, lwn-butyl, 2-n--` butyl, iso-butyl, tert-butyl-, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radical and he~yl radicals, such as the n-hexyl radical.
Examples of radicals represented by R5 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, l-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical, and iso-octyl radicals, such as the 2,2,4-trimethyl-pentyl radical, alkenyl radicals, such as the vinyl and the allyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl radical; alkaryl radicals, such as o , m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the ~- and ~-phen2thyl radical.
Preferred siloxane copolymers containing alkenyloxy groups are those which contain `~ ;
(a) siloxane units of the fo~mula R2SiQ (1') (b) at least two siloxane unit0 per molecule of the formula ~R2Siol/2 (II') and (c) at least one unit per molecule o~ the formula ol/2R2siQ~siR2ol/2 (III') in which R, Q and Q1 are the same as above.
Exampl~s of the organic compound (l) which contains : 35 more:than two aliphatic.double bonds and is employed in the : :
... ,.......... : j , . ~ -- ~
, ~ :
- ~ ; - . :
:. : .
- ~ . : ' ' ~ ~ ~ 5 3 ~ ~
1st stage of the process of this invention are those of the formula f CH2 CH=CH2 C~H2=C~CH20-CH-C~I2 '-OCH2 CH--CH2 CH3-C-CH2-OCH2cH=cH2 CH2 -0CH2 CH=CH2 CX2 -ocH2cH=cH2 CH3--CH2-C-CH2 0CH2CH=CH2 CH2-OCN2CH=cN2 C:H2 -0CN2 CH=CH2 No-cH2 -c-c~I2 -ocH2 cH=c~2 C~12 -0CH2 CE~=C~2 ~ :
CN2-0CH2CH=cH2 1, :
CH2-ocH2cH=cH2 :
CN2-OCN2CH=cN2 CH2=CHCH2O-C~2--C-CH2-OCH2CH=CH
~ CN2-ocH2cN=cN2 (CH2=CHCN2O~2CHCE(OCH2CH=CH2)~
~` :
~-~3~3~
(CH2=CHCH20)2CHCH2CHtOCH2CH=CH2)2 CH3C(OCH2CH=cH2)3 C(OCH2CH=cH2)4 (cH2=cHcH2o)cH2[CH(ocH2cH=cH2)]3cH2(ocH2cH=cH2) (cH2=cHcH2o)cH2[cH(oc~2cH=cH~)]4cH2(ocH2cH=cH2) Si(OCH2CH=cH2)4 Si[OCH(CH3)CH=CH2]4 P(OCH2CH=CH2)3~
o=p(ocH2cH=cH2)3 and (R60--CEI2--) 4_kC (-cH2-o~H2cH=cH2 ~
in which R6 represents hydrogen or a radical of the formula o CH3C- and k is an average of from 2.5 to 3.5, and more preferably about 2.9. The last mentioned compound is the preferred example.
Examples of the radical represented by Y are those of the formula -CH-CH2- :
. ... . . . -, - . .. . . ..
:
, : . . . . .
2 -~ 3 ~
fH2 -CH3-C-cH2-IC~2-CH3-CH2-f-CH2-C~2 -ClH2-Ho CH2-f-CH2-CH
lcH2-CH3-1Cj-O- H2-C-CH2-`' ~ i -CH-CH-j -CH-CH2-CH-~: `
-CH2-CH-CH-CH-CH2 . ` ~ .
: ':
: 20 -CH2-CH-CH-CH-CH-CH2~
`` : : : :: ~ ~ ~
` : : : :`
:
,, . :, . . : ` `
2 ~
- c -i --si---P and -P=O.
Processes for preparing organic compound ~1) are described in EP-B 46,731 (published 3rd October 1984, F. Lohse et al., Ciba-Geigy AG). The compound of the formula (HOCH2)4 kc(cH2oc~2cH=cH2)k in which k is 2.9, is commercially availa~le, for example from Shell AG and is markete~ as pentaerythritol triallyl ether. The compound of the formula (c~3~oc~2~4-kc(cH2ocH2c~=c~2)k~
in which k is an average o~ from 2.5 to 3.5, and more preferably about 2.9, is obtained by reactin~ the compound mentioned above~with acetic anhydride:or isopropenyl acetate.
Organosiloxanes (2~ having at least one Si-bonded hydrogen atom whlch are preferably employed in the 1st stage 20 ~ of the process of this invention are those of the general:
:formula ~
~ ~ HeRfSiO4-(e+f) '~ (VI) in which R is the same as above, e is O or 1, with an average~of ~rom 0.005 to 1.0, f is 0, 1, 2~:or 3, with an average of from 1.0 ~Q 2.0, and the sum of~e+f lS not~greater :~
than 3.
Organopolysiloxanes (2) having at least one Si~
bonded hydrogen atom which are preferably employed in the 30 ~ ~ process o~ this~ln~ention are tho9e of the general formula~
: ~
.. ..
. ~ ' '. : ": , ' 2~3 HdR3-dsio(siR2o)o~siRHo)psiR3-dHd (VII) in which R is the same as above, d is 0 or l, o is 0 or an integer of from l to 1,000 and p is 0 or an integer o~ from l to 6.
The organopolysiloxanes (2) having at least one Si-bonded hydrogen atom per molecule pre~erably have a viscosity of from 0.5 to 20,000 mPa.s at 25C, and more preferably from 5 to 1,000 mPa.s at 25~C.
Examples of organopolysiloxanes (2) are copolymers uf dimethylhydrogensiloxane and dimethylsiloxane units, copolymers o~ dimethylhydrogensiloxane, dimethylsiloxane and methylhydrogensiloxane units, copolymers of trimPthylsiloxane and methylhydrogensiloxane units, copol~mers o~ trimethyl-siloxane, dimethylsiloxane and methylhydrogensiloxane units, copolymers of dimethylhydrogensiloxane, dim~thylsiloxane and phenylmethylsiloxane units, copolymers of dimethylhydrogen-siloxane and methylsiloxane units and copolymers of dimethyl-hydrogensiloXane and phenylsiloxane units, copolymers of methylhydrogensiloxane and diphenylsiloxane units, copolymers of methylhydrogensiloxane,dimethylsiloxane and phenylsiloxane units and copolymers o~ dimethylhydrogensiloxane, dimethyl-siloxane and phenylsiloxane:units.
Processes for preparing organopolysiloxanes having at least one Si-bonded hydrogen atom per molecule, including those of the preferred type, are gene~ally known.
The organic compound (1) is employed in the process of this invention in amounts such that the ratio of the aliphatic double bond in the organic cmmpound ~1) to the Si-bonded hydrogen in the organopolysiloxane (2) is preferably : 30 from 1.5 : 1 to 20 : 1, and more preferably ~rom 2 : 1 to 10 :~
: 1. The organic compound ~l) can be combin~d with the :- -organopolysiloxane (2) almost as~de~ired within very wide :
limits, depending on:their functionality and their molecular weight. However, a C=C : siH: ratio of greater than 20 leads exclusively to monohydrosilylation o~ the organic compound (1), which is not preferred~
. ,, , . : ......... . . ......... ~ . , .
., : , ,. . - - : ~, , :. :
, . :
, ~3~3~
The same catalysts ~hich have b~en or could have been employed to promote the addition of Si-bonded hydrogen to an aliphatic double bond can also be us~d as catalysts (3) which promote the addition of Si-bondPd hydrogen to an aliphatic multiple bond in the 1st stage of the process of this invention. The catalysts (3) are preferably a metal from the group of platinum metals or a compound or a complex from the group of platinum metals. Examples of such catalysts are metallic and finely divided platinum, which can be supported on inert carriers, such as silicon dioxide, aluminum oxide or active charcoal, and compounds or complexes of platinum, such as platinum halides, for example PtCl4, H2PtCl6 6H20, Na2PtCl4 4H20, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H2PtCl6 6H20 and cyclohexanone, platinum-vinylsiloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetramethyl-disiloxane complexes which contain or are free of detectable inorganically bonded halogen, bis-~gamma-picoline)-platinum dichloride, trimethylenedipyridineplatinum dichloride, dicyclopentadieneplatinum dichloride, dimethylsul~oxide-ethyleneplatinum (II) dichloride and reaction products of platinum tetrachloride with an olefin and primary amine or secondary amine or a primary and secondary amine according to U.S. Patent No. 4,292,434, such as th~ reaction product of platinumtetrachloride dissolved in l-oc~ene with sec-butyla-mine, or ammonium~platinum complexes according:to EP-B
110,370.
