CA2342153A1 - Perfluorinated organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes - Google Patents
Perfluorinated organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes Download PDFInfo
- Publication number
- CA2342153A1 CA2342153A1 CA002342153A CA2342153A CA2342153A1 CA 2342153 A1 CA2342153 A1 CA 2342153A1 CA 002342153 A CA002342153 A CA 002342153A CA 2342153 A CA2342153 A CA 2342153A CA 2342153 A1 CA2342153 A1 CA 2342153A1
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- polymerizable
- perfluorinated
- cyclosiloxanes
- cyclosiloxane
- 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 60
- 125000000962 organic group Chemical group 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 71
- -1 siloxanes Chemical class 0.000 claims abstract description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 35
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 34
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 23
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 21
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 20
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000004587 chromatography analysis Methods 0.000 description 16
- 238000003760 magnetic stirring Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 150000001408 amides Chemical class 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 12
- SNYNNFDVNITLRQ-UHFFFAOYSA-N 2,2,4,4,6,6,8-heptamethyl-1,3,5,7,2,4,6,8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 SNYNNFDVNITLRQ-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 10
- LSLXQHYRRJOSKF-UHFFFAOYSA-N 3-(2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propyl 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propoxy]propoxy]propanoate Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(CCCOC(=O)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)O[Si](C)(C)O1 LSLXQHYRRJOSKF-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 9
- 101150041968 CDC13 gene Proteins 0.000 description 8
- 238000006459 hydrosilylation reaction Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920005573 silicon-containing polymer Polymers 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 238000004611 spectroscopical analysis Methods 0.000 description 7
- SOAJODGLQZBKJQ-UHFFFAOYSA-N 3-(2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propan-1-ol Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(CCCO)O[Si](C)(C)O1 SOAJODGLQZBKJQ-UHFFFAOYSA-N 0.000 description 6
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- PWMITERXCIMRAY-UHFFFAOYSA-N 6-(tritylamino)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1NC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PWMITERXCIMRAY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- URZHQOCYXDNFGN-UHFFFAOYSA-N 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O1 URZHQOCYXDNFGN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920005684 linear copolymer Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- YQJPWWLJDNCSCN-UHFFFAOYSA-N 1,3-diphenyltetramethyldisiloxane Chemical compound C=1C=CC=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=CC=C1 YQJPWWLJDNCSCN-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- AQQBRCXWZZAFOK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O AQQBRCXWZZAFOK-UHFFFAOYSA-N 0.000 description 1
- IJDRCJGYWUCJTR-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propoxy]propoxy]propanoic acid Chemical compound OC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F IJDRCJGYWUCJTR-UHFFFAOYSA-N 0.000 description 1
- QDHLRGOEEBWEIB-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propoxy]propoxy]propanoyl fluoride Chemical compound FC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F QDHLRGOEEBWEIB-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LDWXYHAJMZSINF-UHFFFAOYSA-N 2-ethenyl-2,4,4,6,6,8,8,10,10-nonamethyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C=C)O[Si](C)(C)O1 LDWXYHAJMZSINF-UHFFFAOYSA-N 0.000 description 1
- LTIUDPOSFOYSKA-UHFFFAOYSA-N 2-ethenyl-2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C=C)O[Si](C)(C)O1 LTIUDPOSFOYSKA-UHFFFAOYSA-N 0.000 description 1
- FYQFWFHDPNXORA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C FYQFWFHDPNXORA-UHFFFAOYSA-N 0.000 description 1
- FFCOZHVTELDEPN-UHFFFAOYSA-N 3-(2,4,4,6,6,8,8,10,10,12,12,14,14-tridecamethyl-1,3,5,7,9,11,13-heptaoxa-2,4,6,8,10,12,14-heptasilacyclotetradec-2-yl)propyl 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropro Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(CCCOC(=O)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)O[Si](C)(C)O[Si](C)(C)O1 FFCOZHVTELDEPN-UHFFFAOYSA-N 0.000 description 1
- MYBUOESWKZLEGP-UHFFFAOYSA-N 3-(2,4,4,6,6,8,8,10,10-nonamethyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecan-2-yl)propyl 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propoxy]propoxy]propanoat Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(CCCOC(=O)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)O[Si](C)(C)O1 MYBUOESWKZLEGP-UHFFFAOYSA-N 0.000 description 1
- YWTJKELSGBTRLD-UHFFFAOYSA-N 3-(2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(CCCOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)O[Si](C)(C)O1 YWTJKELSGBTRLD-UHFFFAOYSA-N 0.000 description 1
- AMTGHFWVSAEQIB-UHFFFAOYSA-N 3-(2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propyl 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propoxy]propanoate Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(CCCOC(=O)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(OC(F)(F)C(F)(F)C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)O[Si](C)(C)O1 AMTGHFWVSAEQIB-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- ISPWSRVEMSGMKS-UHFFFAOYSA-N 3-[[3-hydroxypropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-ol Chemical compound OCCC[Si](C)(C)O[Si](C)(C)CCCO ISPWSRVEMSGMKS-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ABBZJHFBQXYTLU-UHFFFAOYSA-N but-3-enamide Chemical compound NC(=O)CC=C ABBZJHFBQXYTLU-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical group CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- GSANOGQCVHBHIF-UHFFFAOYSA-N tetradecamethylcycloheptasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 GSANOGQCVHBHIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- 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
- C08G77/045—Polysiloxanes containing less than 25 silicon 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
Compositions of unstrained perfluorinated organo substituted cyclosiloxanes of formula (I) wherein m is an integer of 1 to 12; n is an integer of 1 to 4; X
is a divalent radical which may include O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O)CH2; and RF is a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or RF is a perfluorinated ether radical of general formula (II) wherein p is an integer of 1 to 10 are described, along with copolymer compositions prepared from these cyclopolysiloxanes and from mixtures of these cyclosiloxanes and other siloxanes.
is a divalent radical which may include O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O)CH2; and RF is a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or RF is a perfluorinated ether radical of general formula (II) wherein p is an integer of 1 to 10 are described, along with copolymer compositions prepared from these cyclopolysiloxanes and from mixtures of these cyclosiloxanes and other siloxanes.
Description
PERFLUORINATED ORGANO SUBSTITUTED
CYCLOSILOXANES AND COPOLYMERS PREPARED FROM THESE CYCLOSILOXANES
FIELD OF THE INVENTION
The present invention relates to the preparation of cyclosiloxanes with one perfluorinated substituent and their ring-opening polymerization into silicone copolymers.
BACKGROUND OF THE INVENTION
One of the most important methods of preparing silicone polymers and copolymers is via ring-opening polymerization. Most commonly it is carried out by the polymerization of unstrained cyclosiloxanes, generally cyclic tetramers or pentamers, where no heat is generated upon polymerization. Typically the polymer constitutes up to approximately 90 percent of the resulting equilibrium mixture depending upon the substituents on the cyclosiloxane, the degree of polymerization achieved, and the amount of any solvent used in the polymerization. The amount of cyclosiloxanes that have been observed in equilibrium with many silicone polymers is described in Siloxane Polymers, Chapter 3, S.J. Clarson and J.A. Semlyen, ed., Ellis Horwood - PTR Rentis Hall, Englewood Cliffs, NJ, 1993. Polymerization can also be carried out with cyclic trimers. Cyclic trimers are strained and the polymerization is exothermic. Cyclic trimers are generally more difficult to prepare than cyclic tetramers and pentamers.
The most common fluorinated silicone is prepared by the ring-opening polymerization of 1,3,5-tris-(3,3,3-trifluoro-propyl)-1,3,5-trimethylcyclotrisiloxane. The weight percent of the fluorocarbon portion of the cyclosiloxane and its resulting homo-polymer is 44% by weight. The exothermic polymerization is driven due to the ring strain that is released upon the opening of the cyclic trimer. The polymerization must be stopped immediately after high polymer has formed, otherwise the polymer reverts to a mixture of cyclics, primarily the unstrained tetramer and pentamer which together constitute about 90% by weight of the cyclic mixture.
United States Patent No. 5,202,453 describes a strained cyclotrisiloxane with a single fluorinated organic substitutent.
This compound was prepared in a two step process from a 1H, 1H, 2H-su~;~rrrru'~'E~~
vinyl terminated oligomer of hexafluoropropene oxide with a combined yield of approximately 50~ based upon the moles of oligomer used. Though not demonstrated in the patent, it was suggested to be ring-opening polymerizable in the presence of alkaline or acid catalysts, presumably under conditions similar to those used for the polymerization of 1,3,5-tris-(3,3,3-trifluoro-propyl)-1,3,5-trimethylcyclotrisiloxane.
Unstrained cyclosiloxanes with one or two large substituents on each Si atom typically are difficult to polymerize as the magnitude of a cyclosiloxane's equilibrium constant increases relative to that of a cyclosiloxane with smaller substituents, while at the same time the maximum concentration of the Si-O bond decreases as the size of the substituent increases. These factors result in a very high proportion of cyclosiloxanes at equilibrium as in the case of 1,3,5-tris-(3,3,3-trifluoropropyl)-1,3,5-tri-methylcyclotrisiloxane. Because of this problem, it is common to prepare a silicone polymer with a small reactive group, often a hydrogen substituent, on the backbone. The hydrosilation of an olefin with a Si-H containing compound is frequently used to prepare organically substituted siloxanes. This hydrosilation is often difficult to perform if the solubility of the group to be substituted on the siloxane backbone is a low in the Si-H
containing silicone polymer. Often a Si-H containing polymer contains sites where the Si-H has undergone hydrolysis to Si-OH
during its preparation, storage, or during the hydrosilation reaction if water is present. Such units can permit the formation of branches or gels during the hydrosilation reaction.
Perfluorinated organic molecules often display very low miscibility in silicone polymers. Hydrosilation reactions often do not proceed to complete conversion of the olefin or the silane reactants. For these reasons it is difficult to achieve a perfluorinated organic substituted silicone polymer by modification of a functional silicone polymer without defects in the structure due to incomplete reaction or defects from the starting Si-H containing polymer.
United States Patent No. 5,247,116 describes a method where unstrained cyclosiloxanes with a single functional group can be SUBSTITUTE SHEET (RULE 26) prepared and subsequently isolated. This functional group may be transformed in a variety of fashions such that a single perfluorinated organic moiety may be introduced to a cyclosiloxane ring. The advantage of such a cyclosiloxane is that the Si-O bond concentration can be significantly higher than that of cyclo-siloxane with a perfluorinated organic substituent at every Si atom, for an equivalent molecular weight of the cyclosiloxane. Furthermore, the equilibrium cyclization constants for the majority of the resulting cyclosiloxanes remain close to that of cyclodi-methylsiloxanes. This results in a much greater fraction of linear siloxanes at equilibrium upon polymerization of the cyclosiloxane even though the starting cyclosiloxane is unstrained.
SUMMARY OF THE PRESENT INVENTION
One object of the present invention is to provide unstrained polymerizable cyclosiloxanes that have one substituent that contains a perf luorinated organic moiety whose structure is given by the general formula (I):
~X-RF
H C v..i CfI~
H3C ~S i o . ~O
O
K~~i-'4~m CH3 Q3;
(I) wherein m is an integer of 1 to 12; n is an integer of 1 to 4;
X is a divalent radical which may include O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O) and CH2; and RF is a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or RF is a perfluorinated ether radical of the general formula (II):
F - (CFCF20)p - CF -CF3 CF3 (II) wherein p is an integer of 1 to 10.
It is an object of the invention to prepare copolymers that result from the ring-opening polymerization of the cyclosiloxanes SUBSTITUTE SHEET (RULE 26) of formula (I) to give a copolymer of the general formula (III):
~3 --~~ i--iJ-~S i-E3 mt C~-Iz (III) ~~~~~X_RF
wherein m, n, X, and RF are defined as in formula (I); and q may be 2 to 1,000,000.
It is an object of the present invention to prepare copolymers from the cyclosiloxanes of formula (I) and cyclodimethylsiloxanes and/or polydimethylsiloxanes such that the resulting copolymer contains a lesser proportion of fluorinated siloxane groups than the cyclosiloxanes of formula (I).
It is an object of the present invention to prepare fluorinated silicones which contain in addition to the siloxy repeating units present in the cyclosiloxanes of formula (I) other siloxy repeating units which include, but are not exclusive to, hydrogenmethylsiloxy, methylvinylsiloxy, methylphenylsiloxy, (cyanoethyl)methylsiloxy, (aminopropyl)methylsiloxy, (hydroxy-propyl)methylsiloxy, and (trifluoropropyl)methylsiloxy units.
These units may be incorporated by the addition of the appropriate cyclosiloxane which contains one or more of these groups.
It is an object of the present invention to prepare copolymers from the cyclosiloxanes of the formula (I) and, optionally, other cyclosiloxanes, where the degree of polymerization is controlled by end-capping. This,is achieved by equilibrating the appropriate cyclosiloxanes with a disiloxane or the disiloxane's equivalent incorporated into a small polysiloxane. A wide variety of di-siloxanes and/or their equivalents in polysiloxanes are known which include, but are not exclusive to, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-di-(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-di(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-di-phenyl-1,1,3,3-tetramethyldisiloxane, 1,3-di-(3-chloropropyl-1,1,3,3-tetramethyldisiloxane, and 1,3-di-(3-methacryloxypropyl)-1,1,3,3-SUBSTITUTE SHEET (RULE 26) tetramethyldisiloxane, and mixtures of any of the foregoing.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The unstrained polymerizable cyclosiloxanes of the present invention are those which have methyl groups at all but one site for substituents. That site contains a perfluorinated organic moiety that may have a variety of molecular weights and functional groups connecting the moiety to the cyclosiloxane ring.