Catalyst (3) is preferably employed in amounts of from 0.5 to 1,000 ppm by weight (parts by weight per million parts by weight), calculated as elemental platinum and based - on the total weight of the organic compound (1) and organo-polysiloxane (2).
The addition reaction (or hydrosilylation reaction) in the 1st stage of t.he process of this invention is preferably carried out under the pressure of the :
-2 ~ 3 ~ 3 ~ ~
surrounding atmosphere, that is, at about 1020 hPa (absolute), but it can also be carried out under higher or lower pressures. The hydrosilylation is preferably carried out at a temperature of from 50OC to 150C~ and more pre-ferably from 80C to 130C.
Inert organic solvents can also be used in the 1st stage of the process of this invention, although the additional use of inert organic solvents is not preferred.
Examples of inert organic solvents are toluene, xylene, octane isomers, butyl acetate~ 1,2-dimethoxyethane, tetrahydrofuran and cyclohexane.
Excess organic compound (1) and the inert organic solvent, if used, are preferably removed by distillation from the siloxane copolymer which contains alkenyl groups and has been prepared in the 1st stage of the process of this invention.
The siloxane copolymers which contain alkenyl groups and have been obtained in the 1st stage of the process of this invention are described in our patent application filed on the same date.
In the 2nd stage of the process of this invention, the double bond in the alkenyl groups A of the formula -OCHR2 CR2 = CH2 is shifted to the carbon atom adjacent to the ether oxygen atom in the presence of catalysts (4) which promote this ~-double bond transfer.
The same catalysts (4) which have been or could have been used for promoting such a shift o~ the double bond can be employed in the 2nd stage of the process of this invention. Examples of catalysts (4) are m allic or ~inely - divided platinum, ruthenium, rhodium and palladium, which may be supported on inert carriers, such as active charcoal, and compounds or complexes of these elements which are soluble in the siloxane copolymers which contain alkenyl groups and have been obtained in the 1st stage o~ the process of this invention or which are fixed on supports, such a~ active charcoal or polymeric phosphine ligands. Examples o~
::
, . .
', ' ... : : ' ' ' ~ ~ `
.: . . ~ : . .. . . .... . . .
3 ~ 5 preferred catalysts (4) are those of the formula RuC12(PPh3)3, RuHCl(PPh3)3, RuHCl(CO)(PPh3)3, RuH2(CO)(PPh3)3 and RuH2(PPh3)4.
The ca~alyst (~) is pxe~erably employed in amounts of from 0.1 to 1,000 ppm by weight, and more preferably from 5 to lOo ppm by weight, calculated as th~ elemental metal and based on the total weight of the organic compound (1) and organopolysiloxane (2).
Strong bases, such as potassium tert-butylate, can also be used as catalysts (4), but these are not preferred because of the high amounts used. The shift o~ double bonds ~sing these strong bases is described in C.C. Price, JACS
83,1772 ~1961) and G. Kesslin, J. Org. Chem. 31, 2682 (1966).
To shift the double bond to the carbon atom adjacent to the ether oxygen atom in the alkenyl groups A, the siloxane copolymer which contains alkenyl groups and has been obtained ~rom the 1st stage of tha process o~ this invention is mixed with the catalyst (4) and the mixture is heated. The reaction is preferably carried out at a temperature of from 80C to 2007C and more preferably from 120C to 150~C, preferably under the pressure of the surrounding atmosphere, that is, a~ about 1020 hPa (absolute), and preferably over a period of from 0.5 to 20 hours, and more preferably from 4 to 10 hours. Preferably, no solvent is used.
If the organic compound (1) is not removed by distillation in the 1st stage o~ the process of this inve~ntion, the alkenyl groups A in the organic compound (1) are also rearranged into alkenyloxy groups B. The rearranged organic compound (l) can be removed by distillation from the siloxane copolymers which contain alkenyloxy groups and have been prepared in the 2nd stage of the process of this invention. If it is not removed, it is capable o~ undergoing cationic polymerlza~ion or copoly-.
~: : :: : :
$
merization with the alkenyloxy yroups of the siloxane copolymer because of its content of alkenyloxy groups B.
The siloxane copolymer which contains alkenyloxy groups and is obtained in the 2nd stage of the process of this invention i5 a cis/trans isomer mixture in respect to the alkenyloxy groups, the cis isomers usually predominating.
For example, if the alkenyloxy group is a l-propenyloxypropyl radical, the following isomeric mixture is present:
-(cH2~3-o\ fH3 -(CH2)3-o H
C=C C=C
I \ I \
cis- trans-The 2-stage process of this invention proceeds in accordance with the ~ollowing equation, shown by way of example by the use of pentaerythritol-triallyl ether-acetate as the organic compound (1) and an ~,w-dihydrogendimethyl-polysiloxane as the organopolysiloxane (2):
Pt Cat.
CH3C02CH2C(CH20CH2CH=CH2~3 + N(SiMe20)50SiNe2H~ ---> ~;
20~fH2OCH2CH=cH2)2 CH3CO2CH2CCH2O(cH2)3(siMe2O)50si~e2(cH2)3OlH2 T
: C~3CO2CH2cc~20 Q2cH-cH2 -->
CH3CO2CH2CjcH2O(cH2)3(siMe2O)5osiNe2(c~2)3ocH2 Cat (CH2OcH2cH=cH2)2 :
25(CH2OCH=CHCH3)2 CH3CO2CH2CCH2O(CH2)3(siMe2O)505iMe2(cH2)3olH2 ~:
CH3CO2cH27cH20cH=cHcH3 CH3CO2CH2fCH2O(CH2)3(siMe2O)50siMe2~c~2)3~cH2 (cHzocH=cHcH3)2 30The course o~ the reaction and kherefore the resulting end product is kotally dependent on the ratio of C=C double bond in the organiic compound (l) to Si-bonded ~: :
',' j ' ' ' . . . " . : ' ' ~,,' . ' ; '', ., , ' : ' ' ' . ' .
~. 1) 3 ~
hydrogen in the organopolysiloxane (2) which is employed in the 1st stage. Depending on the ratio of C=C:SiH employed, it is always necessary for the ratio of C=C:SiH to ~e greater than 1, siloxane copolymers are obtained which contain free alkenyl groups A of the form-lla -OCH~2CR2=CH2, such as -0CH2CH=CH2 at the chain end and along the chain, it being possible ~or branching to occur along the chain by further reaction of the free alkenyl groups along the chain with the Si-bonded hydrogen atoms of the organopolysiloxane (2). In the 2nd stage, the double bond in the free alkenyl groups A is then shifted and free alkenyloxy groups B of the formula - OCR2=CR2CH3 r such as -OCH=CHCH3 are obtained. The allyloxy groups, -OCH2CH=CH2, have already been rearranged into propenyloxy groups, -OCH=CHCH3, to a small degree (up to 15 mol %) in the 1st stage in the presence of the platinum catalysts, so that in the 2nd stage an equilibrium is established between allyloxy and propeny-loxy groups, in that the ratio of allyloxy groups to propeny-loxy groups is usually 4:96, that is, a conversion of about96% is achieved in respect of the propenyloxy groups.
The various stages of the process of this invention can be carried out in one and the sama r~action vessel in succession or in reaction vessels which are separate from each other. They are preferably carried out in one and the same reaction vessel in succession. The process of this invention can be carried out batchwise, semi-continuously or continuously.
The siloxane copolymers of this invention con~aining alkenyloxy groups can be crosslinked in a cationic polymerization initiated by light. The bis-(dodecylphenyl)-iodonium salts described in U.S. Patent No. 4,279,717 (published 21st July 1981, Eckberg et al., General Electric Company), such as bis-(dodecylphenyl)iodonium ::
:
:
. :
6~
hexafluoroantimonate or bis-(dodecylphenyl) iodonium hexafluoroarsenate, can be used, ~or example, as catalysts for the crosslinking initiated by light.
The invention therefore relates to the use of siloxane copolymers which contain alkenyloxy groups and preferably contain u~its of the formula (I), (II) and if appropriate at least one of the units of the formula (III), (IV), or (V), preferably units o~ the formula ~I'), (II') and ~III'), in compositions which are based on the siloxane copolymers mentioned above and can be crosslinked by light.
The siloxane copolymers of this invention containing alkenyloxy groups are preferably crosslinked by untraviolet light, that having wavelengths in the range of from 200 to 400 nm being preferred. The ultraviolet light can be generated, for example, in xenon lamps or low pressure, medium pressure or high pressure mercury lamps.
Light having a wavelength of 400 to 600 nm, that is to say so-called "halogen light", is also suitable for the ; crosslinking by means of light. The siloxane copolymers of this invention containing alkenyloxy groups can be crosslinked by light in the visible range if commercially available photosensitizers are used.
The cationic polymerization of the siloxane copolymars of this invention containing alkenyloxy groups can of course also be initiated by Bronsted or Lewi~ acids.
The invention also r~lates ~o the use of the siloxane copolymers of this invention containing alkenyloxy groups for the preparation of coatings which can be crosslinked by light.
Examples of surfaces to which the coatings of this invention can be applied are those of paper, wood, cork, plastic films, for example polyethylene films or polypropylene films, ceramic objects, glass, including glass fibers, metals, paperboard, including that of asbestos, and woven and nonwoven cloth of natural or synthetic organic fibers.
~.
: ~ . : . :
-. : , . . . : :1 ~ .
~ t-~3~
The application of the siloxane copolymers of this invention containing alkenyloxy groups to the sur~aces ~o be coated can be carried out in any desired manner which is suitable and in many cases known for the production of coatings from liquid substances, for example by dipping, brushing, pouring, spraying, rollin~ on, printing, for example by means of an offset gravure transfer device, and knife or doctor-blade coating.
Example 1:
About 89 g of 1,1,2,2-tetraallyloxyethane are mixed with 5.4 mg of platinum as a solution of platinum tetrachloride in 1-octene and the mixture is heated to 110C. About 581 g of an ~,w-dihydrogendimethylpoly-siloxane which contains 250 mg of Si-bonded hydrogen are added dropwise to this mixture at 110C under a nitrogen atmosphere, with stirring. After the mixture has been stirred at 110C for about 3 hours, 98% of ~he Si-bonded hydrogen atoms of the ~,w-dihydrogendimethyl-polysiloxane have reacted. All the volatile constituents are then removed by distillation at 120C
under 10-3 hPa. About 110 mg of RuHCl(Ph3P)3 are then added to the xeaction product at 130~C under 1020 hPa (absolute) under a nitrogen atmosphexe and the mixture is stirred at 130C for 16 hours. A clear yellow liquid having a viscosity of about 1100 mPa.s at 25C is obtained. The siloxane copolymer thus obtained essentially contains, in addition to dimethylsiloxane units, siloxane units of the formula fCH=CHCH3 (CH3CH=cHO)2cHcHO(cH2)3siO3/2 and bridged units of the formula CH3CH-CHO fCH=CHCH3 O(CH3)2Si(CH2)30CHC}~O(C}l2)3Si(CH3)20, the ratio of cis isomer to trans isomer in the 1-propenyloxy groups, CH3CH-CH0-, being 70 : 30 according .
.
., : ~ : . ....... , ,. , ,,; .
- , -! ' , `.
, ~
, ' '~' ,'' . ' " ' ' ' ,' ,' " '" ' ' ~, ' . .
~3~
to th~ lH NMR spectrum. The siloxane copolymer containing l-propenyloxy groups has an equivalent weight of about 1300 g per mol of C=C double bond.
Example 2-About 11404 g of trimethyolpropane-allyl ether (preparPd in accordance with EP-B 46,731) having an iodine number (number which specifies how many g of iodine are bonded by 100 g of substance) of 266 are mixed with 3.8 mg of platinum in the form of a solution of platinum tetrachloride in l-octene and the mixture is heated to 105C. About 273 g of an ,w-dihydrogendimethylpoly-siloxane which contains 0.6 g of Si-bonded hydrogen are added dropwise to this mixture at 105C under a nitrogen atmosphere, while stirring. After the mixture has been stirred at 105C for about 4 hours, gg% of the Si-bonded hydrogen atoms of the ~,w dihydrogenmethylpolysiloxane have reacted. All the volatile constituents are then removed by distillation at 120C under 10-3 hPa. About 200 ppm by weight of RuHCl(Ph3P)3 are ~hen added to the reaction product at 130C under 1020 hPa (absolute) under a nitrogen atmosphere and the mixture is stirred at 130'C for 8 hours. About 315 g of a clear, almost colorless oil having a ~iscosity of 380 mm2x s-1 at 25C
are obtained. The siloxane copolymer containing 1-propenyloxy groups~ which is obtained in this manner, has an equivalent weight of abou~ 900 g per mol of C=C
double bond.
Example 3:
About 48 g of pentaerythritol-triallyl ether having an iodine number of 281 (commercially obtainable from Shell) are mixed with 2.2 mg of platinum a a solution of platinum tetrachloride in 1-octene and the mixture is heated to 105C. About 435 g of an ~,w~dihydrogendi methylpolysiloxane which contains 0.046~ by weight of Si-bonded hydrogen are added dropwise to this mixture at 105UC under a nitrogen atmosphere, with stirring. After .
3 ~ ~
the mixture has been stirred at 105C for about 8 hours, 98~ of the Si-bonded hydrogen atoms of the ~,w-dihydrogendimethylpolysiloxane have reacted. All the volatile constituents are then removed by distillation at 120C under 10-3 hPa. After filtration, 76 mg of RuHCl(Ph3P)3 are then added to the reaction product at 130C under 1020 hPa (absolute) under a nitrogen atmosphere and the mixture is stirred at 130C
for 8 hours. A siloxane copolymer is obtained which contains l-propenyloxy groups and has a viscosity of 1190 mm2x 5-l, contains ona l-propenyloxy group per 32 silicon atoms and has an equivalent weight of about 2400 g per mol o~ C=C double bond. The ratio of cis isomer to trans isomer in the l-propenyloxy groups is 70 : 30.
The following data are obtained from the lH-NMR
spectrum lH-NMR spectrum (CDCl3):
trans isomer: ~ = 4.78 ppm (lH, CH3CH=), (30 mol %) 6.22 ppm (lH, = CH-O-~.
cis isomer : ~ = 4.37 ppm ~lH, CH3CH=), (70 mol ~) 5.95 ppm (lH, -CH-0-).
Example 4:
About 2 g of a 50~ solution of bis-(dodecylphenylj-iodonium hexafluorantimonate which has been prepared according to U.S. Patent No. 4,2i9,717 in propylene carbonate are added to lO0 g of the siloxane copolym~r prepared in Example 3. The mixture is applied at a thickness of 3 ~, using a glass rod, to paper coated with polyethylene. Two medium pressure mercury lamps having an output of 80 watt/cm luminous length are positioned at a distance o~ 10 cm from the coated substrate. After UV exposure ~or less than two seconds, a non-tacky coating is obtained which is adhesive-repellent with respect to paper labels coated with acrylate adhesive.
, - , . . . - , ~ ~ . ~, . .. : . .
.. . . . . .
'' ~
:. . . . , :: : ,
(ocR2-cR2cH3)x-4 -CH2CHR2C~R2O-Y-OCHR2CHR2CH2- (X-4~0) (1C~R2CHR~CH2-~ 2, in which R2, Y and x are the same as above.
Description of the Invention The siloxane copolymers containing alkenyloxy groups preferably contain siloxane units of formula (I), at least one siloxane unit per molecule of formula (II) and at least one unit per molecule selected from the group comprising units of formula (III), (IV) and ~V).