The cyclosiloxanes have the general formula (I). The cyclosiloxanes may be produced -by a hydrosilation reaction between a mono Si-H containing cyclodimethylsiloxane, such as heptamethyl-cyclotetrasiloxane or nonamethylcyclopentasiloxane, and a 1H,1H,2H-vinyl substituted fluorinated organic molecule.
The cyclosiloxane of formula ( I ) may be produced by reacting an oligomer of hexafluoropropeneoxide of the structure:
F - (CFCF20)p - CF - CF = O
CF3 CF3 {IV) wherein p is an integer of from 1 to 10, with an organic molecule that contains an amine or alcohol and a terminal vinyl group followed by hydrosilation between that amide or ester with a mono Si-H containing cyclodimethyldisiloxane. Alternately, the mono Si-H containing cyclodimethylsiloxane may undergo hydrosilation with an amine, such as allyl amine or N-methylallyl amine, or an alcohol, such as allyl alcohol, with a terminal vinyl group followed by its reaction with an oligomer of hexafluoropropene-oxide of formula (IV). In some cases, the ester that would result from the reaction between the oligomer of hexafluoropropene oxide of formula (IV) and methanol or ethanol may be used in an amidation or in a traps-esterification reaction to yield the cyclosiloxane of formula (I).
The cyclosiloxanes of formula (I) may be polymerized using an acid or alkaline catalyst in a manner typical of unstrained cyclosiloxanes to a mixture of linear copolymer and cyclic oligomers. The choice of catalyst will be dependent upon the nature of the group X in the cyclosiloxane of formula (I) as is known to those skilled in the art. The linear copolymer may be separated from the cyclic oligomers by extraction with a SUBSTITUTE SHEET (RULE 26) WO 99/62916 PCT/US99/(34341 hydrocarbon. The size of the hydrocarbon may vary depending upon the size of the perfluorinated organic moiety. In general the hydrocarbon will be less than 10 carbons in the chain such that it is sufficiently volatile to be easily removed from the extracted cyclosiloxanes and the copolymer. The resulting copolymer will have the general formula (III). The extracted cyclic oligomers may be repolymerized in like manner to the cyclosiloxanes of formula (I) from whose polymerization mixture it was extracted. The extracted cyclosiloxanes will be of the formula (V):
~nX~tF
IV) wherein n, X, and RF are defined as in formula (I), and r + s =
t and t is 4 to 20 and r is 1 to t.
The degree of polymerization can be controlled by the amount of catalyst used and, to a greater extent, the presence of any chain capping agent which may be included in the polymerization mixture. Capping agents which may be used are typically disiloxanes of the formula (VI):
R - Si(CH3)ZOSi(CH3)2 - R (VI) wherein R is H, methyl, ethyl, phenyl, vinyl, hydroxypropyl, aminopropyl, or any other functional hydrocarbon radical. The choice of the disiloxane will depend upon the specific formulation of the resulting copolymer chosen for the final application of the copolymer as is known to those skilled in the art.
The cyclosiloxane of formula (I) may be copolymerized with a wide variety of cyclosiloxanes and linear siloxanes.
Cyclodimethyl-siloxanes such as octamethylcyclotetrasiloxane or decamethylcyclo-pentasiloxane may be used to produce a copolymer where the ratio of dimethylsiloxy groups to methylperfluoroorganosiloxy group is a value greater than three.
Cyclosiloxanes with functional groups can be incorporated to permit specific processing or impart specific properties to the SUBSTITUTE SHEET (RULE 26) WO 99/62916 PC'T/US99/04341 copolymer depending upon the final application of the copolymer as is known to those skilled in the art. Cyclosilox-anes which may be copolymerized with the cyclosiloxane of formula (I) include, but are not exclusive to, those which contain hydrogenmethylsiloxy, methylvinylsiloxy, methylphenylsiloxy, (cyanoethyl)methylsiloxy, (aminopropyl,)methylsiloxy, (hydroxy-propyl)methylsiloxy, (acryloxypropyl)methylsiloxy, and (methacryl-oxypropyl)methylsiloxy repeating units.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The practice of the present invention is illustrated by the following non-limiting examples. These examples are provided for illustrative purposes only and should not be construed to limit the scope of the claims in any manner whatsoever.
A 50 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 7 . 7 g of 98% ( 3-hydroxypropyl)heptamethylcyclotetrasiloxane (22 mmoles) and 2.3 g of triethylamine (23 mmoles). The mixture was stirred and 15.0 g of 97% perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluoride (21.9 mmoles) was added dropwise. After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid fluoride and most of the cyclosiloxane were consumed with predominately the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer separated from the siloxane layer. The siloxane layer was washed with two 25 mL
portions of water and the siloxane layer was transferred into a 50 mL round bottom flask and distilled at 110°C and 0.3 mm Hg to yield a fraction of 14.7 g (66% yield) of 97% [3-(perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl)oxy-propylJheptamethylcyclotetrasiloxane (14.3 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is given by formula (II) wherein p is 3, or more specifically as shown in formula (VII) below wherein p is 3. The product was analyzed by spectroscopy with the following results:
1H NMR 400 MHz, CDC13: d 0.1 (s 21 H), 0.6 (t 2 H), 1.8 (p 2 H), SUBSTITUTE SHEET (RULE 26) 4.4 (m 2 H); 19F NMR 376 MHz, CDC13: d -81 (CF3), -82 (CF3), -83 (CF3), -85 (CF3), -130 (CFZ), -132 (CFZ), -144 (CF); IR (neat liquid on NaCl): cm 1. 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).
H3C H C H H C H O O F3C C ~F
HsC\ ~~-cs~ yi yi ~C.~ '~C~ ~F
H3C- ~ ~ y ~O H H F3C \F F ~F
~g~H3 ( m I ) Si-c 7 HOC ~
CH:
A 50 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 6 . 2 g of 98% ( 3-hydroxypropyl)heptamethylcyclotetrasiloxane (18 mmoles) and 1.8 g of triethylamine (18 mmoles). The mixture was stirred and 15.0 g of 95% perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl fluoride (17 mmoles) was added dropwise.
After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid fluoride and most of the cyclosiloxane were consumed with predominately the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer was separated from the siloxane layer. The siloxane layer was washed with two 25 mL portions of water and the siloxane layer was transferred into a 50 mL round bottom flask and distilled at 118-28°C ,and 0.05 mmHg to yield a fraction of 14.0 g (71% yield) of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropylJheptamethylcyclotetrasiloxane (12.2 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(0), and R~ is given by formula (II) wherein p is 4, or more specifically as shown in formula (VII) wherein p = 4.
The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDCl3:d 0.1 (s 21 H), 0.6 (t 2 H), 1.8 (p 2 H), 4.4 (m 2 H); IR (neat liquid on NaCl):cm 1. 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 (s), 970 SUBSTITUTE SHEET (RULE 26) (s), 810 (vs), 750 (m).
A 50 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 5 . 1 g of 98% ( 3-hydroxypropyl)heptamethylcyclotetrasiloxane (15 mmoles) and 1.5 g of triethylamine (15 mmoles). The mixture was stirred and 15.0 g of 92% perfluoro-2,5,8,11,14-pentamethyl-3,6,9,12,15-tetraoxaocta-decanoyl fluoride (14 mmoles) was added dropwise.
After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid fluoride and most of the cyclosiloxane were consumed with predominately the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer was separated from the siloxane layer. The siloxane layer was washed with two 25 mL portions of water and the siloxane layer was transferred into a 50 mL round bottom flask and distilled at 128-38°C and 0.05 mmHg to yield a fraction of 13.0 g (71% yield) of >99% [3-(perfluoro-2,5,8,11,14-pentamethyl-3 , 6 , 9 , 1 2 , 1 5 - p a n t a o x a o c t a d a c a n o y 1 ) o x y -propylJheptamethylcyclotetrasiloxane (14.1 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is given by formula (II) wherein p is 5, or more specifically as shown in formula (VII) wherein p = 5. The product was analyzed by spectroscopy with the following results: 1H NMR
400 MHz, CDC13: d 0.1 (s 21 H), 0.6 (t 2 H), I.8 (p 2 H), 4.4 (m 2 H); IR (neat liquid on NaCl): cm 1. 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).
Five different 10 mL round bottom flasks equipped with magnetic stirring bars and fitted with rubber septa were charged with 0.5 g of 98% (3-hydroxypropyl)heptamethylcyclotetrasiloxane (1.5 mmoles) and into 4 of the flasks was added a portion of an inorganic base as indicated in Table 1. All the bases were used as received and were in excess of 98% purity. The mixture was stirred and 1.2 g of 95% perfluoro-2,5,8,11-tetramethyl-3,6,9,12-SUBSTfTUTE SHEET (RULE 26) tetraoxa-pentadecanoyl fluoride (1.4 mmoles) was added dropwise via a 3 mL syringe with a 25 G needle through the septa with an additional 25 G needle placed in the septa to assure that any pressure generated could be released. After complete addition of the acid fluoride a gas chromatographic analysis was run. The differences observed in the reaction mixtures resulting from the use of these different bases are indicated in Table 1.
Base Mass in mequival Ratio*
ents None 16.2 CaH 0.08 1.9 19.7 MgS~54 0.21 1.7 13.3 Mg0 0.07 1.7 14.0 KZHP04 0.31 1.8 68.0 * Ratio of the area of [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl)oxypropyl]heptamethylcyclotetra-siloxane to observed side products excluding those with retention of perfluoro-2,5,8.11-tetramethyl-3,6,9,12-tetraoxapentadecanoic acid or less.
A 3-necked 250 mL round bottom flask equipped with a magnetic stirring bar, a temperature probe, and an addition funnel was charged with 34.6 g of 99~ (3-hydroxypropyl)heptamethylcyclotetra-siloxane (101 mmoles) and 17 . 0 g of K2HP04 ( 97 . 6 mequivalents ) . The mixture was stirred and 87.6 g of hexafluoropropeneoxide oligomer acid fluoride with an average degree of polymerization of 4.4 (119 mmoles) was added dropwise at a rate such that the temperature did not exceed 40°C.
The contents of the pot was placed in a funnel attached to a filter flask with a 1 micron filter in line and collected in the flask when vacuum was applied to the flask. The 100.6 g of liquid in the filter was transferred into a 250 mL round bottom flask and distilled at 51-128°C and 0.05 to 0.25 mmHg to yield a fraction of 68 g (57% yield) of [3-(oligohexafluoropro-peneoxide-oyl)oxypropyl]heptamethylcyclotetrasiloxane (12.2 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is given by formula (II) wherein p is 4.1, or more SUBSTITUTE SHEET (RULE 26) specifically as shown in formula (VII) wherein p averages 4.1, as determined by 19F NMR spectroscopy from the integration ratio's of CF3 signals, and by gas chromatography assuming a relative response of individual homologues proportional to their mass and retention times of homologues determined from monodispersed standards from examples 1 through 3, with a dispersivity index, XW/Xn, of 1.1. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDC13:
d 0.1 (s 21 H), 0.6 (t 2 H), 1.8 (p 2 H), 4.4 (m 2 H); 19F NMR
376 MHz, CDC13: d -81 (CF3), -82 (CF3), -83 (CF3), -85 (CF3), -130 (CF2), -132 (CF2), -145 (CF); IR (neat liquid on NaCl): cm 1. 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 {s), 970 (s), 810 (vs), 750 (m).
A 25 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 4.0 g of (3-hydroxy-propyl)heptamethylcyclotetrasiloxane (12 mmoles) and 1.0 g of pyridine (13 mmoles). The mixture was stirred and 5.0 g of per-fluorooctanoyl chloride (12 mmoles) was added dropwise. After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid chloride and most of the cyciosiloxane were consumed with one product as 96.5%
of the mixture. The contents of the flask were filtered using a 0.45 micron syringe filter into a 50 mL 1-necked round bottom flask. The solids in the flask were washed with 2.5 mL of pentane and this suspension added to the syringe and filtered into the 50 mL flask. The solids in the syringe were washed with an additional 2.5 mL of pentane and filtered into the 50 mL flask.
The contents of the flask were distilled at 82°C and 0.04 mmHg to yield a fraction of [3-(perfluorooctanoyl)oxypropyl]hepta-methylcyclotetrasiloxane which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is a perfluorinated straight chain monovalent alkyl radical of 7 carbons atoms, or more specifically as shown in formula (VIII) below.
SUBSTITUTE SHEET (RULE 26) O
H3C H H H H ') F /F F /r' F\ %
H3C p_c ~C'CrC'p~C~C~C'C~C~C~C~C~F
v ~ W ~ \ / \ / \ / \ / \
H3C-Ss O H H F F F F F F F F
O~ ~Si--t. Hz ~Si--~7 ~CH~
H3C 'CH.
(VIII) A 100 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 4.2 g of allyl alcohol (72 mmoles) and 9.5 g of anhydrous pyridine (120 mmoles ) . The mixture was stirred and 40 g of 97% perfluoro-2, 5, 8-trimethyl-3,6,9-trioxadodecanoyl fluoride (60 mmoles) was added dropwise. After complete addition of the acid fluoride, two phases were present. The stirring was stopped and the contents poured into a separatory funnel. A gas chromatographic analysis of the lower layer displayed no acid fluoride and very little allyl alcohol and the formation of one product in a significant quantity. The bottom ester layer was removed and the top layer discarded. The bottom ester layer was again placed in the separatory funnel and washed with a 20 mL portion of dilute hydrochloric acid. The ester was removed and subsequently washed with another 20 mL portion of dilute hydrochloric acid and then twice with 20 mL portions of water. The ester was transferred into a round bottom flask and distilled at 62-64°C and 3 mmHg to yield a traction of 29.0 g (69% yield) of >99% [3-perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecan-oyl)oxy]-1-propene (41 mmoles).