The invention also relates to a process for pre-paring siloxane copolymers containing alkenyloxy groups, which comprises, in a 1st stage, reacting an organic compound (1) containing more than two aliphatic double bonds, of the general formula Y(OCHR2CR2=C~I2)X
in which R2, Y and x are the same as above, with~an organo-polysiloxane (2) having at least one Si-bonded hydrogen atom per molecule in the presence of a catalyst (3) which promotes zo the addition of Si-bonded hydrogen to an aliphatic double bond, the ratio employed for the aliphatic double bond in the organic compound (l) to the Si-bonded hydrogen in the organo-polysiloxane (2) being a ratio such that siloxane copolymers which contain alkenyl groups and have an average of more than two alkenyl groups A of the formula ~ OC~IR2CR2=CEI2 in which R2 is the same as above, are obtained, and then, ln a 2nd stage, transferring the double bond in the alkenyl groups A to the carbon atom adjacent to the ether oxygen atom by heating the siloxane copolymer containing alkenyl groups obtained in the 1st stage in the presence of a catlyst (4) which promotes such a transfer of the double bond, siloxane ::
: ~
, :.
2 ')S~3:~
copolymers which contain alkenyloxy groups and have an average of more than two alkenyloxy groups B of the formula -OCR~=CR2CH3 in which R2 is the same as above, are obtained.
Preferably, x is 3 or 4 and Y is a trivalent or tetravalent radical.
The organopolysiloxanes o~ this invention con-taining alkenyloxy groups preferably have a visoosity of from 5 to 5x105 mPa.s at 25C, and more preferably ~rom 50 to 50,000 mPa.s at 25C.
Examples of radicals represented by R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, l~n-butyl, 2-n butyl, iso-butyl, tert-butyl, n-pentyl, iso pentyl, neo-pentyl and tert-pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl'radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl - radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical; cycloalkyl radicals, ~uch as cyclo-pentyl, cyclohexyl and cycloheptyl radicals and methylcyclo-hexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the ~- and ~-phenethyl rad'ical. The methyl radical is an example of the preferred radical.
Examples of halogenated radicals represented by R
are halogenoalkyl radicals, such as the 3,3,3-trifluoro-n- -propyl radical, the 2,2,2,2',2',2'-hexa~luoroisopropyl radical and the heptafluoroisopropyl radical, and halogenaryl radicals, such as the o-, m- and p-chlorophenyl radical.
Examples of alkyl radicals represented by R1 are the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl and tert-butyl radical. The methyl and ; ethyl radicals are the pre~erred radicals. Examples of alkyl ' , , .
, ~
.
, .
.
' ' ~ ~ ~ ~ 3 ~ ~
radicals represented by Rl which are substituted by an ether oxygen atom are the methoxyethyl and ethoxyethyl radicals.
The radical represented by R2 is preferably a hydrogen atom.
Examples of alkyl radicals represented by R3 are the methyl, ethyl, n-propyl, iso-pxopyl, lwn-butyl, 2-n--` butyl, iso-butyl, tert-butyl-, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radical and he~yl radicals, such as the n-hexyl radical.
Examples of radicals represented by R5 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, l-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical, and iso-octyl radicals, such as the 2,2,4-trimethyl-pentyl radical, alkenyl radicals, such as the vinyl and the allyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl radical; alkaryl radicals, such as o , m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the ~- and ~-phen2thyl radical.
Preferred siloxane copolymers containing alkenyloxy groups are those which contain `~ ;
(a) siloxane units of the fo~mula R2SiQ (1') (b) at least two siloxane unit0 per molecule of the formula ~R2Siol/2 (II') and (c) at least one unit per molecule o~ the formula ol/2R2siQ~siR2ol/2 (III') in which R, Q and Q1 are the same as above.
Exampl~s of the organic compound (l) which contains : 35 more:than two aliphatic.double bonds and is employed in the : :
... ,.......... : j , . ~ -- ~
, ~ :
- ~ ; - . :
:. : .
- ~ . : ' ' ~ ~ ~ 5 3 ~ ~
1st stage of the process of this invention are those of the formula f CH2 CH=CH2 C~H2=C~CH20-CH-C~I2 '-OCH2 CH--CH2 CH3-C-CH2-OCH2cH=cH2 CH2 -0CH2 CH=CH2 CX2 -ocH2cH=cH2 CH3--CH2-C-CH2 0CH2CH=CH2 CH2-OCN2CH=cN2 C:H2 -0CN2 CH=CH2 No-cH2 -c-c~I2 -ocH2 cH=c~2 C~12 -0CH2 CE~=C~2 ~ :
CN2-0CH2CH=cH2 1, :
CH2-ocH2cH=cH2 :
CN2-OCN2CH=cN2 CH2=CHCH2O-C~2--C-CH2-OCH2CH=CH
~ CN2-ocH2cN=cN2 (CH2=CHCN2O~2CHCE(OCH2CH=CH2)~
~` :
~-~3~3~
(CH2=CHCH20)2CHCH2CHtOCH2CH=CH2)2 CH3C(OCH2CH=cH2)3 C(OCH2CH=cH2)4 (cH2=cHcH2o)cH2[CH(ocH2cH=cH2)]3cH2(ocH2cH=cH2) (cH2=cHcH2o)cH2[cH(oc~2cH=cH~)]4cH2(ocH2cH=cH2) Si(OCH2CH=cH2)4 Si[OCH(CH3)CH=CH2]4 P(OCH2CH=CH2)3~
o=p(ocH2cH=cH2)3 and (R60--CEI2--) 4_kC (-cH2-o~H2cH=cH2 ~
in which R6 represents hydrogen or a radical of the formula o CH3C- and k is an average of from 2.5 to 3.5, and more preferably about 2.9. The last mentioned compound is the preferred example.
Examples of the radical represented by Y are those of the formula -CH-CH2- :
. ... . . . -, - . .. . . ..
:
, : . . . . .
2 -~ 3 ~
fH2 -CH3-C-cH2-IC~2-CH3-CH2-f-CH2-C~2 -ClH2-Ho CH2-f-CH2-CH
lcH2-CH3-1Cj-O- H2-C-CH2-`' ~ i -CH-CH-j -CH-CH2-CH-~: `
-CH2-CH-CH-CH-CH2 . ` ~ .
: ':
: 20 -CH2-CH-CH-CH-CH-CH2~
`` : : : :: ~ ~ ~
` : : : :`
:
,, . :, . . : ` `
2 ~
- c -i --si---P and -P=O.
Processes for preparing organic compound ~1) are described in EP-B 46,731 (published 3rd October 1984, F. Lohse et al., Ciba-Geigy AG). The compound of the formula (HOCH2)4 kc(cH2oc~2cH=cH2)k in which k is 2.9, is commercially availa~le, for example from Shell AG and is markete~ as pentaerythritol triallyl ether. The compound of the formula (c~3~oc~2~4-kc(cH2ocH2c~=c~2)k~
in which k is an average o~ from 2.5 to 3.5, and more preferably about 2.9, is obtained by reactin~ the compound mentioned above~with acetic anhydride:or isopropenyl acetate.
Organosiloxanes (2~ having at least one Si-bonded hydrogen atom whlch are preferably employed in the 1st stage 20 ~ of the process of this invention are those of the general:
:formula ~
~ ~ HeRfSiO4-(e+f) '~ (VI) in which R is the same as above, e is O or 1, with an average~of ~rom 0.005 to 1.0, f is 0, 1, 2~:or 3, with an average of from 1.0 ~Q 2.0, and the sum of~e+f lS not~greater :~
than 3.
Organopolysiloxanes (2) having at least one Si~
bonded hydrogen atom which are preferably employed in the 30 ~ ~ process o~ this~ln~ention are tho9e of the general formula~
: ~
.. ..
. ~ ' '. : ": , ' 2~3 HdR3-dsio(siR2o)o~siRHo)psiR3-dHd (VII) in which R is the same as above, d is 0 or l, o is 0 or an integer of from l to 1,000 and p is 0 or an integer o~ from l to 6.
The organopolysiloxanes (2) having at least one Si-bonded hydrogen atom per molecule pre~erably have a viscosity of from 0.5 to 20,000 mPa.s at 25C, and more preferably from 5 to 1,000 mPa.s at 25~C.
Examples of organopolysiloxanes (2) are copolymers uf dimethylhydrogensiloxane and dimethylsiloxane units, copolymers o~ dimethylhydrogensiloxane, dimethylsiloxane and methylhydrogensiloxane units, copolymers of trimPthylsiloxane and methylhydrogensiloxane units, copol~mers o~ trimethyl-siloxane, dimethylsiloxane and methylhydrogensiloxane units, copolymers of dimethylhydrogensiloxane, dim~thylsiloxane and phenylmethylsiloxane units, copolymers of dimethylhydrogen-siloxane and methylsiloxane units and copolymers of dimethyl-hydrogensiloXane and phenylsiloxane units, copolymers of methylhydrogensiloxane and diphenylsiloxane units, copolymers of methylhydrogensiloxane,dimethylsiloxane and phenylsiloxane units and copolymers o~ dimethylhydrogensiloxane, dimethyl-siloxane and phenylsiloxane:units.
Processes for preparing organopolysiloxanes having at least one Si-bonded hydrogen atom per molecule, including those of the preferred type, are gene~ally known.
The organic compound (1) is employed in the process of this invention in amounts such that the ratio of the aliphatic double bond in the organic cmmpound ~1) to the Si-bonded hydrogen in the organopolysiloxane (2) is preferably : 30 from 1.5 : 1 to 20 : 1, and more preferably ~rom 2 : 1 to 10 :~
: 1. The organic compound ~l) can be combin~d with the :- -organopolysiloxane (2) almost as~de~ired within very wide :
limits, depending on:their functionality and their molecular weight. However, a C=C : siH: ratio of greater than 20 leads exclusively to monohydrosilylation o~ the organic compound (1), which is not preferred~
. ,, , . : ......... . . ......... ~ . , .
., : , ,. . - - : ~, , :. :
, . :
, ~3~3~
The same catalysts ~hich have b~en or could have been employed to promote the addition of Si-bonded hydrogen to an aliphatic double bond can also be us~d as catalysts (3) which promote the addition of Si-bondPd hydrogen to an aliphatic multiple bond in the 1st stage of the process of this invention. The catalysts (3) are preferably a metal from the group of platinum metals or a compound or a complex from the group of platinum metals. Examples of such catalysts are metallic and finely divided platinum, which can be supported on inert carriers, such as silicon dioxide, aluminum oxide or active charcoal, and compounds or complexes of platinum, such as platinum halides, for example PtCl4, H2PtCl6 6H20, Na2PtCl4 4H20, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H2PtCl6 6H20 and cyclohexanone, platinum-vinylsiloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetramethyl-disiloxane complexes which contain or are free of detectable inorganically bonded halogen, bis-~gamma-picoline)-platinum dichloride, trimethylenedipyridineplatinum dichloride, dicyclopentadieneplatinum dichloride, dimethylsul~oxide-ethyleneplatinum (II) dichloride and reaction products of platinum tetrachloride with an olefin and primary amine or secondary amine or a primary and secondary amine according to U.S. Patent No. 4,292,434, such as th~ reaction product of platinumtetrachloride dissolved in l-oc~ene with sec-butyla-mine, or ammonium~platinum complexes according:to EP-B
110,370.
Catalyst (3) is preferably employed in amounts of from 0.5 to 1,000 ppm by weight (parts by weight per million parts by weight), calculated as elemental platinum and based - on the total weight of the organic compound (1) and organo-polysiloxane (2).
The addition reaction (or hydrosilylation reaction) in the 1st stage of t.he process of this invention is preferably carried out under the pressure of the :
-2 ~ 3 ~ 3 ~ ~
surrounding atmosphere, that is, at about 1020 hPa (absolute), but it can also be carried out under higher or lower pressures. The hydrosilylation is preferably carried out at a temperature of from 50OC to 150C~ and more pre-ferably from 80C to 130C.
Inert organic solvents can also be used in the 1st stage of the process of this invention, although the additional use of inert organic solvents is not preferred.
Examples of inert organic solvents are toluene, xylene, octane isomers, butyl acetate~ 1,2-dimethoxyethane, tetrahydrofuran and cyclohexane.
Excess organic compound (1) and the inert organic solvent, if used, are preferably removed by distillation from the siloxane copolymer which contains alkenyl groups and has been prepared in the 1st stage of the process of this invention.
The siloxane copolymers which contain alkenyl groups and have been obtained in the 1st stage of the process of this invention are described in our patent application filed on the same date.
In the 2nd stage of the process of this invention, the double bond in the alkenyl groups A of the formula -OCHR2 CR2 = CH2 is shifted to the carbon atom adjacent to the ether oxygen atom in the presence of catalysts (4) which promote this ~-double bond transfer.
The same catalysts (4) which have been or could have been used for promoting such a shift o~ the double bond can be employed in the 2nd stage of the process of this invention. Examples of catalysts (4) are m allic or ~inely - divided platinum, ruthenium, rhodium and palladium, which may be supported on inert carriers, such as active charcoal, and compounds or complexes of these elements which are soluble in the siloxane copolymers which contain alkenyl groups and have been obtained in the 1st stage o~ the process of this invention or which are fixed on supports, such a~ active charcoal or polymeric phosphine ligands. Examples o~
::
, . .
', ' ... : : ' ' ' ~ ~ `
.: . . ~ : . .. . . .... . . .
3 ~ 5 preferred catalysts (4) are those of the formula RuC12(PPh3)3, RuHCl(PPh3)3, RuHCl(CO)(PPh3)3, RuH2(CO)(PPh3)3 and RuH2(PPh3)4.
The ca~alyst (~) is pxe~erably employed in amounts of from 0.1 to 1,000 ppm by weight, and more preferably from 5 to lOo ppm by weight, calculated as th~ elemental metal and based on the total weight of the organic compound (1) and organopolysiloxane (2).
Strong bases, such as potassium tert-butylate, can also be used as catalysts (4), but these are not preferred because of the high amounts used. The shift o~ double bonds ~sing these strong bases is described in C.C. Price, JACS
83,1772 ~1961) and G. Kesslin, J. Org. Chem. 31, 2682 (1966).
To shift the double bond to the carbon atom adjacent to the ether oxygen atom in the alkenyl groups A, the siloxane copolymer which contains alkenyl groups and has been obtained ~rom the 1st stage of tha process o~ this invention is mixed with the catalyst (4) and the mixture is heated. The reaction is preferably carried out at a temperature of from 80C to 2007C and more preferably from 120C to 150~C, preferably under the pressure of the surrounding atmosphere, that is, a~ about 1020 hPa (absolute), and preferably over a period of from 0.5 to 20 hours, and more preferably from 4 to 10 hours. Preferably, no solvent is used.
If the organic compound (1) is not removed by distillation in the 1st stage o~ the process of this inve~ntion, the alkenyl groups A in the organic compound (1) are also rearranged into alkenyloxy groups B. The rearranged organic compound (l) can be removed by distillation from the siloxane copolymers which contain alkenyloxy groups and have been prepared in the 2nd stage of the process of this invention. If it is not removed, it is capable o~ undergoing cationic polymerlza~ion or copoly-.
~: : :: : :
$
merization with the alkenyloxy yroups of the siloxane copolymer because of its content of alkenyloxy groups B.
The siloxane copolymer which contains alkenyloxy groups and is obtained in the 2nd stage of the process of this invention i5 a cis/trans isomer mixture in respect to the alkenyloxy groups, the cis isomers usually predominating.
For example, if the alkenyloxy group is a l-propenyloxypropyl radical, the following isomeric mixture is present:
-(cH2~3-o\ fH3 -(CH2)3-o H
C=C C=C
I \ I \
cis- trans-The 2-stage process of this invention proceeds in accordance with the ~ollowing equation, shown by way of example by the use of pentaerythritol-triallyl ether-acetate as the organic compound (1) and an ~,w-dihydrogendimethyl-polysiloxane as the organopolysiloxane (2):
Pt Cat.