A 3-necked 25 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 10.0 g of >99% [3-(perfluoro-2,5,8-tri-methyl-3,6,9-trioxadecan-oyl)oxy]-1-propene and 4.0 g of hepta-methylcyclotetrasiloxane (14 mmoles). The mixture was heated to 80°C and 10 ~L of a Pt 1,3-divinyltetramethyldisiloxane complex in xylene (3% Pt) was added via a syringe. The temperature was SU8ST1TUTE SHEET (RULE 26) increased. When the temperature exceeded 90°C an exothermic reaction occurred with a rapid increase in temperature to 105°C
which soon cooled to below 100°C. After a gas chromatographic analysis indicated a low conversion, the temperature was increased to 100°C and an additional 5 pL of the platinum catalyst solution was added to the mixture resulting in another exothermic reaction. The heating was then stopped and an additional gas chromatographic analysis indicated that although all of the reagents were consumed the desired product, [3-(perfluoro-2,5,8-trimethyl-3,6,9-trioxa-dodecan-oyl)oxypropyl]heptamethylcyclotetrasiloxane, constituted only 18%
of the mixture.
A 100 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 9.0 g of allyl amine (160 mmoles). The liquid was stirred and 40 g of 97%
perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluoride (60 mmoles) was added dropwise. Dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer separated from the amide layer. The amide layer was washed again with dilute hydrochloric acid and twice with water. The amide layer was transferred into a round bottom flask and distilled at 101°C and 3 mmHg to yield a fraction of 21.6 (52% yield) of >99% N-allylperfluoro-2,5,8-trimethyl-3,6,9-trioxado-decanamide (31 mmoles).
A 3-necked 25 mL flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 10.0 g of >99% N-allyl-perfluoro-2,5,8-trimethyl-3,6,9-tri-oxadodecanamide (14 mmoles) and 4.0 g of heptamethylcyclotetra-siloxane (14 mmoles). The mixture was heated to 100°C and 10 uL
of a Pt 1,3-divinyltetramethyldisiloxane complex in xylene (3%
Pt) was added via a syringe. An exothermic reaction occurred with a rapid increase in temperature to 147°C which cooled after 10 minutes. A gas chromatographic analysis indicated high conversion to a single product. The contents of the flask were distilled at 116-20°C and 0.04 mmHg to yield a fraction of 5.7 g (43% yield) of >99% N-(3-heptamethylcyclotetrasiloxan-yl)propylperfluoro-SUBSTITUTE SHEET (RULE 26) 2,5,8-trimethyl-3,6,9-trioxadodecanamide (6 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is NHC(O), and RF is given by formula (II) wherein p is 3, or more specifically as shown in formula (IX) below where R = H and p =
3. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDC13: d 0.1 (m 21 H), 0.6 (t 2 H), 1.7 (p 2 H), 3.4 (m 2 H), 6.7 (s 1 H); IR (neat liquid on NaCl): cm 1. 3460 (m), 2970 (m), 1705 (s), 1550 (m), 1310 (m), 1245 (vs), 1200 (s), 1150 (s), 1070 {vs), 995 (s), 970 (s), 810 (vs), 750 (m).
H3C~ ~O-Si"; C ~C; C~N~ ~C~ ~~ ~F
H3C-S i O H H R F;C F F F
O~ ~S ~H3 Si--~ CH3 (IX) A 100 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 5.0 g of N-methylallyl amine (70 mmoles). The liquid was stirred and 17.5 g of 97% per-fluoro-2,5,8- trimethyl-3,6,9-trioxadodecanoyl fluoride (26 mmoles) was added dropwise. The reaction mixture was transferred into a separatory funnel and the amide layer was washed twice with dilute hydrochloric acid and once with water.
The amide layer was traps-ferred into a round bottom flask and distilled at 98°C and 2 . 4 mmHg to yield a fraction of 14 . 3 g ( 77%
yield) of >99% N-allyl-N-methyl-perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanamide {20 mmoles).
A 3-necked 25 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 7.0 g of >99% N-allyl-N-methylperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanamide (10 mmoles) and 2.8 g of heptamethylcyclotetrasiloxane (10 mmoles). The mixture was heated to 106°C and 10 pL of a Pt 1,3-divinyltetramethyl-disiloxane complex in xylene (3% Pt) was added via a syringe. An exothermic reaction occurred with a rapid increase in temperature SUBSTITUTE SHEET (RULE 26) WO 99/62916 PCTlUS99/04341 to 155°C which cooled after 3 minutes. A gas chromatographic analysis indicated high conversion to a single product. The contents of the flask were distilled at 100-05°C and 0.04 mmHg to yield a fraction of 5.2 g (53% yield) of >99% N-(3-heptamethylcyclotetrasiloxan-yl)propyl-N-methylperfluoro-2,5,8-trimethyl-3,6,9trioxadodecanamide (5.2 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is N(CH3)C(O), and RF is given by formula (II) wherein p is 3, or more specifically as shown in formula (IX) where R = CH3 and p = 3. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDC13: d 0.1 (m 21 H), 0.5 (m 2 H), 1.7 (m 2 H), 3.1 (m 3 H), 3.5 (m 2 H); IR (neat liquid on NaCl): cm 1. 2970 (m), 1685 (s), 1410 (w), 1300 (m), 1245 (vs), 1200 (s), 1140 (m), 1080 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).
A 500 mL round bottom flask equipped with a magnetic stirring bar, a temperature probe, a condenser, and an addition funnel was charged with 11.0 g of allyl amine (193 mmoles) and 15 g of pyridine (190 mmoles). The liquid was stirred and 150 g of hexa-fluoropropeneoxide oligomer acid fluoride, with a degree of polymerization of 4.4 (205 mmoles) was added dropwise. The contents of the flask were transferred to a separatory funnel and washed twice with dilute hydrochloric acid and subsequently washed twice with water. The amide layer was transferred into a round bottom flask. The product was distilled at 95-190°C and 5.1 mmHg to yield a fraction of 125 g (84% yield) of N-allyl-oligohexafluoropropene-oxide-oyi amide.
A 3-necked 250 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 5.0 g of N-ailyl-oligohexafluoropropene-oxide-oyl amide (6.5 mmoles) and 30 g of heptamethylcyclotetra-siloxane (106 mmoles). The mixture was heated to i00°C and 30 uL
of a Pt 1,3-divinyltetramethyldisiloxane complex (3% Pt) was added via a syringe. An additional 70 g of N-allyl-oligohexafluoropropene-oxide-oyl amide (91 mmoles) was added dropwise. After addition of the allyl amide was complete, 5 uL
additional Pt 1,3-divinyltetra-methyldisiloxane complex in xylene SUBSTITUTE SHEET (RULE 26) (3% Pt) was injected into the flask. The resulting liquid was transferred into a distillation flask and 78 g (69% yield) of 91%
N-(3-heptamethylcyclotetra-siloxan-yl)propyloligohexafluoro-propeneoxide-oyl amide (91 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is NHC(O), and RF is given by formula (II) wherein p is 3.2, or more specifically as shown in formula ( IX) where R = H and p is an average of 3.2 as determined by gas chromatography, assuming a relative response of individual homologues proportional to their mass and retention times of homologues determined from a mono-dispersed standard from example 8, with a dispersivity index, XW/Xn, of 1. 1. The ma jor impurities in the product were unreacted N-allyloligohexafluoropropeneoxide-oyl amides.
In a 1.5 dram vial containing 1.0 g of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]-heptamethylcyclotetrasiloxane (0.87 mmoles) was injected 2.0 pL
of trifluoromethanesulfonic acid (0.023 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that flowed slowly when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 4 hours. Little or no change in the oil was apparent. To the vial was added 0.01 g of Mg0 (0.2 mequivalents) and the oil warmed with the heating gun to disperse the salt. After the mixture cooled, 1 mL of pentane was added to the vial and the mixture was shaken. Upon settling, two liquid phases and a solid phase were apparent. The liquid layers were filtered from the solid using a 3 mL syringe equipped with a 0.45 micron filter into a 3 dram vial. The 1.5 dram vial and syringe were rinsed with pentane and the liquid injected through the filter into the 3 dram vial such that an approximately 20% by volume perfluoroethersiloxane mixture in pentane resulted.
The two phases were dispersed by shaking and immediately a 3 NL sample was drawn into a syringe and injected into a gas chromatograph. Signals were observed in the chromatographic trace which had a pattern of four groups of signals. The two groups SUBSTITUTE SHEET (RULE 26) with the shorter retention time each displayed four narrow well resolved signals which decreased in intensity with increasing retention time. The latter two groups displayed many poorly resolved signals. The retention times of the first group were identical to that of octamethylcyclotetrasiloxane, decamethyl-cyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetra-decamethylcycloheptasiloxane. The largest peak of the second group had the retention time of [3-(per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]hepta-methylcyclotetrasiloxane. Since a complete redistri-bution of the siloxane units should result during polymerization, the molar ratio of octamethylcyclotetrasiloxane:decamethylcyclopenta-siloxane should equal K4/K4:K5(0.75)/K4:K6(0.75)Z/K4 for random placement of siloxane units where the dimethylsiloxane units constitute 75% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer.
Assuming a molar response factor for the homologues in the gas chromatographic trace which is proportional to the molecular weight the homologue, the observed molar ratio of octamethyl-cyclotetrasiloxane:decamethylcyclopentasiloxane of 10:4:1 agreed with the theoretical ratio of 10:4:1. The second group consisted of [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapenta-decan-oyl)oxypropyl]heptamethylcyclotetrasiloxane, [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]-nonamethylcyclopentasiloxane, [3-(per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]undeca-methylcyclohexasiloxane, and [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]tridecamethylcyclo-heptasiloxane. The molar ratio of [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]hepta-methylcyclotetrasiloxane:[3-(per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]nonamethylcyclopenta-siloxane:[3-(perfluoro-2,5,8,11-tetra-methyl-3,6,9,12-tetra-oxapentadecan-oyl)oxypropyl]undecamethylcyclohexasiloxane was observed to be 10:5:2 in the gas chromatographic trace which agreed with the theoretical 10:5:2 ratio from K4/K4:1.25K5(0.75)/K4:1.5K6(0.75)2/K4. The match of these ratios SUBSTITUTE SHEET (RULE 25) confirmed that complete and random redistribution occurred and that a high molecular weight copolymer was formed.
The upper layer was drawn from the lower layer using a syringe and placed in a scintillation vial. An additional 3 mL
of pentane was added to the 3 dram vial containing the lower layer and the vial shaken. The top layer was again removed via a syringe and placed in the scintillation vial. Evaporation of the pentane from the solution in the scintillation vial under a stream of nitrogen at room temperature resulted in 0.2 g of an oil which was indistinguishable in a gas chromatographic trace from that of the original dispersion with the exception that the signal from pentane was nearly gone, the signals for octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane were diminished significantly, and the signal for dodecamethylcyciohexasiloxane was slightly reduced relative to the peak for [3-(perfiuoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]heptamethylcyclotetra-siloxane.
A gas chromatographic trace of the lower layer in the 3 dram vial displayed almost no signals from the equilibrium cyclo-siloxanes. The pentane swelling the copolymer was removed by heating the vial on a hot plate while passing a stream of nitrogen over the surface. This resulted in 0.6 g of a gum which displayed no flow upon cooling when the vial was placed on its side for a period of 2 hours, indicating that the molecular weight of the copolymer was high.
Into a 1.5 dram vial containing 1.0 g of >99% N-(3-hepta-methylcyclotetrasiloxan-yl)propyl-N-methylperfluoro-2,5,8-tri-methyl-3,6,9-trioxadodecanamide (0.87 mmoles) was injected 2.0 uL of trifluoromethanesulfonic acid (0.023 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that flowed slowly when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 4 hours. The resulting viscous linear-cyclic mixture was similar in nature to that which resulted from the polymerization of 99%
[3-(perfluoro-2,5,8,i1-tetramethyl-3,6,9,12-tetraoxapentadecan-SUBSTITUTE SHEET (RULE 26) WO 99/b291b PCT/US99/04341 oyl)-oxypropyl]-heptamethylcyclotetrasiloxane in Example 11.
Into a 1.5 dram vial containing 1.0 g of >99% N-(3-hepta-methylcyclotetrasiloxan-yl)propylperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanamide (0.87 mmoles) was injected 2.0 uL of trifluoro-methanesulfonic acid (0.023 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that displayed almost no flow when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 4 hours. A viscous linear-cyclic mixture resulted that was much more viscous than the mixture from the polymerization of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)-oxypropyl]heptamethyl-cyclotetrasiloxane in Example 11.
Into a 1.5 dram vial containing 2.0 g of [3-(oligohexa-fluoropropeneoxide-oyl)oxypropyl]heptamethylcyclotetrasiloxane (1.7 mmoles) from Example 5 was injected 3.0 NL of trifluoromethane-sulfonic acid (0.035 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that flowed slowly when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 4 hours. To the mixture was added 0.021 of Mg0 (0.52 mmoles) and the mixture warmed with a heating gun to aid in mixing of the powder. A
linear-cyclic mixture, similar in nature to that which resulted from the polymerization of 99% (3-(perfluoro-2,5,8,11-tetra-m a t h y 1 - 3 , 6 , 9 , 1 2 - t a t r a o x a p a n t a - d a c a n -oyl)oxypropyl]heptamethylcyclotetrasiloxane in Example 11, was observed by gas chromatographic analysis.
Into a 1.5 dram vial containing 2.0 g of N-(3-heptamethyl-cyclotetrasiloxan-yl)propyloligohexafluoropropeneoxide-oyl amide (1.7 mmoles) from Example 10 was injected 3.0 NL of trifluoro-methanesulfonic acid (0.035 mmoles) and the mixture was shaken.