CH3C02CH2C(CH20CH2CH=CH2~3 + N(SiMe20)50SiNe2H~ ---> ~;
20~fH2OCH2CH=cH2)2 CH3CO2CH2CCH2O(cH2)3(siMe2O)50si~e2(cH2)3OlH2 T
: C~3CO2CH2cc~20 Q2cH-cH2 -->
CH3CO2CH2CjcH2O(cH2)3(siMe2O)5osiNe2(c~2)3ocH2 Cat (CH2OcH2cH=cH2)2 :
25(CH2OCH=CHCH3)2 CH3CO2CH2CCH2O(CH2)3(siMe2O)505iMe2(cH2)3olH2 ~:
CH3CO2cH27cH20cH=cHcH3 CH3CO2CH2fCH2O(CH2)3(siMe2O)50siMe2~c~2)3~cH2 (cHzocH=cHcH3)2 30The course o~ the reaction and kherefore the resulting end product is kotally dependent on the ratio of C=C double bond in the organiic compound (l) to Si-bonded ~: :
',' j ' ' ' . . . " . : ' ' ~,,' . ' ; '', ., , ' : ' ' ' . ' .
~. 1) 3 ~
hydrogen in the organopolysiloxane (2) which is employed in the 1st stage. Depending on the ratio of C=C:SiH employed, it is always necessary for the ratio of C=C:SiH to ~e greater than 1, siloxane copolymers are obtained which contain free alkenyl groups A of the form-lla -OCH~2CR2=CH2, such as -0CH2CH=CH2 at the chain end and along the chain, it being possible ~or branching to occur along the chain by further reaction of the free alkenyl groups along the chain with the Si-bonded hydrogen atoms of the organopolysiloxane (2). In the 2nd stage, the double bond in the free alkenyl groups A is then shifted and free alkenyloxy groups B of the formula - OCR2=CR2CH3 r such as -OCH=CHCH3 are obtained. The allyloxy groups, -OCH2CH=CH2, have already been rearranged into propenyloxy groups, -OCH=CHCH3, to a small degree (up to 15 mol %) in the 1st stage in the presence of the platinum catalysts, so that in the 2nd stage an equilibrium is established between allyloxy and propeny-loxy groups, in that the ratio of allyloxy groups to propeny-loxy groups is usually 4:96, that is, a conversion of about96% is achieved in respect of the propenyloxy groups.
The various stages of the process of this invention can be carried out in one and the sama r~action vessel in succession or in reaction vessels which are separate from each other. They are preferably carried out in one and the same reaction vessel in succession. The process of this invention can be carried out batchwise, semi-continuously or continuously.
The siloxane copolymers of this invention con~aining alkenyloxy groups can be crosslinked in a cationic polymerization initiated by light. The bis-(dodecylphenyl)-iodonium salts described in U.S. Patent No. 4,279,717 (published 21st July 1981, Eckberg et al., General Electric Company), such as bis-(dodecylphenyl)iodonium ::
:
:
. :
6~
hexafluoroantimonate or bis-(dodecylphenyl) iodonium hexafluoroarsenate, can be used, ~or example, as catalysts for the crosslinking initiated by light.
The invention therefore relates to the use of siloxane copolymers which contain alkenyloxy groups and preferably contain u~its of the formula (I), (II) and if appropriate at least one of the units of the formula (III), (IV), or (V), preferably units o~ the formula ~I'), (II') and ~III'), in compositions which are based on the siloxane copolymers mentioned above and can be crosslinked by light.
The siloxane copolymers of this invention containing alkenyloxy groups are preferably crosslinked by untraviolet light, that having wavelengths in the range of from 200 to 400 nm being preferred. The ultraviolet light can be generated, for example, in xenon lamps or low pressure, medium pressure or high pressure mercury lamps.
Light having a wavelength of 400 to 600 nm, that is to say so-called "halogen light", is also suitable for the ; crosslinking by means of light. The siloxane copolymers of this invention containing alkenyloxy groups can be crosslinked by light in the visible range if commercially available photosensitizers are used.
The cationic polymerization of the siloxane copolymars of this invention containing alkenyloxy groups can of course also be initiated by Bronsted or Lewi~ acids.
The invention also r~lates ~o the use of the siloxane copolymers of this invention containing alkenyloxy groups for the preparation of coatings which can be crosslinked by light.
Examples of surfaces to which the coatings of this invention can be applied are those of paper, wood, cork, plastic films, for example polyethylene films or polypropylene films, ceramic objects, glass, including glass fibers, metals, paperboard, including that of asbestos, and woven and nonwoven cloth of natural or synthetic organic fibers.
~.
: ~ . : . :
-. : , . . . : :1 ~ .
~ t-~3~
The application of the siloxane copolymers of this invention containing alkenyloxy groups to the sur~aces ~o be coated can be carried out in any desired manner which is suitable and in many cases known for the production of coatings from liquid substances, for example by dipping, brushing, pouring, spraying, rollin~ on, printing, for example by means of an offset gravure transfer device, and knife or doctor-blade coating.
Example 1:
About 89 g of 1,1,2,2-tetraallyloxyethane are mixed with 5.4 mg of platinum as a solution of platinum tetrachloride in 1-octene and the mixture is heated to 110C. About 581 g of an ~,w-dihydrogendimethylpoly-siloxane which contains 250 mg of Si-bonded hydrogen are added dropwise to this mixture at 110C under a nitrogen atmosphere, with stirring. After the mixture has been stirred at 110C for about 3 hours, 98% of ~he Si-bonded hydrogen atoms of the ~,w-dihydrogendimethyl-polysiloxane have reacted. All the volatile constituents are then removed by distillation at 120C
under 10-3 hPa. About 110 mg of RuHCl(Ph3P)3 are then added to the xeaction product at 130~C under 1020 hPa (absolute) under a nitrogen atmosphexe and the mixture is stirred at 130C for 16 hours. A clear yellow liquid having a viscosity of about 1100 mPa.s at 25C is obtained. The siloxane copolymer thus obtained essentially contains, in addition to dimethylsiloxane units, siloxane units of the formula fCH=CHCH3 (CH3CH=cHO)2cHcHO(cH2)3siO3/2 and bridged units of the formula CH3CH-CHO fCH=CHCH3 O(CH3)2Si(CH2)30CHC}~O(C}l2)3Si(CH3)20, the ratio of cis isomer to trans isomer in the 1-propenyloxy groups, CH3CH-CH0-, being 70 : 30 according .
.
., : ~ : . ....... , ,. , ,,; .
- , -! ' , `.
, ~
, ' '~' ,'' . ' " ' ' ' ,' ,' " '" ' ' ~, ' . .
~3~
to th~ lH NMR spectrum. The siloxane copolymer containing l-propenyloxy groups has an equivalent weight of about 1300 g per mol of C=C double bond.
Example 2-About 11404 g of trimethyolpropane-allyl ether (preparPd in accordance with EP-B 46,731) having an iodine number (number which specifies how many g of iodine are bonded by 100 g of substance) of 266 are mixed with 3.8 mg of platinum in the form of a solution of platinum tetrachloride in l-octene and the mixture is heated to 105C. About 273 g of an ,w-dihydrogendimethylpoly-siloxane which contains 0.6 g of Si-bonded hydrogen are added dropwise to this mixture at 105C under a nitrogen atmosphere, while stirring. After the mixture has been stirred at 105C for about 4 hours, gg% of the Si-bonded hydrogen atoms of the ~,w dihydrogenmethylpolysiloxane have reacted. All the volatile constituents are then removed by distillation at 120C under 10-3 hPa. About 200 ppm by weight of RuHCl(Ph3P)3 are ~hen added to the reaction product at 130C under 1020 hPa (absolute) under a nitrogen atmosphere and the mixture is stirred at 130'C for 8 hours. About 315 g of a clear, almost colorless oil having a ~iscosity of 380 mm2x s-1 at 25C
are obtained. The siloxane copolymer containing 1-propenyloxy groups~ which is obtained in this manner, has an equivalent weight of abou~ 900 g per mol of C=C
double bond.
Example 3:
About 48 g of pentaerythritol-triallyl ether having an iodine number of 281 (commercially obtainable from Shell) are mixed with 2.2 mg of platinum a a solution of platinum tetrachloride in 1-octene and the mixture is heated to 105C. About 435 g of an ~,w~dihydrogendi methylpolysiloxane which contains 0.046~ by weight of Si-bonded hydrogen are added dropwise to this mixture at 105UC under a nitrogen atmosphere, with stirring. After .
3 ~ ~
the mixture has been stirred at 105C for about 8 hours, 98~ of the Si-bonded hydrogen atoms of the ~,w-dihydrogendimethylpolysiloxane have reacted. All the volatile constituents are then removed by distillation at 120C under 10-3 hPa. After filtration, 76 mg of RuHCl(Ph3P)3 are then added to the reaction product at 130C under 1020 hPa (absolute) under a nitrogen atmosphere and the mixture is stirred at 130C
for 8 hours. A siloxane copolymer is obtained which contains l-propenyloxy groups and has a viscosity of 1190 mm2x 5-l, contains ona l-propenyloxy group per 32 silicon atoms and has an equivalent weight of about 2400 g per mol o~ C=C double bond. The ratio of cis isomer to trans isomer in the l-propenyloxy groups is 70 : 30.
The following data are obtained from the lH-NMR
spectrum lH-NMR spectrum (CDCl3):
trans isomer: ~ = 4.78 ppm (lH, CH3CH=), (30 mol %) 6.22 ppm (lH, = CH-O-~.
cis isomer : ~ = 4.37 ppm ~lH, CH3CH=), (70 mol ~) 5.95 ppm (lH, -CH-0-).
Example 4:
About 2 g of a 50~ solution of bis-(dodecylphenylj-iodonium hexafluorantimonate which has been prepared according to U.S. Patent No. 4,2i9,717 in propylene carbonate are added to lO0 g of the siloxane copolym~r prepared in Example 3. The mixture is applied at a thickness of 3 ~, using a glass rod, to paper coated with polyethylene. Two medium pressure mercury lamps having an output of 80 watt/cm luminous length are positioned at a distance o~ 10 cm from the coated substrate. After UV exposure ~or less than two seconds, a non-tacky coating is obtained which is adhesive-repellent with respect to paper labels coated with acrylate adhesive.
, - , . . . - , ~ ~ . ~, . .. : . .
.. . . . . .
'' ~
:. . . . , :: : ,
Claims (9)
1. A siloxane copolymer which contains alkenyloxy groups and contains (a) siloxane units of the formula (I) in which R is selected from the group consisting of hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical and halogenated hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical.
R1 is a radical selected from the group consisting of alkyl radicals having from 1 to 4 carbon atom(s) per radical which can be substituted by an ether oxygen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3 and the sum of a+b is not greater than 3, (b) at least one siloxane unit per molecule of the formula (II) in which R is the same as above c is 0, 1 or 2 and Q represents a radical of the formula -CH2CHR2CHR2OY(OCR2=CR2CH3)x-1 in which R2 is a radical selected from the group consisting of a hydrogen atom or a methyl radical, Y is a trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having from 2 to 20 carbon atoms per radical which can be substituted with a group from the formula - OH, - OR3, - OSiR43, - , or - X, or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula ?P, ?P=O or ?SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X is a halogen atom and R5 is a monovalent hydrocarbon radical having form 1 to 8 carbon atoms(s) per radical or Y represents a tetravalent element selected from the group consisting of , and x is 3, 4, 5 or 6 and optionally (c) at least one unit per molecule selected from the group consisting of units of the formula (III), (IV), and (V) in which R and c are the same as above, Q1 represents a radical of the formula Q2 represents a radical of the formula and Q3 represents a radical of the formula (x-4>0) in which R2, Y and x are tha same as above.
R1 is a radical selected from the group consisting of alkyl radicals having from 1 to 4 carbon atom(s) per radical which can be substituted by an ether oxygen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3 and the sum of a+b is not greater than 3, (b) at least one siloxane unit per molecule of the formula (II) in which R is the same as above c is 0, 1 or 2 and Q represents a radical of the formula -CH2CHR2CHR2OY(OCR2=CR2CH3)x-1 in which R2 is a radical selected from the group consisting of a hydrogen atom or a methyl radical, Y is a trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having from 2 to 20 carbon atoms per radical which can be substituted with a group from the formula - OH, - OR3, - OSiR43, - , or - X, or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula ?P, ?P=O or ?SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X is a halogen atom and R5 is a monovalent hydrocarbon radical having form 1 to 8 carbon atoms(s) per radical or Y represents a tetravalent element selected from the group consisting of , and x is 3, 4, 5 or 6 and optionally (c) at least one unit per molecule selected from the group consisting of units of the formula (III), (IV), and (V) in which R and c are the same as above, Q1 represents a radical of the formula Q2 represents a radical of the formula and Q3 represents a radical of the formula (x-4>0) in which R2, Y and x are tha same as above.
2. The siloxane copolymer containing alkenyloxy groups of claim 1, whieh contains siloxane units of formula (I), at least one siloxane unit per molecule of formula (II) and at least one unit per molecule selected from the group consisting of units of formulas (III), (IV) and (V).
3. The siloxane copolymer containing alkenyloxy groups of claim 1 which contains (a) siloxane units represented by the formula R2SiO (I) (b) at least two siloxane units per molecule represented by the formula QR2SiO1/2 (II) and (c) at least one siloxane unit per molecule represented by the formula O1/2R2SiQ1SiR2O1/2 (III) in which R is selected from the group consisting o hydro-carbon radicals having from 1 to 18 carbon atom(s) per radical, and halogenated hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical, Q is a radical of the formula -CH2-CHR2CHR20Y(OCR2=CR2CH3)x-1 Q1 is a radical of the formula R2 is a radical selected from the group consisting of a hydrogen atom and a methyl radical, x is 3, 4, 5 or 6 and Y is a trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having from 2 to 20 carbon atoms per radical, which can be substituted by groups of the formula - OH, - OR3, - oSiR43, - - X
or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula =P, =P=O or -SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X is a halogen atom, and R5 is a monovalent hydrocarbon radical having from 1 to 8 carbon atom(s) per radical, or Y represents a tetravalent element selected from the group consisting of
or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula =P, =P=O or -SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X is a halogen atom, and R5 is a monovalent hydrocarbon radical having from 1 to 8 carbon atom(s) per radical, or Y represents a tetravalent element selected from the group consisting of
4. The siloxane copolymer containing alkenyloxy groups of claim 2 which contains (a) siloxane units represented by the formula R2SiO (I'), (b) at least two siloxane units per molecule of formula (II) represented by the formula QR2SiO1/2 (II') and (c) at least one siloxane unit per molecule of formula (III) represented by the formula Ol/2R2SiQ1SiR2O1/2 (III') in which R is selected from the group consisting of hydro-carbon radicals having from 1 to 18 carbon atom(s) per radical, and halogenated hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical, Q is a radical of the formula -CH2-CHR2CHR20Y(OCR2=CR2CH3)x-1 Q1 is a radical of the formula R2 is a radical selected from the group consisting of a hydrogen atom and a methyl radical, x is 3, 4, 5 or 6 and Y is a trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having from 2 to 20 carbon atoms per radical, which can be substituted by groups of the formula - OH, - OR3, - OSiR43, - X
or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula =P, =P=O or =SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X is a halogen atom, and R5 is a monovalent hydrocarbon radical having from 1 to 8 carbon atom(s) per radical, or Y represents a tetravalent element selected from the group consisting of -C- , -Si- and -?-
or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula =P, =P=O or =SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X is a halogen atom, and R5 is a monovalent hydrocarbon radical having from 1 to 8 carbon atom(s) per radical, or Y represents a tetravalent element selected from the group consisting of -C- , -Si- and -?-
5. A process for preparing a siloxane copolymer containing alkenyloxy groups of claim 1, which comprises in a first stage reacting an organic compound (1) containing more than two aliphatic double bonds, of the general formula Y(OCHR2CR2=CH2)x R2 is a radical selected from the gxoup consisting of a hydrogen atom and a methyl radical, x is 3, 4, 5 or 6 and Y is a trivalent, tetravalent, pentavalent or hexavalent hydrocarbon radical having from 2 to 20 carbon atoms per radical, which can be substituted by groups of the formula - OH, - OR3, - oSiR43, - X
or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula =P, =P=O or =SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X is a halogen atom, and R5 is a monovalent hydrooarbon radical having from 1 to 8 carbon atom(s) per radical, or Y represents a tetravalent element selected from the group consisting of the elements with an organopolysiloxane (2) having at least one Si-bonded hydrogen atom per molecule in the presence of a catalyst (3 which promotes the addition of Si-bonded hydrogen to an aliphatic double bond, in which the ratio of the aliphatic \
double bond in the organic compound (1) to the Si-bonded hydrogen in the organopolysiloxane (2) is such that siloxane copolymers are obtained which contain alkenyl groups and have an average of more than two alkenyl groups A of the formula -OCHR2CR2=CH2 in which R2 is the same as above,and in a 2nd stage, shifting the double bond in the alkenyl groups A to the carbon atom adjacent to the either oxygen atom by heating the siloxane copolymer containing alkenyl groups obtained in the 1st stage in the presence of a catalyst (4) which promotes a shift of the double bond, in which siloxane copolymers are obtained which contain alkenyloxy groups and have an average of more than two alkenyloxy groups B of the formula -OCR2=CR2CH3, in which R2 is the same as above.