The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that SUBSTITUTE SHEET (RULE 26) displayed almost no flow when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 24 hours. The mixture became hazy in appearance at room temperature but became clear upon warming. To the mixture was added 0.012 of Mg0 (0.30 mmoles) and the mixture warmed with a heating gun to aid in mixing of the powder. A linear-cyclic mixture, similar in nature to that which resulted from the polymerization of 99$ [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9.12-tetraoxapentadecan-oyl)oxypropyl]heptamethyl-cyclotetrasiloxane in Example 11, was observed by gas chromatographic analysis.
Into a 1.5 dram vial containing 2.0 g of N-(3-heptamethyl-cyclotetrasiloxan-yl}propyloligohexafluoropropeneoxide-oyl amide (1.7 mmoles) from Example 10 was injected 19.0 uL of tetrabutyl-ammonium fluoride in tetrahydrofuran (0.019 mmoles) and the mixture was shaken. The vial was warmed gently with a heating gun over a period of 10 minutes. After cooling to room temperature, a viscous mixture was noted. The heating of the vial was repeated 6 times until a heavy oil, that displayed very slow flow when the vial was inverted at room temperature, resulted and no apparent increase in viscosity was observed upon subsequent heating. The oil was warmed again and let stand for 24 hours. The mixture remained clear in appearance at room temperature. The vial was then heated strongly with the formation of bubbles, presumably from the decomposition of the tetrabutylammonium salt with the liberation of tributylamine and butene. A linear-cyclic mixture, similar. in nature to that which resulted in Example 15 was observed by gas chromatographic analysis.
A 3-necked 50 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 10.0 g of 1H,1H,2H-perfluoro-1-octene (28.9 mmoles) and 10.0 g of heptamethylcyclotetrasiloxane (35.4 mmoles ) . The mixture was heated to 90°C and 5 NL of a Pt 1, 3-divinyltetra-methyldisiloxane complex in xylene (3% Pt) was added via a syringe. An exothermic reaction occurred with a rapid SUBSTITUTE SHEET (RULE 26) increase in temperature to 130°C which cooled after 3 minutes.
A gas chromato-graphic analysis indicated a low conversion to a single product. The addition of 20 uL of the 1,3-divinyltetramethyldisiloxane complex (3% Pt) did not result in higher conversion. The contents of the flask were distilled at 80°C and <2 mmHg to yield a fraction of 4.2 g (23% yield) of (6.7 mmoles), which corresponds to formula (I) wherein m is 1, n is 1, X is CH2 and RF is a perfluorinated straight chain monovalent alkyl radical of 6 carbon atoms, or more specifically as shown in formula (X) below where q = 5. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDC13:
d 0.1 (m 21 H), 0.8 (m 2 H), 2.1 (m 2 H); IR (neat liquid on NaCl): cm 1. 2970 (m), 2870 (w), 1445 (w), 1405 (w), 1370 (w), 1265 {s), 1240 (s), 1205 (m), 1175 (w), 1150 (m), 990 (vs), 810 (vs).
Fv ~F
H3C' .O
H3C-Si O H H F F
~S ~H3 ~Si--~~ CFi=
HOC CHI ( x ) Into a 1.5 dram vial containing 2.0 g of 99% 1H,1H,2H,2H,1-(heptamethylcyclotetrasiloxan-yl)perfluorooctane (3.2 mmoles) from Example 17 was injected 3.0 uL of trifluoromethanesulfonic acid (0.035 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a gum, which displayed almost no flow when the vial was inverted at room temperature, resulted.
The gum was warmed again and let stand for 24 hours. To the vial was added 0.021 g of Mg0 (0.52 mmoles) and the mixture warmed with a heating gun to aid in the dispersion of the powder. A
linear-cyclic mixture, similar in nature to that which resulted from the polymerization of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)-oxypropyl]heptamethylcyclotetrasiloxane in Example 11, was observed by gas chromatographic analysis.
SU8ST1TUTE SHEET (RULE 26) Into a 1.5 dram vial containing 0.20 g of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]-heptamethylcyclotetrasiloxane (0.18 mmoles) from Example 2 and 9.5 g of octamethylcyclotetrasiloxane (32.0 mmoles) was injected 15 uL of trifluoromethanesulfonic acid (0.17 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a gum, which dis-played almost no flow when the vial was inverted at room~temp-erature, resulted. The gum was warmed again and let stand for 24 hours. To the vial was added 0.1 g of Mg0 (2.5 mmoles) and the mixture warmed with a heating gun to aid in dispersion of the powder. A linear-cyclic mixture resulted which was observed by gas chromatographic analysis. Since a complete redistribution of the siioxane units should result during polymerization, the molar ratio of octamethylcyclotetra-siloxane:decamethylcyclopentasiloxane:dodecamethylcyclohexa-siloxane should equal K4/K4:K5(0.997)/K4:-K6(0.997)2/K4 for random placement of siloxane units where the dimethylsiloxane units constitute 99.7% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer.
Assuming a molar response factor for the homologues in the gas chromatographic trace which is proportional to the molecular weight of the homologue, the observed molar ratio of octamethyl-cyclotetrasiloxane:decamethylcyclopentasiloxane:dodecamethyl-cyclohexasiloxane of 10:5.1:1.3 agreed well with the theoretical ratio of 10:5.2:1.8. The mole ratio of octamethylcyclotetrasilox-ane:[3-(perfluoro-2,6,8,11-tetramethyl-3,6,9,12-tetraoxapenta-decan-oyl)oxypropyl]heptamethylcyclotetrasiloxane was determined to be 100:2 which agreed well with the theoretical ratio of 100:1.2 from the relationship K4(0.997)4:4K4(0.997)3{0.003) for a random polymerization to high molecular weight.
Into a 1.5 dram vial containing 0.20 g of 99% [3-(perfluoro-2,5,8,11,14-pentamethyl-3,6,9,12,15-pentaoxapentadecan-oyl)oxy-propylJheptamethylcyclotetrasiloxane (0.17 mmoles), 1.90 g of octamethylcyclotetrasiloxane (6.4 mmoles) and 0.020 g of 1,3,5,7-SUBSTITUTE SHEET (RULE 26) WO 99/62916 PCf/US99/04341 tetravinyltetramethylcyclotetrasiloxane (0.006 mmoles) was injected 3 NL of trifluoromethanesulfonic acid (0.03 mmoles) and the mixture was shaken. The vial was warmed gently with a heating gun and the viscosity increased over a period of 30 minutes. The mixture was warmed again and let stand for 24 hours. To the vial was added 0.02 g of Mg0 (0.4 mmoles) and the mixture warmed with a heating gun to aid in dispersion of the powder. A linear-cyclic mixture resulted which was dissolved in 6 mL of cyclohexane and analyzed by gas chromatography. Since a compete redistribution of the siloxane units should result during polymerization, the molar ratio of octamethylcyclotetrasiloxane:decamethylcyclo-pentasiloxane:dodecamethylcyclohexasiloxane should equal K4/K4:K5(0.993)/K4:K6(0.993)2/-K4for random placement of siloxane units where the dimethyl-siloxane units constitute 99.3% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer. Assuming a molar response factor for the homologues in the gas chromatographic trace which is proportional to the molecular weight of the homologue, the observed molar ratio of octamethylcyclotetrasiloxane:decamethyl-cyclopentasiloxane:dodecamethylcyclohexasiloxane of 10:5.5:1.7 agreed well with the theoretical ratio of 10:5.2: 1.8. Small peaks were observed in gas chromatographic trace which had retention times for that of vinylheptamethylcyclotetrasiloxane and vinylnonamethylcyclopenta-siloxane indicating that the methylvinylsiloxane units from the 1,3,5,7-tetravinyltetramethyl-cyclotetrasiloxane were randomly dispersed through the copolymer and cyclic oligomers.
Into a 1.5 dram vial containing 0. 15 g of 94% [ 3-(perfluoro-2,5-dimethyl-3,6-dioxanonan-oyl)oxypropyl]heptamethylcyclotetra-siloxane (0.17 mmoles), 2.15 g of octamethylcyclotetrasiloxane (7.2 mmoles) and 0.033 g of 1,3-divinyl-1,1,3,3-tetramethyldi-siloxane (0.15 mmoles) was injected 3 pL of trifluoromethane-sulfonic acid (0.03 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes. To the vial was added 0.05 g of Mg0 (1 mmole). A copolymer-cyclic mixture was dissolved in 3 mL of SUBSTITUTE SHEET (RULE 26) WO 99/62916 PC'T/US99/0434I
cyclohexane and analyzed by gas chromatography. Since a complete redistribution of the siloxane units should result during polymerization, the molar ratio of octamethylcyclotetrasilox-ane:decamethylcyclopentasiloxane:dodecamethylcyclohexasiloxane should equal K4/K4:K5(0.994)/K4:K6(0.994)2/K4for random placement of siloxane units where the dimethylsiloxane units constitute 99.4 of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer as a macromolecule with a degree of polymerization of approximately 200 was targeted by the proportions of cyclosiloxanes to disiloxanes used. Assuming a molar response factor for the homologues in the gas chromatographic trace which is proportional to the molecular weight of the homologue, the observed molar ratio of octamethylcyclotetrasiloxane:decamethylcyclopenta-siloxane:dodecamethylcyclohexasiloxane of 10:6.4:2.1 agreed with the theoretical ratio of 10:5.2:1.8. No unreacted 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was observed in the gas chromatographic trace.
The present invention may be embodied in other specific forms without departing from~the spirit of essential attributes thereof, and accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.
The above-referenced patents and publications are hereby incorporated by reference.
SUBSTITUTE SHEET (RULE 26)
CYCLOSILOXANES AND COPOLYMERS PREPARED FROM THESE CYCLOSILOXANES
FIELD OF THE INVENTION
The present invention relates to the preparation of cyclosiloxanes with one perfluorinated substituent and their ring-opening polymerization into silicone copolymers.
BACKGROUND OF THE INVENTION
One of the most important methods of preparing silicone polymers and copolymers is via ring-opening polymerization. Most commonly it is carried out by the polymerization of unstrained cyclosiloxanes, generally cyclic tetramers or pentamers, where no heat is generated upon polymerization. Typically the polymer constitutes up to approximately 90 percent of the resulting equilibrium mixture depending upon the substituents on the cyclosiloxane, the degree of polymerization achieved, and the amount of any solvent used in the polymerization. The amount of cyclosiloxanes that have been observed in equilibrium with many silicone polymers is described in Siloxane Polymers, Chapter 3, S.J. Clarson and J.A. Semlyen, ed., Ellis Horwood - PTR Rentis Hall, Englewood Cliffs, NJ, 1993. Polymerization can also be carried out with cyclic trimers. Cyclic trimers are strained and the polymerization is exothermic. Cyclic trimers are generally more difficult to prepare than cyclic tetramers and pentamers.
The most common fluorinated silicone is prepared by the ring-opening polymerization of 1,3,5-tris-(3,3,3-trifluoro-propyl)-1,3,5-trimethylcyclotrisiloxane. The weight percent of the fluorocarbon portion of the cyclosiloxane and its resulting homo-polymer is 44% by weight. The exothermic polymerization is driven due to the ring strain that is released upon the opening of the cyclic trimer. The polymerization must be stopped immediately after high polymer has formed, otherwise the polymer reverts to a mixture of cyclics, primarily the unstrained tetramer and pentamer which together constitute about 90% by weight of the cyclic mixture.
United States Patent No. 5,202,453 describes a strained cyclotrisiloxane with a single fluorinated organic substitutent.
This compound was prepared in a two step process from a 1H, 1H, 2H-su~;~rrrru'~'E~~
vinyl terminated oligomer of hexafluoropropene oxide with a combined yield of approximately 50~ based upon the moles of oligomer used. Though not demonstrated in the patent, it was suggested to be ring-opening polymerizable in the presence of alkaline or acid catalysts, presumably under conditions similar to those used for the polymerization of 1,3,5-tris-(3,3,3-trifluoro-propyl)-1,3,5-trimethylcyclotrisiloxane.
Unstrained cyclosiloxanes with one or two large substituents on each Si atom typically are difficult to polymerize as the magnitude of a cyclosiloxane's equilibrium constant increases relative to that of a cyclosiloxane with smaller substituents, while at the same time the maximum concentration of the Si-O bond decreases as the size of the substituent increases. These factors result in a very high proportion of cyclosiloxanes at equilibrium as in the case of 1,3,5-tris-(3,3,3-trifluoropropyl)-1,3,5-tri-methylcyclotrisiloxane. Because of this problem, it is common to prepare a silicone polymer with a small reactive group, often a hydrogen substituent, on the backbone. The hydrosilation of an olefin with a Si-H containing compound is frequently used to prepare organically substituted siloxanes. This hydrosilation is often difficult to perform if the solubility of the group to be substituted on the siloxane backbone is a low in the Si-H
containing silicone polymer. Often a Si-H containing polymer contains sites where the Si-H has undergone hydrolysis to Si-OH
during its preparation, storage, or during the hydrosilation reaction if water is present. Such units can permit the formation of branches or gels during the hydrosilation reaction.
Perfluorinated organic molecules often display very low miscibility in silicone polymers. Hydrosilation reactions often do not proceed to complete conversion of the olefin or the silane reactants. For these reasons it is difficult to achieve a perfluorinated organic substituted silicone polymer by modification of a functional silicone polymer without defects in the structure due to incomplete reaction or defects from the starting Si-H containing polymer.
United States Patent No. 5,247,116 describes a method where unstrained cyclosiloxanes with a single functional group can be SUBSTITUTE SHEET (RULE 26) prepared and subsequently isolated. This functional group may be transformed in a variety of fashions such that a single perfluorinated organic moiety may be introduced to a cyclosiloxane ring. The advantage of such a cyclosiloxane is that the Si-O bond concentration can be significantly higher than that of cyclo-siloxane with a perfluorinated organic substituent at every Si atom, for an equivalent molecular weight of the cyclosiloxane. Furthermore, the equilibrium cyclization constants for the majority of the resulting cyclosiloxanes remain close to that of cyclodi-methylsiloxanes. This results in a much greater fraction of linear siloxanes at equilibrium upon polymerization of the cyclosiloxane even though the starting cyclosiloxane is unstrained.
SUMMARY OF THE PRESENT INVENTION
One object of the present invention is to provide unstrained polymerizable cyclosiloxanes that have one substituent that contains a perf luorinated organic moiety whose structure is given by the general formula (I):
~X-RF
H C v..i CfI~
H3C ~S i o . ~O
O
K~~i-'4~m CH3 Q3;
(I) wherein m is an integer of 1 to 12; n is an integer of 1 to 4;
X is a divalent radical which may include O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O) and CH2; and RF is a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or RF is a perfluorinated ether radical of the general formula (II):
F - (CFCF20)p - CF -CF3 CF3 (II) wherein p is an integer of 1 to 10.
It is an object of the invention to prepare copolymers that result from the ring-opening polymerization of the cyclosiloxanes SUBSTITUTE SHEET (RULE 26) of formula (I) to give a copolymer of the general formula (III):
~3 --~~ i--iJ-~S i-E3 mt C~-Iz (III) ~~~~~X_RF
wherein m, n, X, and RF are defined as in formula (I); and q may be 2 to 1,000,000.
It is an object of the present invention to prepare copolymers from the cyclosiloxanes of formula (I) and cyclodimethylsiloxanes and/or polydimethylsiloxanes such that the resulting copolymer contains a lesser proportion of fluorinated siloxane groups than the cyclosiloxanes of formula (I).
It is an object of the present invention to prepare fluorinated silicones which contain in addition to the siloxy repeating units present in the cyclosiloxanes of formula (I) other siloxy repeating units which include, but are not exclusive to, hydrogenmethylsiloxy, methylvinylsiloxy, methylphenylsiloxy, (cyanoethyl)methylsiloxy, (aminopropyl)methylsiloxy, (hydroxy-propyl)methylsiloxy, and (trifluoropropyl)methylsiloxy units.
These units may be incorporated by the addition of the appropriate cyclosiloxane which contains one or more of these groups.
It is an object of the present invention to prepare copolymers from the cyclosiloxanes of the formula (I) and, optionally, other cyclosiloxanes, where the degree of polymerization is controlled by end-capping. This,is achieved by equilibrating the appropriate cyclosiloxanes with a disiloxane or the disiloxane's equivalent incorporated into a small polysiloxane. A wide variety of di-siloxanes and/or their equivalents in polysiloxanes are known which include, but are not exclusive to, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-di-(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-di(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-di-phenyl-1,1,3,3-tetramethyldisiloxane, 1,3-di-(3-chloropropyl-1,1,3,3-tetramethyldisiloxane, and 1,3-di-(3-methacryloxypropyl)-1,1,3,3-SUBSTITUTE SHEET (RULE 26) tetramethyldisiloxane, and mixtures of any of the foregoing.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The unstrained polymerizable cyclosiloxanes of the present invention are those which have methyl groups at all but one site for substituents. That site contains a perfluorinated organic moiety that may have a variety of molecular weights and functional groups connecting the moiety to the cyclosiloxane ring.
The cyclosiloxanes have the general formula (I). The cyclosiloxanes may be produced -by a hydrosilation reaction between a mono Si-H containing cyclodimethylsiloxane, such as heptamethyl-cyclotetrasiloxane or nonamethylcyclopentasiloxane, and a 1H,1H,2H-vinyl substituted fluorinated organic molecule.
The cyclosiloxane of formula ( I ) may be produced by reacting an oligomer of hexafluoropropeneoxide of the structure:
F - (CFCF20)p - CF - CF = O
CF3 CF3 {IV) wherein p is an integer of from 1 to 10, with an organic molecule that contains an amine or alcohol and a terminal vinyl group followed by hydrosilation between that amide or ester with a mono Si-H containing cyclodimethyldisiloxane. Alternately, the mono Si-H containing cyclodimethylsiloxane may undergo hydrosilation with an amine, such as allyl amine or N-methylallyl amine, or an alcohol, such as allyl alcohol, with a terminal vinyl group followed by its reaction with an oligomer of hexafluoropropene-oxide of formula (IV). In some cases, the ester that would result from the reaction between the oligomer of hexafluoropropene oxide of formula (IV) and methanol or ethanol may be used in an amidation or in a traps-esterification reaction to yield the cyclosiloxane of formula (I).
The cyclosiloxanes of formula (I) may be polymerized using an acid or alkaline catalyst in a manner typical of unstrained cyclosiloxanes to a mixture of linear copolymer and cyclic oligomers. The choice of catalyst will be dependent upon the nature of the group X in the cyclosiloxane of formula (I) as is known to those skilled in the art. The linear copolymer may be separated from the cyclic oligomers by extraction with a SUBSTITUTE SHEET (RULE 26) WO 99/62916 PCT/US99/(34341 hydrocarbon. The size of the hydrocarbon may vary depending upon the size of the perfluorinated organic moiety. In general the hydrocarbon will be less than 10 carbons in the chain such that it is sufficiently volatile to be easily removed from the extracted cyclosiloxanes and the copolymer. The resulting copolymer will have the general formula (III). The extracted cyclic oligomers may be repolymerized in like manner to the cyclosiloxanes of formula (I) from whose polymerization mixture it was extracted. The extracted cyclosiloxanes will be of the formula (V):
~nX~tF
IV) wherein n, X, and RF are defined as in formula (I), and r + s =
t and t is 4 to 20 and r is 1 to t.
The degree of polymerization can be controlled by the amount of catalyst used and, to a greater extent, the presence of any chain capping agent which may be included in the polymerization mixture. Capping agents which may be used are typically disiloxanes of the formula (VI):
R - Si(CH3)ZOSi(CH3)2 - R (VI) wherein R is H, methyl, ethyl, phenyl, vinyl, hydroxypropyl, aminopropyl, or any other functional hydrocarbon radical. The choice of the disiloxane will depend upon the specific formulation of the resulting copolymer chosen for the final application of the copolymer as is known to those skilled in the art.
The cyclosiloxane of formula (I) may be copolymerized with a wide variety of cyclosiloxanes and linear siloxanes.
Cyclodimethyl-siloxanes such as octamethylcyclotetrasiloxane or decamethylcyclo-pentasiloxane may be used to produce a copolymer where the ratio of dimethylsiloxy groups to methylperfluoroorganosiloxy group is a value greater than three.
Cyclosiloxanes with functional groups can be incorporated to permit specific processing or impart specific properties to the SUBSTITUTE SHEET (RULE 26) WO 99/62916 PC'T/US99/04341 copolymer depending upon the final application of the copolymer as is known to those skilled in the art. Cyclosilox-anes which may be copolymerized with the cyclosiloxane of formula (I) include, but are not exclusive to, those which contain hydrogenmethylsiloxy, methylvinylsiloxy, methylphenylsiloxy, (cyanoethyl)methylsiloxy, (aminopropyl,)methylsiloxy, (hydroxy-propyl)methylsiloxy, (acryloxypropyl)methylsiloxy, and (methacryl-oxypropyl)methylsiloxy repeating units.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The practice of the present invention is illustrated by the following non-limiting examples. These examples are provided for illustrative purposes only and should not be construed to limit the scope of the claims in any manner whatsoever.
A 50 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 7 . 7 g of 98% ( 3-hydroxypropyl)heptamethylcyclotetrasiloxane (22 mmoles) and 2.3 g of triethylamine (23 mmoles). The mixture was stirred and 15.0 g of 97% perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluoride (21.9 mmoles) was added dropwise. After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid fluoride and most of the cyclosiloxane were consumed with predominately the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer separated from the siloxane layer. The siloxane layer was washed with two 25 mL
portions of water and the siloxane layer was transferred into a 50 mL round bottom flask and distilled at 110°C and 0.3 mm Hg to yield a fraction of 14.7 g (66% yield) of 97% [3-(perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl)oxy-propylJheptamethylcyclotetrasiloxane (14.3 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is given by formula (II) wherein p is 3, or more specifically as shown in formula (VII) below wherein p is 3. The product was analyzed by spectroscopy with the following results:
1H NMR 400 MHz, CDC13: d 0.1 (s 21 H), 0.6 (t 2 H), 1.8 (p 2 H), SUBSTITUTE SHEET (RULE 26) 4.4 (m 2 H); 19F NMR 376 MHz, CDC13: d -81 (CF3), -82 (CF3), -83 (CF3), -85 (CF3), -130 (CFZ), -132 (CFZ), -144 (CF); IR (neat liquid on NaCl): cm 1. 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).
H3C H C H H C H O O F3C C ~F
HsC\ ~~-cs~ yi yi ~C.~ '~C~ ~F
H3C- ~ ~ y ~O H H F3C \F F ~F
~g~H3 ( m I ) Si-c 7 HOC ~
CH:
A 50 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 6 . 2 g of 98% ( 3-hydroxypropyl)heptamethylcyclotetrasiloxane (18 mmoles) and 1.8 g of triethylamine (18 mmoles). The mixture was stirred and 15.0 g of 95% perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl fluoride (17 mmoles) was added dropwise.
After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid fluoride and most of the cyclosiloxane were consumed with predominately the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer was separated from the siloxane layer. The siloxane layer was washed with two 25 mL portions of water and the siloxane layer was transferred into a 50 mL round bottom flask and distilled at 118-28°C ,and 0.05 mmHg to yield a fraction of 14.0 g (71% yield) of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropylJheptamethylcyclotetrasiloxane (12.2 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(0), and R~ is given by formula (II) wherein p is 4, or more specifically as shown in formula (VII) wherein p = 4.
The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDCl3:d 0.1 (s 21 H), 0.6 (t 2 H), 1.8 (p 2 H), 4.4 (m 2 H); IR (neat liquid on NaCl):cm 1. 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 (s), 970 SUBSTITUTE SHEET (RULE 26) (s), 810 (vs), 750 (m).
A 50 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 5 . 1 g of 98% ( 3-hydroxypropyl)heptamethylcyclotetrasiloxane (15 mmoles) and 1.5 g of triethylamine (15 mmoles). The mixture was stirred and 15.0 g of 92% perfluoro-2,5,8,11,14-pentamethyl-3,6,9,12,15-tetraoxaocta-decanoyl fluoride (14 mmoles) was added dropwise.
After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid fluoride and most of the cyclosiloxane were consumed with predominately the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer was separated from the siloxane layer. The siloxane layer was washed with two 25 mL portions of water and the siloxane layer was transferred into a 50 mL round bottom flask and distilled at 128-38°C and 0.05 mmHg to yield a fraction of 13.0 g (71% yield) of >99% [3-(perfluoro-2,5,8,11,14-pentamethyl-3 , 6 , 9 , 1 2 , 1 5 - p a n t a o x a o c t a d a c a n o y 1 ) o x y -propylJheptamethylcyclotetrasiloxane (14.1 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is given by formula (II) wherein p is 5, or more specifically as shown in formula (VII) wherein p = 5. The product was analyzed by spectroscopy with the following results: 1H NMR
400 MHz, CDC13: d 0.1 (s 21 H), 0.6 (t 2 H), I.8 (p 2 H), 4.4 (m 2 H); IR (neat liquid on NaCl): cm 1. 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).
Five different 10 mL round bottom flasks equipped with magnetic stirring bars and fitted with rubber septa were charged with 0.5 g of 98% (3-hydroxypropyl)heptamethylcyclotetrasiloxane (1.5 mmoles) and into 4 of the flasks was added a portion of an inorganic base as indicated in Table 1. All the bases were used as received and were in excess of 98% purity. The mixture was stirred and 1.2 g of 95% perfluoro-2,5,8,11-tetramethyl-3,6,9,12-SUBSTfTUTE SHEET (RULE 26) tetraoxa-pentadecanoyl fluoride (1.4 mmoles) was added dropwise via a 3 mL syringe with a 25 G needle through the septa with an additional 25 G needle placed in the septa to assure that any pressure generated could be released. After complete addition of the acid fluoride a gas chromatographic analysis was run. The differences observed in the reaction mixtures resulting from the use of these different bases are indicated in Table 1.
Base Mass in mequival Ratio*
ents None 16.2 CaH 0.08 1.9 19.7 MgS~54 0.21 1.7 13.3 Mg0 0.07 1.7 14.0 KZHP04 0.31 1.8 68.0 * Ratio of the area of [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl)oxypropyl]heptamethylcyclotetra-siloxane to observed side products excluding those with retention of perfluoro-2,5,8.11-tetramethyl-3,6,9,12-tetraoxapentadecanoic acid or less.
A 3-necked 250 mL round bottom flask equipped with a magnetic stirring bar, a temperature probe, and an addition funnel was charged with 34.6 g of 99~ (3-hydroxypropyl)heptamethylcyclotetra-siloxane (101 mmoles) and 17 . 0 g of K2HP04 ( 97 . 6 mequivalents ) . The mixture was stirred and 87.6 g of hexafluoropropeneoxide oligomer acid fluoride with an average degree of polymerization of 4.4 (119 mmoles) was added dropwise at a rate such that the temperature did not exceed 40°C.
The contents of the pot was placed in a funnel attached to a filter flask with a 1 micron filter in line and collected in the flask when vacuum was applied to the flask. The 100.6 g of liquid in the filter was transferred into a 250 mL round bottom flask and distilled at 51-128°C and 0.05 to 0.25 mmHg to yield a fraction of 68 g (57% yield) of [3-(oligohexafluoropro-peneoxide-oyl)oxypropyl]heptamethylcyclotetrasiloxane (12.2 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is given by formula (II) wherein p is 4.1, or more SUBSTITUTE SHEET (RULE 26) specifically as shown in formula (VII) wherein p averages 4.1, as determined by 19F NMR spectroscopy from the integration ratio's of CF3 signals, and by gas chromatography assuming a relative response of individual homologues proportional to their mass and retention times of homologues determined from monodispersed standards from examples 1 through 3, with a dispersivity index, XW/Xn, of 1.1. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDC13:
d 0.1 (s 21 H), 0.6 (t 2 H), 1.8 (p 2 H), 4.4 (m 2 H); 19F NMR
376 MHz, CDC13: d -81 (CF3), -82 (CF3), -83 (CF3), -85 (CF3), -130 (CF2), -132 (CF2), -145 (CF); IR (neat liquid on NaCl): cm 1. 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 {s), 970 (s), 810 (vs), 750 (m).
A 25 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 4.0 g of (3-hydroxy-propyl)heptamethylcyclotetrasiloxane (12 mmoles) and 1.0 g of pyridine (13 mmoles). The mixture was stirred and 5.0 g of per-fluorooctanoyl chloride (12 mmoles) was added dropwise. After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid chloride and most of the cyciosiloxane were consumed with one product as 96.5%
of the mixture. The contents of the flask were filtered using a 0.45 micron syringe filter into a 50 mL 1-necked round bottom flask. The solids in the flask were washed with 2.5 mL of pentane and this suspension added to the syringe and filtered into the 50 mL flask. The solids in the syringe were washed with an additional 2.5 mL of pentane and filtered into the 50 mL flask.
The contents of the flask were distilled at 82°C and 0.04 mmHg to yield a fraction of [3-(perfluorooctanoyl)oxypropyl]hepta-methylcyclotetrasiloxane which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is a perfluorinated straight chain monovalent alkyl radical of 7 carbons atoms, or more specifically as shown in formula (VIII) below.
SUBSTITUTE SHEET (RULE 26) O
H3C H H H H ') F /F F /r' F\ %
H3C p_c ~C'CrC'p~C~C~C'C~C~C~C~C~F
v ~ W ~ \ / \ / \ / \ / \
H3C-Ss O H H F F F F F F F F
O~ ~Si--t. Hz ~Si--~7 ~CH~
H3C 'CH.
(VIII) A 100 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 4.2 g of allyl alcohol (72 mmoles) and 9.5 g of anhydrous pyridine (120 mmoles ) . The mixture was stirred and 40 g of 97% perfluoro-2, 5, 8-trimethyl-3,6,9-trioxadodecanoyl fluoride (60 mmoles) was added dropwise. After complete addition of the acid fluoride, two phases were present. The stirring was stopped and the contents poured into a separatory funnel. A gas chromatographic analysis of the lower layer displayed no acid fluoride and very little allyl alcohol and the formation of one product in a significant quantity. The bottom ester layer was removed and the top layer discarded. The bottom ester layer was again placed in the separatory funnel and washed with a 20 mL portion of dilute hydrochloric acid. The ester was removed and subsequently washed with another 20 mL portion of dilute hydrochloric acid and then twice with 20 mL portions of water. The ester was transferred into a round bottom flask and distilled at 62-64°C and 3 mmHg to yield a traction of 29.0 g (69% yield) of >99% [3-perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecan-oyl)oxy]-1-propene (41 mmoles).
A 3-necked 25 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 10.0 g of >99% [3-(perfluoro-2,5,8-tri-methyl-3,6,9-trioxadecan-oyl)oxy]-1-propene and 4.0 g of hepta-methylcyclotetrasiloxane (14 mmoles). The mixture was heated to 80°C and 10 ~L of a Pt 1,3-divinyltetramethyldisiloxane complex in xylene (3% Pt) was added via a syringe. The temperature was SU8ST1TUTE SHEET (RULE 26) increased. When the temperature exceeded 90°C an exothermic reaction occurred with a rapid increase in temperature to 105°C
which soon cooled to below 100°C. After a gas chromatographic analysis indicated a low conversion, the temperature was increased to 100°C and an additional 5 pL of the platinum catalyst solution was added to the mixture resulting in another exothermic reaction. The heating was then stopped and an additional gas chromatographic analysis indicated that although all of the reagents were consumed the desired product, [3-(perfluoro-2,5,8-trimethyl-3,6,9-trioxa-dodecan-oyl)oxypropyl]heptamethylcyclotetrasiloxane, constituted only 18%
of the mixture.
A 100 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 9.0 g of allyl amine (160 mmoles). The liquid was stirred and 40 g of 97%
perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluoride (60 mmoles) was added dropwise. Dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer separated from the amide layer. The amide layer was washed again with dilute hydrochloric acid and twice with water. The amide layer was transferred into a round bottom flask and distilled at 101°C and 3 mmHg to yield a fraction of 21.6 (52% yield) of >99% N-allylperfluoro-2,5,8-trimethyl-3,6,9-trioxado-decanamide (31 mmoles).
A 3-necked 25 mL flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 10.0 g of >99% N-allyl-perfluoro-2,5,8-trimethyl-3,6,9-tri-oxadodecanamide (14 mmoles) and 4.0 g of heptamethylcyclotetra-siloxane (14 mmoles). The mixture was heated to 100°C and 10 uL
of a Pt 1,3-divinyltetramethyldisiloxane complex in xylene (3%
Pt) was added via a syringe. An exothermic reaction occurred with a rapid increase in temperature to 147°C which cooled after 10 minutes. A gas chromatographic analysis indicated high conversion to a single product. The contents of the flask were distilled at 116-20°C and 0.04 mmHg to yield a fraction of 5.7 g (43% yield) of >99% N-(3-heptamethylcyclotetrasiloxan-yl)propylperfluoro-SUBSTITUTE SHEET (RULE 26) 2,5,8-trimethyl-3,6,9-trioxadodecanamide (6 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is NHC(O), and RF is given by formula (II) wherein p is 3, or more specifically as shown in formula (IX) below where R = H and p =
3. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDC13: d 0.1 (m 21 H), 0.6 (t 2 H), 1.7 (p 2 H), 3.4 (m 2 H), 6.7 (s 1 H); IR (neat liquid on NaCl): cm 1. 3460 (m), 2970 (m), 1705 (s), 1550 (m), 1310 (m), 1245 (vs), 1200 (s), 1150 (s), 1070 {vs), 995 (s), 970 (s), 810 (vs), 750 (m).
H3C~ ~O-Si"; C ~C; C~N~ ~C~ ~~ ~F
H3C-S i O H H R F;C F F F
O~ ~S ~H3 Si--~ CH3 (IX) A 100 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 5.0 g of N-methylallyl amine (70 mmoles). The liquid was stirred and 17.5 g of 97% per-fluoro-2,5,8- trimethyl-3,6,9-trioxadodecanoyl fluoride (26 mmoles) was added dropwise. The reaction mixture was transferred into a separatory funnel and the amide layer was washed twice with dilute hydrochloric acid and once with water.
The amide layer was traps-ferred into a round bottom flask and distilled at 98°C and 2 . 4 mmHg to yield a fraction of 14 . 3 g ( 77%
yield) of >99% N-allyl-N-methyl-perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanamide {20 mmoles).
A 3-necked 25 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 7.0 g of >99% N-allyl-N-methylperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanamide (10 mmoles) and 2.8 g of heptamethylcyclotetrasiloxane (10 mmoles). The mixture was heated to 106°C and 10 pL of a Pt 1,3-divinyltetramethyl-disiloxane complex in xylene (3% Pt) was added via a syringe. An exothermic reaction occurred with a rapid increase in temperature SUBSTITUTE SHEET (RULE 26) WO 99/62916 PCTlUS99/04341 to 155°C which cooled after 3 minutes. A gas chromatographic analysis indicated high conversion to a single product. The contents of the flask were distilled at 100-05°C and 0.04 mmHg to yield a fraction of 5.2 g (53% yield) of >99% N-(3-heptamethylcyclotetrasiloxan-yl)propyl-N-methylperfluoro-2,5,8-trimethyl-3,6,9trioxadodecanamide (5.2 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is N(CH3)C(O), and RF is given by formula (II) wherein p is 3, or more specifically as shown in formula (IX) where R = CH3 and p = 3. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDC13: d 0.1 (m 21 H), 0.5 (m 2 H), 1.7 (m 2 H), 3.1 (m 3 H), 3.5 (m 2 H); IR (neat liquid on NaCl): cm 1. 2970 (m), 1685 (s), 1410 (w), 1300 (m), 1245 (vs), 1200 (s), 1140 (m), 1080 (vs), 995 (s), 970 (s), 810 (vs), 750 (m).
A 500 mL round bottom flask equipped with a magnetic stirring bar, a temperature probe, a condenser, and an addition funnel was charged with 11.0 g of allyl amine (193 mmoles) and 15 g of pyridine (190 mmoles). The liquid was stirred and 150 g of hexa-fluoropropeneoxide oligomer acid fluoride, with a degree of polymerization of 4.4 (205 mmoles) was added dropwise. The contents of the flask were transferred to a separatory funnel and washed twice with dilute hydrochloric acid and subsequently washed twice with water. The amide layer was transferred into a round bottom flask. The product was distilled at 95-190°C and 5.1 mmHg to yield a fraction of 125 g (84% yield) of N-allyl-oligohexafluoropropene-oxide-oyi amide.
A 3-necked 250 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 5.0 g of N-ailyl-oligohexafluoropropene-oxide-oyl amide (6.5 mmoles) and 30 g of heptamethylcyclotetra-siloxane (106 mmoles). The mixture was heated to i00°C and 30 uL
of a Pt 1,3-divinyltetramethyldisiloxane complex (3% Pt) was added via a syringe. An additional 70 g of N-allyl-oligohexafluoropropene-oxide-oyl amide (91 mmoles) was added dropwise. After addition of the allyl amide was complete, 5 uL
additional Pt 1,3-divinyltetra-methyldisiloxane complex in xylene SUBSTITUTE SHEET (RULE 26) (3% Pt) was injected into the flask. The resulting liquid was transferred into a distillation flask and 78 g (69% yield) of 91%
N-(3-heptamethylcyclotetra-siloxan-yl)propyloligohexafluoro-propeneoxide-oyl amide (91 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is NHC(O), and RF is given by formula (II) wherein p is 3.2, or more specifically as shown in formula ( IX) where R = H and p is an average of 3.2 as determined by gas chromatography, assuming a relative response of individual homologues proportional to their mass and retention times of homologues determined from a mono-dispersed standard from example 8, with a dispersivity index, XW/Xn, of 1. 1. The ma jor impurities in the product were unreacted N-allyloligohexafluoropropeneoxide-oyl amides.
In a 1.5 dram vial containing 1.0 g of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]-heptamethylcyclotetrasiloxane (0.87 mmoles) was injected 2.0 pL
of trifluoromethanesulfonic acid (0.023 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that flowed slowly when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 4 hours. Little or no change in the oil was apparent. To the vial was added 0.01 g of Mg0 (0.2 mequivalents) and the oil warmed with the heating gun to disperse the salt. After the mixture cooled, 1 mL of pentane was added to the vial and the mixture was shaken. Upon settling, two liquid phases and a solid phase were apparent. The liquid layers were filtered from the solid using a 3 mL syringe equipped with a 0.45 micron filter into a 3 dram vial. The 1.5 dram vial and syringe were rinsed with pentane and the liquid injected through the filter into the 3 dram vial such that an approximately 20% by volume perfluoroethersiloxane mixture in pentane resulted.
The two phases were dispersed by shaking and immediately a 3 NL sample was drawn into a syringe and injected into a gas chromatograph. Signals were observed in the chromatographic trace which had a pattern of four groups of signals. The two groups SUBSTITUTE SHEET (RULE 26) with the shorter retention time each displayed four narrow well resolved signals which decreased in intensity with increasing retention time. The latter two groups displayed many poorly resolved signals. The retention times of the first group were identical to that of octamethylcyclotetrasiloxane, decamethyl-cyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetra-decamethylcycloheptasiloxane. The largest peak of the second group had the retention time of [3-(per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]hepta-methylcyclotetrasiloxane. Since a complete redistri-bution of the siloxane units should result during polymerization, the molar ratio of octamethylcyclotetrasiloxane:decamethylcyclopenta-siloxane should equal K4/K4:K5(0.75)/K4:K6(0.75)Z/K4 for random placement of siloxane units where the dimethylsiloxane units constitute 75% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer.
Assuming a molar response factor for the homologues in the gas chromatographic trace which is proportional to the molecular weight the homologue, the observed molar ratio of octamethyl-cyclotetrasiloxane:decamethylcyclopentasiloxane of 10:4:1 agreed with the theoretical ratio of 10:4:1. The second group consisted of [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapenta-decan-oyl)oxypropyl]heptamethylcyclotetrasiloxane, [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]-nonamethylcyclopentasiloxane, [3-(per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]undeca-methylcyclohexasiloxane, and [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]tridecamethylcyclo-heptasiloxane. The molar ratio of [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]hepta-methylcyclotetrasiloxane:[3-(per-fluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]nonamethylcyclopenta-siloxane:[3-(perfluoro-2,5,8,11-tetra-methyl-3,6,9,12-tetra-oxapentadecan-oyl)oxypropyl]undecamethylcyclohexasiloxane was observed to be 10:5:2 in the gas chromatographic trace which agreed with the theoretical 10:5:2 ratio from K4/K4:1.25K5(0.75)/K4:1.5K6(0.75)2/K4. The match of these ratios SUBSTITUTE SHEET (RULE 25) confirmed that complete and random redistribution occurred and that a high molecular weight copolymer was formed.
The upper layer was drawn from the lower layer using a syringe and placed in a scintillation vial. An additional 3 mL
of pentane was added to the 3 dram vial containing the lower layer and the vial shaken. The top layer was again removed via a syringe and placed in the scintillation vial. Evaporation of the pentane from the solution in the scintillation vial under a stream of nitrogen at room temperature resulted in 0.2 g of an oil which was indistinguishable in a gas chromatographic trace from that of the original dispersion with the exception that the signal from pentane was nearly gone, the signals for octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane were diminished significantly, and the signal for dodecamethylcyciohexasiloxane was slightly reduced relative to the peak for [3-(perfiuoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]heptamethylcyclotetra-siloxane.
A gas chromatographic trace of the lower layer in the 3 dram vial displayed almost no signals from the equilibrium cyclo-siloxanes. The pentane swelling the copolymer was removed by heating the vial on a hot plate while passing a stream of nitrogen over the surface. This resulted in 0.6 g of a gum which displayed no flow upon cooling when the vial was placed on its side for a period of 2 hours, indicating that the molecular weight of the copolymer was high.
Into a 1.5 dram vial containing 1.0 g of >99% N-(3-hepta-methylcyclotetrasiloxan-yl)propyl-N-methylperfluoro-2,5,8-tri-methyl-3,6,9-trioxadodecanamide (0.87 mmoles) was injected 2.0 uL of trifluoromethanesulfonic acid (0.023 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that flowed slowly when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 4 hours. The resulting viscous linear-cyclic mixture was similar in nature to that which resulted from the polymerization of 99%
[3-(perfluoro-2,5,8,i1-tetramethyl-3,6,9,12-tetraoxapentadecan-SUBSTITUTE SHEET (RULE 26) WO 99/b291b PCT/US99/04341 oyl)-oxypropyl]-heptamethylcyclotetrasiloxane in Example 11.
Into a 1.5 dram vial containing 1.0 g of >99% N-(3-hepta-methylcyclotetrasiloxan-yl)propylperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanamide (0.87 mmoles) was injected 2.0 uL of trifluoro-methanesulfonic acid (0.023 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that displayed almost no flow when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 4 hours. A viscous linear-cyclic mixture resulted that was much more viscous than the mixture from the polymerization of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)-oxypropyl]heptamethyl-cyclotetrasiloxane in Example 11.
Into a 1.5 dram vial containing 2.0 g of [3-(oligohexa-fluoropropeneoxide-oyl)oxypropyl]heptamethylcyclotetrasiloxane (1.7 mmoles) from Example 5 was injected 3.0 NL of trifluoromethane-sulfonic acid (0.035 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that flowed slowly when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 4 hours. To the mixture was added 0.021 of Mg0 (0.52 mmoles) and the mixture warmed with a heating gun to aid in mixing of the powder. A
linear-cyclic mixture, similar in nature to that which resulted from the polymerization of 99% (3-(perfluoro-2,5,8,11-tetra-m a t h y 1 - 3 , 6 , 9 , 1 2 - t a t r a o x a p a n t a - d a c a n -oyl)oxypropyl]heptamethylcyclotetrasiloxane in Example 11, was observed by gas chromatographic analysis.
Into a 1.5 dram vial containing 2.0 g of N-(3-heptamethyl-cyclotetrasiloxan-yl)propyloligohexafluoropropeneoxide-oyl amide (1.7 mmoles) from Example 10 was injected 3.0 NL of trifluoro-methanesulfonic acid (0.035 mmoles) and the mixture was shaken.
The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a heavy oil, that SUBSTITUTE SHEET (RULE 26) displayed almost no flow when the vial was inverted at room temperature, resulted. The oil was warmed again and let stand for 24 hours. The mixture became hazy in appearance at room temperature but became clear upon warming. To the mixture was added 0.012 of Mg0 (0.30 mmoles) and the mixture warmed with a heating gun to aid in mixing of the powder. A linear-cyclic mixture, similar in nature to that which resulted from the polymerization of 99$ [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9.12-tetraoxapentadecan-oyl)oxypropyl]heptamethyl-cyclotetrasiloxane in Example 11, was observed by gas chromatographic analysis.
Into a 1.5 dram vial containing 2.0 g of N-(3-heptamethyl-cyclotetrasiloxan-yl}propyloligohexafluoropropeneoxide-oyl amide (1.7 mmoles) from Example 10 was injected 19.0 uL of tetrabutyl-ammonium fluoride in tetrahydrofuran (0.019 mmoles) and the mixture was shaken. The vial was warmed gently with a heating gun over a period of 10 minutes. After cooling to room temperature, a viscous mixture was noted. The heating of the vial was repeated 6 times until a heavy oil, that displayed very slow flow when the vial was inverted at room temperature, resulted and no apparent increase in viscosity was observed upon subsequent heating. The oil was warmed again and let stand for 24 hours. The mixture remained clear in appearance at room temperature. The vial was then heated strongly with the formation of bubbles, presumably from the decomposition of the tetrabutylammonium salt with the liberation of tributylamine and butene. A linear-cyclic mixture, similar. in nature to that which resulted in Example 15 was observed by gas chromatographic analysis.
A 3-necked 50 mL round bottom flask was equipped with a magnetic stirring bar, a condenser, and a temperature probe. The flask was charged with 10.0 g of 1H,1H,2H-perfluoro-1-octene (28.9 mmoles) and 10.0 g of heptamethylcyclotetrasiloxane (35.4 mmoles ) . The mixture was heated to 90°C and 5 NL of a Pt 1, 3-divinyltetra-methyldisiloxane complex in xylene (3% Pt) was added via a syringe. An exothermic reaction occurred with a rapid SUBSTITUTE SHEET (RULE 26) increase in temperature to 130°C which cooled after 3 minutes.
A gas chromato-graphic analysis indicated a low conversion to a single product. The addition of 20 uL of the 1,3-divinyltetramethyldisiloxane complex (3% Pt) did not result in higher conversion. The contents of the flask were distilled at 80°C and <2 mmHg to yield a fraction of 4.2 g (23% yield) of (6.7 mmoles), which corresponds to formula (I) wherein m is 1, n is 1, X is CH2 and RF is a perfluorinated straight chain monovalent alkyl radical of 6 carbon atoms, or more specifically as shown in formula (X) below where q = 5. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDC13:
d 0.1 (m 21 H), 0.8 (m 2 H), 2.1 (m 2 H); IR (neat liquid on NaCl): cm 1. 2970 (m), 2870 (w), 1445 (w), 1405 (w), 1370 (w), 1265 {s), 1240 (s), 1205 (m), 1175 (w), 1150 (m), 990 (vs), 810 (vs).
Fv ~F
H3C' .O
H3C-Si O H H F F
~S ~H3 ~Si--~~ CFi=
HOC CHI ( x ) Into a 1.5 dram vial containing 2.0 g of 99% 1H,1H,2H,2H,1-(heptamethylcyclotetrasiloxan-yl)perfluorooctane (3.2 mmoles) from Example 17 was injected 3.0 uL of trifluoromethanesulfonic acid (0.035 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a gum, which displayed almost no flow when the vial was inverted at room temperature, resulted.
The gum was warmed again and let stand for 24 hours. To the vial was added 0.021 g of Mg0 (0.52 mmoles) and the mixture warmed with a heating gun to aid in the dispersion of the powder. A
linear-cyclic mixture, similar in nature to that which resulted from the polymerization of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)-oxypropyl]heptamethylcyclotetrasiloxane in Example 11, was observed by gas chromatographic analysis.
SU8ST1TUTE SHEET (RULE 26) Into a 1.5 dram vial containing 0.20 g of 99% [3-(perfluoro-2,5,8,11-tetramethyl-3,6,9,12-tetraoxapentadecan-oyl)oxypropyl]-heptamethylcyclotetrasiloxane (0.18 mmoles) from Example 2 and 9.5 g of octamethylcyclotetrasiloxane (32.0 mmoles) was injected 15 uL of trifluoromethanesulfonic acid (0.17 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes such that a gum, which dis-played almost no flow when the vial was inverted at room~temp-erature, resulted. The gum was warmed again and let stand for 24 hours. To the vial was added 0.1 g of Mg0 (2.5 mmoles) and the mixture warmed with a heating gun to aid in dispersion of the powder. A linear-cyclic mixture resulted which was observed by gas chromatographic analysis. Since a complete redistribution of the siioxane units should result during polymerization, the molar ratio of octamethylcyclotetra-siloxane:decamethylcyclopentasiloxane:dodecamethylcyclohexa-siloxane should equal K4/K4:K5(0.997)/K4:-K6(0.997)2/K4 for random placement of siloxane units where the dimethylsiloxane units constitute 99.7% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer.
Assuming a molar response factor for the homologues in the gas chromatographic trace which is proportional to the molecular weight of the homologue, the observed molar ratio of octamethyl-cyclotetrasiloxane:decamethylcyclopentasiloxane:dodecamethyl-cyclohexasiloxane of 10:5.1:1.3 agreed well with the theoretical ratio of 10:5.2:1.8. The mole ratio of octamethylcyclotetrasilox-ane:[3-(perfluoro-2,6,8,11-tetramethyl-3,6,9,12-tetraoxapenta-decan-oyl)oxypropyl]heptamethylcyclotetrasiloxane was determined to be 100:2 which agreed well with the theoretical ratio of 100:1.2 from the relationship K4(0.997)4:4K4(0.997)3{0.003) for a random polymerization to high molecular weight.
Into a 1.5 dram vial containing 0.20 g of 99% [3-(perfluoro-2,5,8,11,14-pentamethyl-3,6,9,12,15-pentaoxapentadecan-oyl)oxy-propylJheptamethylcyclotetrasiloxane (0.17 mmoles), 1.90 g of octamethylcyclotetrasiloxane (6.4 mmoles) and 0.020 g of 1,3,5,7-SUBSTITUTE SHEET (RULE 26) WO 99/62916 PCf/US99/04341 tetravinyltetramethylcyclotetrasiloxane (0.006 mmoles) was injected 3 NL of trifluoromethanesulfonic acid (0.03 mmoles) and the mixture was shaken. The vial was warmed gently with a heating gun and the viscosity increased over a period of 30 minutes. The mixture was warmed again and let stand for 24 hours. To the vial was added 0.02 g of Mg0 (0.4 mmoles) and the mixture warmed with a heating gun to aid in dispersion of the powder. A linear-cyclic mixture resulted which was dissolved in 6 mL of cyclohexane and analyzed by gas chromatography. Since a compete redistribution of the siloxane units should result during polymerization, the molar ratio of octamethylcyclotetrasiloxane:decamethylcyclo-pentasiloxane:dodecamethylcyclohexasiloxane should equal K4/K4:K5(0.993)/K4:K6(0.993)2/-K4for random placement of siloxane units where the dimethyl-siloxane units constitute 99.3% of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer. Assuming a molar response factor for the homologues in the gas chromatographic trace which is proportional to the molecular weight of the homologue, the observed molar ratio of octamethylcyclotetrasiloxane:decamethyl-cyclopentasiloxane:dodecamethylcyclohexasiloxane of 10:5.5:1.7 agreed well with the theoretical ratio of 10:5.2: 1.8. Small peaks were observed in gas chromatographic trace which had retention times for that of vinylheptamethylcyclotetrasiloxane and vinylnonamethylcyclopenta-siloxane indicating that the methylvinylsiloxane units from the 1,3,5,7-tetravinyltetramethyl-cyclotetrasiloxane were randomly dispersed through the copolymer and cyclic oligomers.
Into a 1.5 dram vial containing 0. 15 g of 94% [ 3-(perfluoro-2,5-dimethyl-3,6-dioxanonan-oyl)oxypropyl]heptamethylcyclotetra-siloxane (0.17 mmoles), 2.15 g of octamethylcyclotetrasiloxane (7.2 mmoles) and 0.033 g of 1,3-divinyl-1,1,3,3-tetramethyldi-siloxane (0.15 mmoles) was injected 3 pL of trifluoromethane-sulfonic acid (0.03 mmoles) and the mixture was shaken. The vial was warmed with a heating gun and the viscosity increased over a period of 10 minutes. To the vial was added 0.05 g of Mg0 (1 mmole). A copolymer-cyclic mixture was dissolved in 3 mL of SUBSTITUTE SHEET (RULE 26) WO 99/62916 PC'T/US99/0434I
cyclohexane and analyzed by gas chromatography. Since a complete redistribution of the siloxane units should result during polymerization, the molar ratio of octamethylcyclotetrasilox-ane:decamethylcyclopentasiloxane:dodecamethylcyclohexasiloxane should equal K4/K4:K5(0.994)/K4:K6(0.994)2/K4for random placement of siloxane units where the dimethylsiloxane units constitute 99.4 of all siloxane units in the copolymer and polymerization has resulted in a high molecular weight copolymer as a macromolecule with a degree of polymerization of approximately 200 was targeted by the proportions of cyclosiloxanes to disiloxanes used. Assuming a molar response factor for the homologues in the gas chromatographic trace which is proportional to the molecular weight of the homologue, the observed molar ratio of octamethylcyclotetrasiloxane:decamethylcyclopenta-siloxane:dodecamethylcyclohexasiloxane of 10:6.4:2.1 agreed with the theoretical ratio of 10:5.2:1.8. No unreacted 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was observed in the gas chromatographic trace.
The present invention may be embodied in other specific forms without departing from~the spirit of essential attributes thereof, and accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.
The above-referenced patents and publications are hereby incorporated by reference.
SUBSTITUTE SHEET (RULE 26)
Claims (40)
1. A polymerizable cyclosiloxane having one substituent comprising a perfluorinated organic moiety, said cyclosiloxane having the general formula (I) wherein m is an integer of 1 to 12; n is an integer of 1 to 4;
X is a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O), and CH2; and R F comprises a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or R F is a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10.
X is a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O), and CH2; and R F comprises a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or R F is a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10.
2. A polymerizable cyclosiloxane as defined in Claim 1 wherein m is 1 or 2.
3. A polymerizable cyclosiloxane as defined in Claim 2 wherein n is 3 and X is OC(O).
4. A polymerizable cyclosiloxane as defined in Claim 3 wherein R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5.
5. A polymerizable cyclosiloxane as defined in Claim 3 wherein R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms.
6. A polymerizable cyclosiloxane as defined in Claim 2 wherein n is 3 and X is NHC(O).
7. A polymerizable cyclosiloxane as defined in Claim 6 wherein R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5.
8. A polymerizable cyclosiloxane as defined in Claim 6 wherein R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms.
9. A polymerizable cyclosiloxane as defined in Claim 2 wherein n is 3 and X is N(CH3)C(O).
10. A polymerizable cyclosiloxane as defined in Claim 9 wherein R F is a perrfluorinated ether radical of the general formula (II) wherein p is 1 to 5.
11. A polymerizable cyclosiloxane as defined in Claim 9 wherein R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms.
12. A polymerizable cyclosiloxane as defined in Claim 2 wherein n is 1 and X is CH2.
13. A polymerizable cyclosiloxane as defined in Claim 12 wherein R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms.
14. A polymerizable cyclosiloxane as defined in Claim 12 wherein R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5.
15. A copolymer of the general formula:
wherein each m is independently an integer of 1 to 12, each n is independently an integer of 1 to 4, each X is independently a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O), or CH2; each R F is independently either a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms or a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10; and q is from 2 to about 1,000,000.
wherein each m is independently an integer of 1 to 12, each n is independently an integer of 1 to 4, each X is independently a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O), or CH2; each R F is independently either a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms or a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10; and q is from 2 to about 1,000,000.
16. A copolymer as defined in Claim 15 prepared by the ring-opening polymerization of polymerizable cyclosiloxanes having one substituent comprising a perfluorinated organic moiety, said cyclosiloxanes having the general formula (I) wherein m is an integer of 1 to 12; n is an integer of 1 to 4;
X is a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O), and CH2; and R F comprises a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or R F is a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10.
X is a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O), and CH2; and R F comprises a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or R F is a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10.
17. A copolymer prepared by the ring-opening polymerization of polymerizable cyclosiloxanes as defined in Claim 16 wherein n is 3, X is OC(O), and R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5.
18. A copolymer prepared by the ring-opening polymerization of polymerizable cyclosiloxanes as defined in Claim 16 wherein n is 3, X is OC(O), and R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms.
19. A copolymer prepared by the ring-opening polymerization of polymerizable cyclosiloxanes as defined in Claim 16 wherein n is 3, X is NHC(O) and R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5.
20. A copolymer prepared by the ring-opening polymerization of polymerizable cyclosiloxanes as defined in Claim 16 wherein n is 3, X is NHC(O) and R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms.
21. A copolymer prepared by the ring-opening polymerization of polymerizable cyclosiloxanes as defined in Claim 16 wherein n is 3, X is N(CH3)C(O) and R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5.
22. A copolymer prepared by the ring-opening polymerization of polymerizable cyclosiloxanes as defined in Claim 16 wherein n is 3, X is N(CH3)C(O) and R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms.
23. A copolymer prepared by the ring-opening polymerization of polymerizable cyclosiloxanes as defined in Claim 16 wherein n is 1, X is CH2 and R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms.
24. A copolymer prepared by the ring-opening polymerization of polymerizable cyclosiloxanes as defined in Claim 16 wherein n is 1, X is CH2 and R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5.
25. A copolymer prepared by the copolymerization of (a) polymerizable cyclosiloxanes having one substituent comprising a perfluorinated organic moiety, said cyclosiloxane having the general formula (I) wherein m is an integer of 1 to 12; n is an integer of 1 to 4;
X is a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O), and CH2; and R F comprises a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or R F is a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10; and (b) a copolymerization substituent selected from the group consisting of cyclodimethylsiloxanes, polydimethylsiloxanes and mixtures thereof; whereby said copolymer contains a lesser proportion of fluorinated siloxane groups than the cyclosiloxanes of formula (I).
X is a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O), and CH2; and R F comprises a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms; or R F is a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10; and (b) a copolymerization substituent selected from the group consisting of cyclodimethylsiloxanes, polydimethylsiloxanes and mixtures thereof; whereby said copolymer contains a lesser proportion of fluorinated siloxane groups than the cyclosiloxanes of formula (I).
26. A copolymer as defined in Claim 25 prepared by the ring-opening polymerization of (a) said polymerizable cyclosiloxanes wherein n is 3, X is OC(O) and R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5; and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
27. A copolymer as defined in Claim 25 prepared by the ring-opening polymerization of (a) said polymerizable cyclosiloxanes wherein n is 3, X is OC(O) and R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms; and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
28. A copolymer as defined in Claim 25 prepared by the ring-opening polymerization of (a) said polymerizable cyclosiloxanes wherein n is 3, X is NHC(O), and R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5; and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
29. A copolymer as defined in Claim 25 prepared by the ring-opening polymerization of (a) said polymerizable cyclosiloxanes wherein n is 3, X is NHC(O) and R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms; and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
30. A copolymer as defined in Claim 25 prepared by the ring-opening polymerization of (a) said polymerizable cyclosiloxanes wherein n is 3, X is N(CH3)C(O) and R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5; and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
31. A copolymer as defined in Claim 25 prepared by the ring-opening polymerization of (a) said polymerizable cyclosiloxanes wherein n is 3, X is N(CH3)C(O) and R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms; and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
32. A copolymer as defined in Claim 25 prepared by the ring-opening polymerization of (a) said polymerizable cyclosiloxanes wherein n is 1, X is CH2 and R F is a perfluorinated straight chain alkyl radical of 2 to 10 carbon atoms; and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
33. A copolymer as defined in Claim 25 prepared by the ring-opening polymerization of (a) said polymerizable cyclosiloxanes wherein n is 1, X is CH2 and R F is a perfluorinated ether radical of the general formula (II) wherein p is 1 to 5; and (b) octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
34. A copolymer as defined in Claim 15 wherein said copolymer further comprises other siloxy repeating units which are selected from the group consisting of methylhydrogensiloxy, methylvinyl-siloxy, methylphenylsiloxy, methylcyanoethylsiloxy, hydroxypropyl-siloxy, aminopropylmethylsiloxy, trifluoropropylmethylsiloxy, mixtures of any of the foregoing and the like.
35. A copolymer as defined in Claim 25 wherein said copolymer further comprises other siloxy repeating units which are selected from the group consisting of methylhydrogensiloxy, methylvinyl-siloxy, methylphenylsiloxy, methylcyanoethylsiloxy, hydroxypropyl-siloxy, aminopropylmethylsiloxy, trifluoropropylmethylsiloxy, mixtures of any of the foregoing and the like.
36. A copolymer as defined in Claim 16 wherein said polymerization is controlled by capping said copolymer at both ends by equilibrating said cyclosiloxane with an endcapping agent selected from the group of a disiloxane, a disiloxane equivalent incorporated into a small polysiloxane and mixtures thereof.
37. A copolymer as defined in Claim 25 wherein said polymerization is controlled by capping said copolymer at both ends by equilibrating said cyclosiloxane with an endcapping agent selected from the group of a disiloxane, a disiloxane equivalent incorporated into a small polysiloxane and mixtures thereof.
38. A copolymer as defined in Claim 34 wherein said polymerization is controlled by capping said copolymer at both ends by equilibrating said cyclosiloxane with an endcapping agent selected from the group of a disiloxane, a disiloxane equivalent incorporated into a small polysiloxane and mixtures thereof.
39. A copolymer as defined in Claim 35 wherein said polymerization is controlled by capping said copolymer at both ends by equilibrating said cyclosiloxane with an endcapping agent selected from the group of a disiloxane, a disiloxane equivalent incorporated into a small polysiloxane and mixtures thereof.
40. A cyclosiloxane of the formula (V):
wherein n is an integer of 1 to 4, X is a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O)CH2; and R F is a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms, or R F is a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10; r is 1 to t; s is t minus r;
and t is 4 to 20.
wherein n is an integer of 1 to 4, X is a divalent radical selected from the group consisting of O, NH, N(CH3), OC(O), NHC(O), N(CH3)C(O)CH2; and R F is a perfluorinated straight chain or branched chain monovalent alkyl radical of 1 to 25 carbon atoms, or R F is a perfluorinated ether radical of the general formula (II):
wherein p is an integer of 1 to 10; r is 1 to t; s is t minus r;
and t is 4 to 20.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/086,649 | 1998-05-29 | ||
US09/087,185 US5892086A (en) | 1998-05-29 | 1998-05-29 | Perfluorinated ether organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes |
US09/087,185 | 1998-05-29 | ||
US09/086,649 US5914420A (en) | 1998-05-29 | 1998-05-29 | Perfluorinated organo substituted cyylosiloxanes and copolymers prepared from these cyclosiloxahes |
PCT/US1999/004341 WO1999062916A1 (en) | 1998-05-29 | 1999-02-26 | Perfluorinated organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2342153A1 true CA2342153A1 (en) | 1999-12-09 |
Family
ID=26774992
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002342153A Abandoned CA2342153A1 (en) | 1998-05-29 | 1999-02-26 | Perfluorinated organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1082327A4 (en) |
KR (1) | KR20010071337A (en) |
AU (1) | AU2795599A (en) |
CA (1) | CA2342153A1 (en) |
WO (1) | WO1999062916A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110156826B (en) * | 2019-06-20 | 2021-08-31 | 威海新元化工有限公司 | Diphenyl cyclotrisiloxane and preparation method and application thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3876677A (en) * | 1974-06-06 | 1975-04-08 | Gen Electric | Cyclotri-siloxanes containing silicon-bonded fluoroalkoxyalkyl groups |
JPS6471887A (en) * | 1987-09-11 | 1989-03-16 | Shinetsu Chemical Co | Organosilicon compound |
JPH0662647B2 (en) * | 1988-02-12 | 1994-08-17 | 信越化学工業株式会社 | Fluorine-containing organosilicon compound |
US5202453A (en) * | 1989-08-21 | 1993-04-13 | Shin-Etsu Chemical Co., Ltd. | Fluorinated cyclic organic silicon compounds and method for making |
US5548054A (en) * | 1992-03-10 | 1996-08-20 | Kao Corporation | Fluorine-modified silicone derivative, production thereof and cosmetic containing the same |
JPH06300243A (en) * | 1993-04-12 | 1994-10-28 | Mitsubishi Heavy Ind Ltd | Waste tire incineration ash treatment device |
US5412135A (en) * | 1993-04-21 | 1995-05-02 | Shin-Etsu Chemical Co., Ltd. | Organic silicon compounds and curable organopolysiloxane compositions |
US5464917A (en) * | 1993-07-30 | 1995-11-07 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane |
JP3508047B2 (en) * | 1996-11-05 | 2004-03-22 | 株式会社コーセー | Makeup cosmetics |
-
1999
- 1999-02-26 EP EP99908551A patent/EP1082327A4/en not_active Withdrawn
- 1999-02-26 WO PCT/US1999/004341 patent/WO1999062916A1/en not_active Application Discontinuation
- 1999-02-26 KR KR1020007013359A patent/KR20010071337A/en not_active Application Discontinuation
- 1999-02-26 AU AU27955/99A patent/AU2795599A/en not_active Abandoned
- 1999-02-26 CA CA002342153A patent/CA2342153A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP1082327A4 (en) | 2003-04-16 |
KR20010071337A (en) | 2001-07-28 |
AU2795599A (en) | 1999-12-20 |
EP1082327A1 (en) | 2001-03-14 |
WO1999062916A1 (en) | 1999-12-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1075526C (en) | Organosilicone having a carboxyl functional group thereon | |
US5118775A (en) | Fluoroorganopolysiloxane and a process for preparing the same | |
US5298589A (en) | Highly functionalized polycyclosiloxanes and their polymerization into thermally reversible living rubbers | |
US4222952A (en) | Siloxane bond rearrangement effected by solid perfluorinated polymers containing pendant sulfonic acid groups | |
JP5196789B2 (en) | Process for producing POS by ring-opening polymerization and / or redistribution of polyorganosiloxane (POS) in the presence of carbene and POS compound produced by the process | |
US4918210A (en) | Zwitterionic polysiloxane compositions | |
US5914420A (en) | Perfluorinated organo substituted cyylosiloxanes and copolymers prepared from these cyclosiloxahes | |
US5317072A (en) | Condensation process for preparation of organofunctional siloxanes | |
Ścibiorek et al. | Controlled synthesis of amphiphilic siloxane-siloxane block copolymers with carboxyl functions | |
JP4156689B2 (en) | Alkyl substituted siloxane and alkyl substituted polyether fluids | |
EP0797612A1 (en) | Method for preparing essentially cyclene-free polyorganosiloxanes and organofunctional siloxanes | |
US5892086A (en) | Perfluorinated ether organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes | |
JP2716851B2 (en) | Method for producing novel organopolysiloxane | |
US5116928A (en) | Process for preparing a fluoroorganopolysiloxane | |
EP0611785B1 (en) | Process for producing linear organopolysiloxanes | |
CA2342153A1 (en) | Perfluorinated organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes | |
US6093841A (en) | Method for preparing nonreactive aminosilicone oils | |
Cai et al. | Synthesis and chemical modification of poly (divinylsiloxane) | |
JPH107799A (en) | Production of polyorganosiloxane by interfacial polymerization | |
JP2666371B2 (en) | Method for producing fluorosilicone oil | |
US5585451A (en) | Silicone condensation and/or equilibration catalyst and use | |
US5254654A (en) | Monodispersed polydimethylsiloxane-α,ω-diol fluids and α,ω-substituted polydimethylsiloxanes and polydimethylcyclosiloxanes prepared therefrom | |
EP0978526B1 (en) | Process for the preparation of fluorosilicone compounds having hydrolyzable groups | |
JP2002517402A (en) | Perfluorinated organo-substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes | |
RU2087491C1 (en) | Method of synthesis of oligo(chlorovinyl)silsesquioxanes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Dead |