or can be interrupted by at least one oxygen atom or sulfur atom or one carbonyl group, or Y represents a trivalent radical of the formula =P, =P=O or =SiR5 in which R3 is an alkyl radical having from 1 to 6 carbon atom(s) per radical, R4 is a radical selected from the group consisting of a methyl, ethyl, isopropyl, tert-butyl and phenyl radical, X is a halogen atom, and R5 is a monovalent hydrooarbon radical having from 1 to 8 carbon atom(s) per radical, or Y represents a tetravalent element selected from the group consisting of the elements with an organopolysiloxane (2) having at least one Si-bonded hydrogen atom per molecule in the presence of a catalyst (3 which promotes the addition of Si-bonded hydrogen to an aliphatic double bond, in which the ratio of the aliphatic \
double bond in the organic compound (1) to the Si-bonded hydrogen in the organopolysiloxane (2) is such that siloxane copolymers are obtained which contain alkenyl groups and have an average of more than two alkenyl groups A of the formula -OCHR2CR2=CH2 in which R2 is the same as above,and in a 2nd stage, shifting the double bond in the alkenyl groups A to the carbon atom adjacent to the either oxygen atom by heating the siloxane copolymer containing alkenyl groups obtained in the 1st stage in the presence of a catalyst (4) which promotes a shift of the double bond, in which siloxane copolymers are obtained which contain alkenyloxy groups and have an average of more than two alkenyloxy groups B of the formula -OCR2=CR2CH3, in which R2 is the same as above.
6. The process of claim 5, wherein the organic compound (1) has the formula (R6OCH2)4-kC(CH2OCH2CH=CH2)k, in which R6 is selected from the group consisting of a radical of the formula and k is an average of from 2.5 to 3.5.
7. The process of claim 5, wherein the organopolysiloxane (2) having at least one Si-bonded hydrogen atom per molecule has the general formula HdR3-dSiO(SiR2O)o(SiRHO)pSiR3-dHd (VII) in which R is a radical selected from the group consisting of hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical and halogenated hydrocarbon radicals having from 1 to 18 carbon atom(s) per radical, d is 0 or 1, o is 0 or an integer of from 1 to 1000 and p is 0 or an integer of from 1 to 6.
8. A composition which can be crosslinked by means of light which is obtained by using the siloxane copolymer containing alkenyloxy groups of claim 1.
9. A coating which may be obtained by applying a composition which contains the siloxane copolymer containing alkenyloxy groups of claim 1 to a substrate and thereafter the coated substrate is exposed to light.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4002922.0 | 1990-02-01 | ||
| DE19904002922 DE4002922A1 (en) | 1990-02-01 | 1990-02-01 | Alkenyloxy gp.-contg. siloxane! copolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2035396A1 true CA2035396A1 (en) | 1991-08-02 |
Family
ID=6399189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2035396 Abandoned CA2035396A1 (en) | 1990-02-01 | 1991-01-31 | Siloxane copolymers containing alkenyloxy groups, a process for preparing the same and their use |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5231157A (en) |
| EP (1) | EP0439777B1 (en) |
| JP (1) | JPH0737530B2 (en) |
| AT (1) | ATE111126T1 (en) |
| CA (1) | CA2035396A1 (en) |
| DE (2) | DE4002922A1 (en) |
| ES (1) | ES2058745T3 (en) |
| FI (1) | FI96431C (en) |
| MX (1) | MX174357B (en) |
| NO (1) | NO178667C (en) |
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| US5486422A (en) * | 1994-04-19 | 1996-01-23 | Dow Corning Corporation | Photo-crosslinkable silicones and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2983745A (en) * | 1956-07-18 | 1961-05-09 | Dow Corning | Silpropoxanes |
| US3197432A (en) * | 1962-07-02 | 1965-07-27 | Gen Electric | Transparent resinous organopolysiloxanes |
| DE2655877A1 (en) * | 1976-12-09 | 1978-06-15 | Wacker Chemie Gmbh | PROCESS FOR MANUFACTURING AND USING SILANES |
| DE2918254C2 (en) * | 1979-05-05 | 1984-08-30 | Th. Goldschmidt Ag, 4300 Essen | Process for the production of crosslinked organopolysiloxanes and their use in adhesive coating compositions |
| US4709067A (en) * | 1986-05-20 | 1987-11-24 | Union Carbide Corporation | Method for preparing methacryloxy and acryloxy containing organosilanes and organosilicones |
| JPS6363684A (en) * | 1986-09-04 | 1988-03-22 | Shin Etsu Chem Co Ltd | Organosilicon compound |
| EP0266895A3 (en) * | 1986-10-03 | 1990-03-07 | Dow Corning Corporation | Dioxolane, diol and diacrylate silicon compounds and method for their preparation and use |
| US4911986A (en) * | 1987-02-09 | 1990-03-27 | Dow Corning Corporation | Curable silicone compositions comprising vinyl monomer |
-
1990
- 1990-02-01 DE DE19904002922 patent/DE4002922A1/en not_active Withdrawn
- 1990-12-18 AT AT90124495T patent/ATE111126T1/en not_active IP Right Cessation
- 1990-12-18 EP EP19900124495 patent/EP0439777B1/en not_active Expired - Lifetime
- 1990-12-18 ES ES90124495T patent/ES2058745T3/en not_active Expired - Lifetime
- 1990-12-18 DE DE59007063T patent/DE59007063D1/en not_active Expired - Fee Related
-
1991
- 1991-01-25 JP JP764891A patent/JPH0737530B2/en not_active Expired - Lifetime
- 1991-01-30 FI FI910441A patent/FI96431C/en not_active IP Right Cessation
- 1991-01-31 NO NO910363A patent/NO178667C/en unknown
- 1991-01-31 US US07/648,107 patent/US5231157A/en not_active Expired - Fee Related
- 1991-01-31 CA CA 2035396 patent/CA2035396A1/en not_active Abandoned
- 1991-02-01 MX MX024378A patent/MX174357B/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5436309A (en) * | 1993-04-19 | 1995-07-25 | Dow Corning Corporation | Photo-crosslinkable silicones comprising oxyalkylene styrene groups and their use |
| US5486422A (en) * | 1994-04-19 | 1996-01-23 | Dow Corning Corporation | Photo-crosslinkable silicones and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0439777A3 (en) | 1991-10-23 |
| NO178667C (en) | 1996-05-08 |
| EP0439777A2 (en) | 1991-08-07 |
| DE59007063D1 (en) | 1994-10-13 |
| JPH0737530B2 (en) | 1995-04-26 |
| DE4002922A1 (en) | 1991-08-08 |
| FI96431B (en) | 1996-03-15 |
| FI96431C (en) | 1996-06-25 |
| US5231157A (en) | 1993-07-27 |
| NO910363L (en) | 1991-08-02 |
| NO178667B (en) | 1996-01-29 |
| ES2058745T3 (en) | 1994-11-01 |
| ATE111126T1 (en) | 1994-09-15 |
| MX174357B (en) | 1994-05-10 |
| NO910363D0 (en) | 1991-01-31 |
| FI910441A0 (en) | 1991-01-30 |
| EP0439777B1 (en) | 1994-09-07 |
| JPH05320346A (en) | 1993-12-03 |
| FI910441A (en) | 1991-08-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |