MXPA96002965A - Polifunctional perhalogenic polygenagroxilians and their obtenc procedures - Google Patents
Polifunctional perhalogenic polygenagroxilians and their obtenc proceduresInfo
- Publication number
- MXPA96002965A MXPA96002965A MXPA/A/1996/002965A MX9602965A MXPA96002965A MX PA96002965 A MXPA96002965 A MX PA96002965A MX 9602965 A MX9602965 A MX 9602965A MX PA96002965 A MXPA96002965 A MX PA96002965A
- Authority
- MX
- Mexico
- Prior art keywords
- equal
- less
- pos
- clause
- branched
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 12
- 230000002209 hydrophobic Effects 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 3
- 230000003373 anti-fouling Effects 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 70
- 150000003254 radicals Chemical class 0.000 claims description 66
- 239000003054 catalyst Substances 0.000 claims description 47
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Chemical class N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 125000003545 alkoxy group Chemical group 0.000 claims description 32
- 229910052697 platinum Inorganic materials 0.000 claims description 32
- -1 hydrocarbon radical Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 241000894007 species Species 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 102000014961 Protein Precursors Human genes 0.000 claims description 12
- 108010078762 Protein Precursors Proteins 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000000969 carrier Substances 0.000 claims description 9
- 230000001588 bifunctional Effects 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 210000003414 Extremities Anatomy 0.000 claims description 7
- 230000000875 corresponding Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004430 oxygen atoms Chemical group O* 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 206010001488 Aggression Diseases 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 230000016571 aggressive behavior Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- 101700041438 SWI2 Proteins 0.000 claims 1
- 230000001464 adherent Effects 0.000 claims 1
- 229910000099 calcium monohydride Inorganic materials 0.000 claims 1
- QHWAQXOSHHKCFK-UHFFFAOYSA-N hexylcyclohexane Chemical compound CCCCCCC1CCCCC1 QHWAQXOSHHKCFK-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 claims 1
- 230000000181 anti-adherence Effects 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 230000001131 transforming Effects 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- 230000002194 synthesizing Effects 0.000 description 27
- 229920002545 silicone oil Polymers 0.000 description 24
- 229920001296 polysiloxane Polymers 0.000 description 22
- 229920002795 polyhydroxyoctanoate Polymers 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 11
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 7
- RINCXYDBBGOEEQ-UHFFFAOYSA-N Succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- 230000006399 behavior Effects 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000008079 hexane Substances 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N Hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N Perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IMVVEWPCRIJQCA-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-icosafluorodec-1-ene Chemical group FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F IMVVEWPCRIJQCA-UHFFFAOYSA-N 0.000 description 3
- 210000004417 Patella Anatomy 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N Tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 230000002035 prolonged Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 210000001503 Joints Anatomy 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive Effects 0.000 description 2
- 239000003911 antiadherent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic Effects 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052803 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229940094933 n-dodecane Drugs 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial Effects 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011528 polyamide (building material) Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-Trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichloro-1,2,2-trifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- FCBZNZYQLJTCKR-UHFFFAOYSA-N 1-prop-2-enoxyethanol Chemical compound CC(O)OCC=C FCBZNZYQLJTCKR-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- CYEKUDPFXBLGHH-UHFFFAOYSA-N 3-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1 CYEKUDPFXBLGHH-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N Benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- BPMGYFSWCJZSBA-UHFFFAOYSA-N C[SiH](C)O[SiH3] Chemical class C[SiH](C)O[SiH3] BPMGYFSWCJZSBA-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N Decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 210000002414 Leg Anatomy 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N Methyl radical Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 240000005428 Pistacia lentiscus Species 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L Platinum(II) chloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OHNGJKYLXUCBBU-UHFFFAOYSA-N bis(ethenyl)-ethyl-triethylsilyloxysilane Chemical compound CC[Si](CC)(CC)O[Si](CC)(C=C)C=C OHNGJKYLXUCBBU-UHFFFAOYSA-N 0.000 description 1
- 125000005340 bisphosphate group Chemical group 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 230000003301 hydrolyzing Effects 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000003367 polycyclic group Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reduced Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000035897 transcription Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
The present invention relates to polyfunctional, chemically stable perfluorinated polyorganosiloxanes (POS) comprising, on the one hand, fluorinated side grafts resulting from the hydrosilylation of perfluorinated olefins by SiH and having alkyl and / or alkyl ester clamps, and On the other hand, other non-perfluorinated functional E-motifs that can give them diverse and varied physical and chemical properties, which offers them commercial outlets for many applications. For example, those POS are those of the following formula: according to another of its aspects, the invention has as its object a procedure for preparing those polyfunctional perfluorinated POS. It is applied in the following cases: anti-f to lower the surface tension, anti-fouling, anti-adhesion, lubricant, oleophobic and / or hydrophobic, coatings;
Description
POLIFUNCTIONAL PERHALOGENIC POLYGENAGROXILIANS AND THEIR PROCEDURES FOR OBTAINING
DESCRIPTION The field of the invention is that of the (per) halogenated polyorganosiloxanes (POS) that come from a hydrosilylation reaction of (per) halogenated olefins (ie alpha-olefins), a reaction which can also be presented as the addition of a hydrogenated silicon compound on a halogenated reagent having one or more ethylenic (s) or alcinyl (s) unsaturation (s). Without this being limiting, the most particular objective halogen of the invention is fluorine. The present invention also relates to
cyclic or non-halogenated poly (poly) organosiloxanes, preferably fluorinated, having at least one silicon atom substituted by at least one halogenated radical Rf (ie fluorinated). The present invention also relates to a process for preparing such type of compounds. The role of halogens and in particular fluorine and the carbon / fluorine bond, in the contribution of specific properties to organic polymer systems, is a well-known notion in the chemistry of polymers. Above all, it is known that fluorination and more precisely the introduction of perfluorinated motifs in polymers, leads to: a modification of the surface energies in the sense of the decrease; an improvement of thermal and chemical stability; - likewise, organophobic and oleophobic properties. Since the 1970s, this type of functionalization by halogenation, and in particular by means of perfluorination, is applied to silicone polymers, in particular of the cyclic polyorganosiloxane type or not. In this way, silicones grafted with fluorinated motifs are available, which find applications in the textile field as an anti-stain or anti-dirt agent or which can be used as lubricants, as specific anti-adherent agents in relation to certain adhesives (silicones of strong adhesive power), as anti-fat agents, or then also anti-foam. The silicone fluids can also be formulated with different thickeners, to form mastics or any other sealing and / or joining material (put together).
Under reticulated form, these silicones can be put into the form of various technical parts by molding or extrusion. For more details on these silicones, one can refer to the article by OGDEN R. PIERCE entitled "Fluorosilicons" - 1970 - John Wíley & Sons inc, pages 1 to 15. A first strategy of known industrial synthesis of silicones of perfluorinated motifs, consists essentially of "hydrolyzing" a dihalogenhydrogen-organosiloxane, such as MeHSiCl2 (Me = methyl), with an unsaturated compound carrying a motif perfluorinated and of the general formula: CH2-TCH-Rf (Rf = perfluorinated motif). The addition of the silane on this olefin leads to a perfluorinated dihalogen-organosiloxane, which can be hydrolyzed to produce a functionalized silicone, which for example can be a cyclic tetramer. It is possible to subject the latter to a redistribution to obtain a perfluorinated linear polyorganosiloxane (POS). The hydrosilylation reactions which are involved in this type of synthesis and which carry out various combinations of hybrid silicones and perfluorinated olefins, are known to be catalyzed by means of selected metal compounds and in particular certain metals of group VIII such as platinum. In this way, Pt / Sn complexes were used as hydrosilylation catalysts. See US Patent No. 4 089 882 (SHINETSU). This synthesis strategy seems to be relatively complex and therefore 5 face. With the concern of industrial simplification, a second synthesis strategy based on the direct hydrosilylation of a silicone with SiH motifs with the help of alpha-fluorinated olefin has been proposed.
say type CH2 = CH-Rf; that Rf motif is directly linked to the olefinic CH by means of an atom of
- carbon carrier of at least one fluorine atom. Here, again, various metal catalysts of group VIII, in particular based on platinum, are used in the
frame of this hydrosilylation reaction. However, it became clear that these catalysts did not allow to achieve very high yields. In particular, conventional industrial platinum-based hydrosilylation catalysts (for example of the KARSTEDT type) are not
very effective. In addition, it was found that important quantities of by-products are produced and this, of course, to the detriment of the perfluorination of silicas. In those known perfluorinated POSs, the radical Rf is directly linked to the Si of the silicone chain. In other words, the patella corresponds in this case to: -CH2-CH2- (CH2) m with m = 0. In US Pat. No. 5,233,071, these patellae are put into operation. They come from the hydrosilylation of
alpha-olefins. But to reduce the deficiencies of the hydrosilylation catalysts that were used previously, the procedure described in that patent, resorts to organometallic complexes based on cobalt [(Co2COg, Co2C06) (PR3) with R = alkyl, aryl).
A technical proposal of this kind was revealed as not being sufficient, because the
- reaction times that were obtained, are of the order of a few days and it is essential to use a significant amount of catalyst (1-2%), which is particularly critical for the economy of the procedure. A non-negligible drawback of these cobalt-based complexes is that they catalyze other reactions than hydrosilylation. In particular, they can participate in polymerization processes by breaking the epoxy cycles. This lack of specificity is particularly annoying. In addition, these catalysts are not industrial. U.S. Patent No. 5,348,769 discloses linear or cyclic polyorganosiloxanes, comprising siloxyls D motifs substituted by a first perfluorinated functional motif of formula -R ^ ZRf, as well as other D motifs, carriers of a second type of Functional motif of the etherhydroxyl type The patella or the bridge joining Si to Rf of the first perfluorinated functional motif consists mainly of: - (CH2)? Z with x = 2, 3 or 4 and Z = NHCO, NHS02, 02C , OCH2CH3, NHCH2CH2 or CH2CHOHCH2 Preferably, the catalyst that is put into work is chloroplatinic acid.This type of technique is not the simplest, because it requires the previous preparation of perfluoroalkylated olefinic reagent.This significantly lengthens the synthesis durations and, as a consequence, the cost of the procedure increases, except for those pads whose precursors are perfluoroalkylated alpha-olefins of the formula CH2 = CH-Rf, the previous technical literature also describes bridges whose olefin precursors unique are of the type CH2 = CH- -Rf; the chemical bond between L and Rf, is an ester bond. The latter results from the reaction of a carboxylic function with a perfluorinated perhalogenated alcohol. Generally, this carboxylic function is the product of the hydrolysis of an acid anhydride. It is in that way, that the PCT patent application WO
94/12561 discloses POS grafted with fluorinated motifs only in the alpha and omega positions at the ends of the silicone chains. These alpha-omega alkylperfluorinated POS do not present optimal properties, in terms of the reduction of surface tension, as well as oleophobia and hydrophobicity. European Patent Application No. 0 640 644 describes perfluorinated silicone derivatives (Rf) which can be used in cosmetic formulations. These perfluorinated silicone derivatives are characterized by siloxyl D motifs, perfluorinated graft carriers of three different types, namely:
CH - (CH ^ -Rf (CHj), O CH I | - CH, 0- (CH2) -Rf (CHj) r_ (oR, r _o (CH,) or- Rf
(1) (2)
(CH,) - O CH,
(3)
with R? , R 3J _ = alkyl, ie CH 3;
2 less than or equal to 16, i.e. i = 3; 1 less than or equal to 6; less than or equal to p less than or equal to 200; 0 less than or equal to r less than or equal to 50. the number of siloxyl motifs D grafted in this manner is between 1 and 200; X, Y = single bond, -CO-, alkylene in Cj-Cg; These perfluorinated grafts (1) to (3) have in common, the presence of ether-oxid bonds within the patella that links the perfluorinated radical Rf to silicon.
These ether bonds are as many breakpoints as possible by chemical attack, under certain
- - terms . This is a major drawback for those known perfluorinated POSs, since it is clear that in certain applications, the labile character of the perfluorinated functions is not admissible. It is clear from this review of the prior art that there are no halogenated POS, preferably perfluorinated, chemically stable and comprising, on the one hand, 20 fluorinated side grafts resulting from the hydrosilylation of olefins perfluorinated by SiH and having alkyl splints and / or alkyl esters, excluding ethers and, on the other hand, other non-perfluorinated functional reasons that can give them diverse and varied physical and chemical properties, which offers them outputs in many applications. In addition, the prior art discloses still less that type of POS that can be obtained in a simple, economic and therefore perfectly industrial way. In these circumstances, one of the essential objectives of the present invention is to reduce this lack in this type of halogenated POS,
preferably (per) fluorinated, and better still, to provide new perfluorinated POSs that have a first
- type of non-perfluorinated functional grafts and a second type of perfluorinated bifid grafts each having one or two parallel perfluorinated chains; of that
way, these POS are endowed with a crystalline character, which makes them particularly adapted to the anti-dirt application. Another essential objective of the invention is that of providing a process for the preparation of halogenated POS 20, preferably (per) fluorinated; that process is of the type of those in which at least one halogenated (ie, fluorinated) olefin is reacted and at least one olefinic precursor of a different functionality from the fluorinated grafts or "which can be with a POS comprising at least a SiH motif and in the presence of an effective amount of catalyst according to a hydrosilylation mechanism.This procedure must be carried out with the available starting materials or products that can easily
to prepare themselves and that they should also rely on a simple methodology to be put into action, not needing sophisticated equipment and that allow achieving high performance and purity behaviors in final perfluorinated POS. Another essential objective of the invention is that of offering a process of perhalogenation (perfluorination) of the type mentioned above, which is characterized by an excellent kinetics of hydrosilylation and by an important rate of
± 5 conversion of the SiH siRoRf motifs with Ro = divalent point and Rf = perfluorinated motif. Another essential objective of the present invention is that of making available, a perhalogenation process, preferably (per) fluorination, of the POS carriers of SiH, which make it possible to resort to traditional hydrosilylation catalysts, simple to manipulate and inexpensive , for example, of platinic nature (KARSTEDT), and this without sacrificing the imperatives of optimal performance efficiency, of -25 purity of the final products and of specificity.
Another essential objective of the invention is that the aforementioned process makes it possible to obtain, in a simple and inexpensive manner, perfluorinated POS (ie silicone oil) which are at least di-functional. These objectives, among others, are achieved by means of the present invention which is mainly related to new perhalogenated POS, preferably perfluorinated, as well as a new perhalogenation process, by hydrosilylation of the POS carriers of SiH; this procedure is one of those that allow obtaining the new POS. Therefore, in the first place, the present invention relates to polyorganosiloxanes (POS) (per) halogenated, preferably (per) fluorinated, of general formulas (I) and (I ') below:
(p) in which: - a + b + p = 3; a = 2.3; b, p = O, 1; z is between 0 & 200, preferably between 1 & 90; 5 ~ vl is between 0 & 10, preferably between 0 & 5; and is comprised between 0 & 50, preferably between 0 & 25: e is between 1 & 200, preferably between 1 & 90; with the conditions according to which: -_. / _ \ if z is not equal to 0, then 5 is less than or equal to z + y1 + e less than or equal to 200, preferably 10 less than or equal to z + yj + y + and less
or equal to 100, & [z / (z + y + -? + e + 2)]. 100 greater than or equal to 3, preferably 5; / _ \ if z = 0, then 5 is less than or equal to Y + Y "l + e less than or equal to 100, b is not equal to 0 in at least one of the monovalent M 20 terminal siloxyl motifs; if e is not equal to 0, then 5 is less than or equal to az + yj + y + and less than or equal to 200, preferably 10 is less than or equal to az + yj ^ + y + and less than or equal to 100 & z / (z + and + - + e + 2)]. 100
- ^ 5 greater than or equal to 3", preferably 5;
/ _ \ if e = 0, then 5 is less than or equal to y + y ^ + z less than or equal to 100, p is not equal to 0 in at least one of the motifs M; * 1 less than or equal to z 'less than or equal to 9; preferably 1 less than or equal to z 'less than or equal to
4. 5; * 0 less than or equal to y '- ^ less than or equal to 0.5; preferably 0 less than or equal to y'j less than or equal to 0.25; * 0 less than or equal to y1 less than or equal to 5; preferably 0 less than or equal to y 'less than or equal to 0.5; * each radical R1, R2, on the one hand, is identical or different from its counterparts of the same exponent and the other radical of different exponent and, on the other hand, represents a linear or branched (cyclo) alkyl group on C - ^ - C ^ r preferably c? ~ ce > an aryl, an aralkyl, an alkylaryl; these groups are optionally substituted, * Gf is a functionally halogenated monovalent radical, preferably (per) fluorinated, of identical or different nature in the z or z1 of siloxyl D motifs, and / or the two siloxyl M motifs in which it is present & which is of the average formula below: (GO - z? - (z ^ -j ^ .- R? ^
/ _ \ with h = O .1; g = O .1; j = 0.1 & = l or 2: 5 / _ \ with the condition according to which at least one residue Gf is present in the POS (I) or (II), preferably, the residues Gf are present at least at a height of 60 mol%; / _? %? is a divalent radical of formula: 10 CmH2m > with m greater than or equal to 2 and with the condition according to L_ which if m = 2, then at least a part of the residues Gf are residues in which g is not equal to 0; / _ \ Z is a mono, di or trivalent radical of formula:
to . OR
II / ° c- II 20 O
one or both of the free valencies of the carbonyl (s) are linked to -Z3Rf & , in the case where only one of the mentioned free valencies is attached to -Z3Rf, then the other is attached to a -25 hydroxyl;
O II
JC -: R 'II or
at least one of the free valencies of the carbonyls is attached to -Z3Rf, & in the case where only one of said free valences is linked to -Z3Rf, then the other is linked to an alkoxy, in C ^ -C, linear or branched. Ra = H, aryl or straight or branched lower alkyl in Cj-C, preferably in CH3;
Y- - - OH d. OR
h = 0 dans Gf, * h = O in Gf; * one or both of the free valencies of the (or of the) carbonyls are attached to -Z3Rf, & in the case where only one of said free valencies is linked to -Z3-Rf, then the other is attached to a linear or branched hydroxyl or alkoxy, in C - ^ - C8. ?
* one and / or the other of the two free valences different from the valence - », is (are) joined to -Z3Rf,
- & in the case where only one of the mentioned free valencies is linked to -Z3-Rf, then the other is bound to OH or to an alkoxy, in C ^ -C, linear or
branched; ?
* one and / or the two different valences 20 different from the valence - », is (are) joined to -Z3Rf, &; in the case where only one of said free valencies is linked to -Z3-Rf, then the other is linked to OH or an alkoxy, in C ^ -Cg, linear or branched; -25 * Rb = H or lower alkyl in C ^ Cg, linear or branched; methyl is preferred; - > W represents a hydrocarbon radical or not, in particular aliphatic and / or alkenyl and / or aromatic; 5 furthermore, W is free of ether-oxide linkage -0-; / _ \ Z3 is a divalent radical of formula: - u-cnH2n * with n greater than or equal to l & U = O, S, NH, NHS02, preferably O; 10 / __ \ Rf is a perhalogenated radical, preferably perfluorinated, and more preferably still a linear or branched perfluoroalkyl radical of one of the following formulas: - C .cqF2q - CF3 with q greater than or equal to 0; 15 mm (jF2g - H with q greater than or equal to 1; •• - "NRrfS02 C" F "- CF3 with q greater than or equal to 0 and Rrf = H, aryl or lower alkyl in straight or branched C ^ -C8 ( preferably CH3); "" - »NRrfS02 C" Fq - CF3 with q greater than or equal to 20 and 1 and Rr as defined above; * E is a monovalent functional residue, other than Gf defined above, of identical or different nature in the siloxyl motifs D and / or the two siloxyl motifs M where it is present and selected, preferably between the groups having at least one of the following functionalities E- ^ a E- ^ 3: / _ \ E? = - (zl) h = 0.1"(z2) g = 0.1- 5 in which: * Z- ^ has the same definition as the one given above for the definition of Gf, with m greater than or equal to 2; Q * Z2 corresponds to: .ae. O II ^ -
II O 5 with at least one of the free valences of a carbonyl, attached to an OH, or then also those two valences are both bound to the same oxygen atom:
.ße. / 0 0 -'CH sco- with the two free valences of the carbonyls, each linked to an alkoxy in straight or branched C - ^ - C8;
O ou - -NHj
the free valence of the carbonyl is attached to a linear or branched C ^-C alkoxy, or then also to an OH; ?and.
with at least one of the free valences of a carbonyl, attached to an OH, to a linear or branched alkoxy in C ^ -Cg, or then also those two free valences are both bonded to the same oxygen atom; ?and.
* one and / or the other of the two free valences different from the valence - ^, is (are) joined to Z3Rf, & in the case that only one of these two valences is linked to -Z3-Rf, then the other is linked to OH or to an alkoxy, in C-Cg, linear or branched:? e.
Rb
* R "= H or -alkyl lower in j-Cg, linear or branched, methyl is preferred; * Zlf Z2 are identical or different to their corresponding ones involved in Gf and described above; * W is as defined above for Gf; / _ \ E = amine; E3 = alkoxy; E4 = acyl; E5 = alkoxy; Eg = hydroxy, E7 = trialkoxysilyl; Eg = amide; E9 = ester; E10 = phenol; E1; L = arylalkoxy; E ^ 2 = aryloxy;
E13 = ether-hydroxy.
The Applicant had the merit of producing these new POS (per) halogenated, preferably (per) fluorinated, thanks to the judicious selection, on the one hand, of
different species of perfluorinated Gf grafts and, on the other hand, at least one second functionality carried by the lateral E grafts that belong to one or several different species from each other, but above all
different from Gf, due to the lack of perfluorinated remains. According to the invention, the graft species Gf that must be taken into consideration are, above all: those of the alkylene ring fC ^ jH ^ - with m greater than or equal to 2; - those with an alkylene ring - (CmH2m) m + 2 (m greater than or equal to 0), extended by a hydrocarbon radical W di- or tri-valent, free of ether -0- and having one or more perfluorinated radicals Rf; -_ - those with alkylene-patella (CmH2m) m (m greater than 2), prolonged, either by W, omega-hydroxylated and alkoxylated by a radical whose extremity
free = Rf, either by W alkoxylated by two radicals carrying Rf; that of alkylene-patella (CmH2m) - (m greater than 0), prolonged by a radical belonging to the general family of radicals W, di- or tri-valent,
and joined or that is inscribed in a cyclic unit whose valence (s) free (s) different (s) from that joined to the Si, ensures (n) the link with the (or the) remaining (s) eventual (s) (en) Z3Rf and / or with alkyl, alkoxy or hydroxyl substituents; -25 that of alkylene end-chain (c 2m ^ ~ ^ m greater than 0), prolonged by a trivalent silyl residue in which the free valence (s) different from that bound to Si, ensures (n) the bond with the eventual residue (s) Z3Rf and / or with alkyl, alkoxy or hydroxyl substituents; - and finally those with a free radical of divalent alkylene (h = 0), but having a radical W directly connected on the si and 10 carrier, on the other hand, of at least one radical Rf. All those grafts perfluorinated by Rf have the advantage of being chemically stable. Another major advantage of the grafts according to the invention is that they can be obtained with the aid of industrial catalysts, for example those based on platinum such as the KARSTEDT catalyst. In addition to the fact that they are used in small quantities, these catalysts are intrinsically inexpensive. In this way, the cost of the new perhalogenated (perfluorinated) silicon compounds according to the invention is reduced. This cost is much lower as the ball-and-socket structure allows access to rapid hydrosilylation kinetics, high yields and high rates of conversion of the SiH motifs SiGf.
In practice, the monovalent radical Rf corresponds to -CgF2q-CF3, with q comprised between 2 and 20, preferably between 5 and 12 and, more preferably still, between 7 and 10. In practice, it can also be work, mixtures of Rf whose q = 7, 8 and 9 According to an advantageous arrangement of the invention, the fluorinated polyorganosiloxanes with which it relates, comprise one or more grafts Gf in which: h = 0 or lg = l with z2 that it comprises a group W corresponding to a mono- or poly-cyclic saturated, unsaturated or aromatic radical, substituted or not, and which is preferably selected from the following cycles:
Therefore, one of the essential characteristics of the POS of the invention is to be carriers of one or more functional residues E of a different nature and grafted, preferably on siloxyl D motifs; these residues are selected, for example, from the following groups: * an epoxy-functional E- ^ group, preferably selected from the following groups: 3-glycidoxypropyl, 4-ethanediyl (1,2-epoxycyclohexyl); * and / or an E- ^ isocyanate group, preferably selected from the following groups:
* and / or an aminofunctional E2 group, preferably selected: - either between the following groups: NH2- (CH2) 2-NH- (CH2) 3-; NH2- (CH2) 3- - either amine, secondary or tertiary functions, included in a cyclic hydrocarbon chain (hals), of the formula:
wherein: ° R20 radicals, identical or different from each other, are selected from alkyl radicals, linear or branched, having from 1 to 3 carbon atoms, phenyl and benzyl; R21 is selected from a hydrogen atom, linear or branched alkyl radicals, having from 1 to 12 carbon atoms, alkylcarbonyl radicals wherein the alkyl moiety is a linear or branched moiety having from 1 to 8 carbon atoms. carbon, the phenyl and benzyl radicals and an O radical; ° t is an integer selected from 0 and 1; 10 ° the preferred radicals R20 are methyl, the radical R21 is a hydrogen atom or a methyl radical - and t is advantageously an integer equal to 1; And / or a hydroxy-functional group Eg, preferably selected from the following groups: 3-hydroxypropyl, 3- (2-hydroxyethoxy) -propyl. These other functionalities Ex to E13, that is, different from the perfluorinated Gf grafts, offer the possibility of building perfluorinated silicones endowed with other functionalities, both multiple and varied. 20 This is particularly interesting in the perspective of specifically adapting each POS to a specific application. It is clear that, taking into account their chemical reactivity, E grafts can be precursors in certain -25 cases, of pending perfluorinated groups, especially of Gf type. Then, they are supports for the connections of Rf residues or, in other words, potential precursors of Rf joints (Rf pre-rings): that is, anhydrides, carboxyls, alcohols, isocyanates, etc. 5 But the possibilities of substitutions are not limited, of course, to perfluorinated groups. The fixation of any reactive group (crosslinking) on the E-grafts can be planned. According to a preferred embodiment of the invention, the OSs are linear and have the following average formula. { I-D:
(U)? 5 in which: * Gf corresponds to the definition given in the preceding, with h = g = 1 or h = l & g = 0; * E = E- ^ to E13; 20 * R1, R2, are as defined above, preferably methyl, propyl or butyl; * c- ^ + d- ^ = 3, preferably c- = 2, d- - 1; * c2 + d2 = 3, preferably c2 = 2, d2 = 1;
* 1 less than or equal to Z less than or equal to 90, preferably 1 less than or equal to Z less than or equal to 50; * 1 less than or equal to and less than or equal to 5 100, preferably 1 less than or equal to and less than or equal to 60; * 0 less than or equal to y ^ less than or equal to 10, preferably 0 less than or equal to y- ^ less than or equal to 5; 10 * 0 less than or equal to and less than or equal to
50, preferably 0 less than or equal to and less than or
-_ equal to 25; Even more preferably, the POS (I) according to the invention are perfluorinated linear polymers of
following formula (1-1.1):
with y, j, z, e, Gf & E as defined in the above and Ralfa, identical or different represent: H or C 1 -C 8 alkyl.
According to a variant of the invention, the POS are shorter polymers, even oligomers of the following formula (1-1.2):
(1.1.2)
in which: + Gf is as defined in the above 1; + R1 identical or different from its similar ones of the same index = R1, as defined in the foregoing; or then it also corresponds to a • functionality (E) as defined in the foregoing, preferably an epoxy-functional radical; + R2 identical or different from its similar ones of the same index, which has the same index and definition as the one given in the foregoing; + a1 + b1 = a2 + b2 = 3 alf a2 = 2 or 3; b ^, b2 = 0 or 1; 0 less than or equal to and less than or equal to 20 100, preferably 0 less than or equal to and less than or equal to 10; 0 less than or equal to p less than or equal to 50, preferably 0 less than or equal to p less than or equal to 5; -2"5 -> the formula in which RJ- = CH3, b-j_ = 1, b2 = 0;
Gf: - (CHjJj-C
with R 10, R 11 equal or different and representing OH alkoxy Cj-Cg or Z3Rf according to the preceding, at least one of the radicals R10, R11 = Z3Rf,? = 0, y = 0 or 1; 10 - > the formula in which R1 = CH3, bj = b2 = 0:
COR10 / GI: - (CH ^ -CH \ COR11 15 y = 0, p = 1 to 10, preferably 1; -> are particularly preferred.
twenty
-25 For example, those POS are the following oligomers
Me I e3S¡O- (S¡O-SiMe,
Fp, -S¡Me2OSiMe2-H
fifteen
-25 -H Advantageously, Gf is selected from the list of the following groups: .a. -CmH2? N -.Rf with m greater than or equal to 2, h = l, g = 0, j = 0, k = l
.b.
with: 10 - h = 1, greater than or equal to O, g = l, j = 0 or 1, k = 1; -_ - - R3 = H, alkyl in C - ^ - C, - R4, R5 = identical or different from each other and correspond to ~ (CH2) -U superi0r or equal to or * * 15 - R °, R7 = identical or different from each other, represent Z3 - Rf with Z3 = -O-; (CH2) -S is between 0 and 10; one at least corresponds to
Z3_Rf; .c. 20 - (CH J; CR 3
in which: - h = 1, m greater than or equal to O, g = l, j = 0 or 1, k = 1, i = 2 to 10; -25 - R, R, R 'are such as, are defined above;
with: - h = 0 or 1, m greater than or equal to O, g = l, i = 2 to 10, j = 1, k = l; - R. R are as defined above; .and.
with: - h = 1, greater than or equal to O, g = 1, i = 2 to 10,
3 = 0 or l, k = l; - R6 is as defined above; .F. & its mixtures
According to the invention, a subgroup of particular Gf grafts, called "bifid grafts", is considered to be very special, taking into account the remarkable characteristics that can be conferred on the POSs on which they are grafted. Therefore, the invention also relates to POS of the type of those that are defined and characterized in that they comprise at least one species (I) and / or (II) substituted by at least one perhalogenated Gf residue, preferably perfluorinated, selected in the subgroup of the following radicals: - > (i)
ff C _R »
with: Ra, R9 independently = H or lower alkyl, 1"6 'branched ineal, preferably CH3; R10, R11 independently = OH alkoxy Cj-C, linear or branched, or Z3-Rf, at least one of those radicals R10, R11 represents -Z3Rf, i = 0 to 10, preferably 0 to 3, and still more preferably i = 1; - > (ii)
.10 / CHRS (CH ^ SiR * V with R9, Ra, R10, R11 &i as defined above; - > (iii)
with R9, R10, R11 & i as defined above; he
The hexyl ring may optionally be substituted. - > & the mixtures of the radicals that precede.
At this stage of the description, it is convenient to dwell a little on this particularly interesting species of POS compounds according to the invention, which are the perhalogenated (perfluorinated) POSs with bifid grafts as defined above. More precisely, one is interested here in the Gf whose two legs are each constituted by a radical
perhalogenated (perfluorinated) Z3Rf. These biofluorinated bifid Gf grafts are crystalline and primarily provide some crystallinity to the POSs they replace. This optimizes the water-repelling properties of the latter, which are thus well adapted as an active product in antifouling compositions, among others. These bifluorinated grafts can be associated, above all, with monoperfluorinated and / or non-perfluorinated bifid Gf. The POSs of this species are characterized in that they comprise at least one species (I) and / or (II) substed by: - at least one perhalogenated Gf residue, preferably perfluorinated, of formula (i), (ii) or ( iii), above; - - - the radicals R10, R11 of the formula considered to correspond to Z3-Rf; preferably to:
fifteen - . 15 - ~ 0 -CnH2 ~ Cq F2"CF3 (q = Q)
- & optionally by at least one residue Gf (i), 20 (ii) or (iii), in which one of the radicals R10, R11 is
Z3-Rf; - & the other of these radicals R10, R11 is different from Z3-Rf and advantageously corresponds to: linear or branched C-Cg OH-alkoxy. -25 The rates of substion of the POS of this species by biofluorinated and / or monoperfluorinated and / or non-perfluorinated bifid Gf can perfectly be controlled by the man of the trade, at the moment of synthesis. For the 5 grafted POS, these are the desired applications that determine the convenient regulations of those replacement rates. Within this species, the bifid Gf of the alkylmalonil (i) are the ones that are taken most in consideration in practice. By analogy to the bifid Gf grafts that are
- described above, the grafts E can be built on the same structure. As a result, another advantageous feature of the POS according to the invention,
it may be that they comprise at least one species
(I) and / or (II) substed by at least one residue E selected in the subgroup of radicals E (ie), (üe) and
(iiie), which correspond to the radicals Gf (i), (ii) and
(iii), respectively, as defined above,
with the small difference that R10, R11 are the same or different and correspond only to: OH, alkoxy in
Cj ^ -Cg linear or branched. All these grafts Gf and E confer novelty and great technical interest to the POS, to which they refer. "25 Taking into account the precisions given above regarding the POS according to the invention and its grafts Gf and E, it can be deduced that the preferred POS according to the invention are poly (dimethyl-methylperfluoroalkyl) 5 siloxanes or poly (methylalkylmethylperfluoroalkyl) siloxanes, with the first group alkyl = (propyl, butyl, pentyl, hexyl, etc ...) Certain linear perfluorinated POS compounds of average formula (1.1) (I.1.1) and (1.1.2), have
Naturally their corresponding cyclics of average formula (II.1); but, in this case, the sum of the z1 +
- and 'i + y' + e 'is less than or equal to 10, preferably
. According to an optional but advantageous embodiment of the invention, the POSs comprise per molecule: - at least one siloxyl motif T and also siloxyl motifs T = [R8Si? 3 / 2J with R8 of the same definition as that of R1, R2 , Gf or E, as given 20 above. & eventually siloxyl motifs Q = [Yes? 4/2]. In the case of the functional characteristics of the products according to the invention, it is necessary to emphasize the fact that the mono- or polyfunctional fluoro-polyorganosiloxanes described above have? remarkable properties of low surface tension and oleophobic and / or hydrophobic, in other properties. These properties can be adjusted by controlling the proportions of grafted or non-grafted D motifs that are present in the fluorinated POS. This corresponds to the molar proportions z, z ', y- ^, Y' i, Y, Y *, e, e 'that are given with the formulas defined above. It should be noted that values of m = 1 or 2 in Z ^ of Gf, are the guarantees of a good thermal behavior for the fluorinated POS under consideration. This property can be interesting especially in the context of an application of fluorinated POS lubricant. It is also interesting to note that, in the case in which the fluorinated POSs comprise a functionality E4 aminated on a motif D or possibly T, this is not without having repercussions on the coefficient of friction of the oil in question. This is again an exploitable advantage in lubrication. According to a variant of the invention, the functionality (s) E can optionally be carried for M or T reasons. The fluorinated POS according to the invention can be in the form of more viscous oil but also in the form of Q and / or resins. or resins that result from the cross-linking of the linear or cyclic POS chains, by means of cross-linking functionalities that these resins can present. Another object of the invention is constituted by a process for preparing (per) halogenated POS, preferably (per) fluorinated, cyclic or linear characterized in that it consists essentially of reacting: A) - at least one polyalkylhydrogen-siloxane oil, of polymethylhydrogensiloxane preference; 10 B) - with at least one (per) halogenated, preferably (per) fluorinated olefin, precursor of Gf and of formula (Gfp) ZlpRf in which:? 5 * Zlp = olefinic precursor of Z ^; * Rf as defined above; O- and / or with at least one (per) halogenated, preferably (per) fluorinated olefin of the formula: Zlpz2p in which: * Zlp = olefinic precursor of Zj_; * Z2p = olefinic precursor of Z2;
-25 D) - in the presence of an effective amount of metal hydrosilylation catalyst, preferably based on platinum; the reaction product A + C is optionally placed in the presence of a reagent of the type Z3_Rf with Z3p = precursor of Z3pRf with Z3p = precursor of Z3 and Rf as defined above, so that grafts Gf = Z-jRf are obtained and / or = Z1Z2Z3Rf; E) - finally with an Ep reagent formed by
an olefinic precursor of E; Ep can be hydrosylated with the = SiH of the POS in the presence of D. - Radical precursors of the radicals that are present in the final POS, are identified by the "p" index attached to the index (s) that already
indicated. According to a variant, the precursor Ep is of the type: zlpz2p with zlp 'Olefinic precursor of Z- ^ and Z2p precursor of Z2; Z ^, Z2, Zlp, Z2p are identical or different from their corresponding ones that intervene in Gf and are described
above; In this mode of implementation, radicals -Z- ^ Z ^ grafted onto the POS are put in presence with at least one reactive compound carrying a group having at least one E functionality, in order to produce grafts: - Z1 &2E.
In the case of the Z2p of the anhydride type, it can be considered to subject at least a part of these anhydride functions, to a hydrolysis, in order to generate free carboxyl extremities, and then an esterification of at least a part of the carboxylic extremities mentioned with the aid of reagents of the type precursors Z3p-Rf; Z3p is a hydrogenated precursor of Z3, as defined above, the same as Rf. The remaining free carboxyl limbs are part of the grafts E. Instead of, or in addition to, the reagents Z3p-Rf, it is possible to use at least one reactive compound from a group having at least one E-functionality. According to another variant , we proceed by preconstruction of an olefinic global precursor radical Gfp and / or Ep that is then fixed on the POS. In other words, this variant consists essentially in reacting: A) - at least one polyalkylhydrogen-siloxane oil, preferably polymethylhydrogensiloxane; F) - with at least one halogenated olefin, preferably (per) fluorinated, precursor of Gf and of formula (Gfp):
(- ^ - E ^ J- ^ k in which: * Zlp is the olefinic precursor of the radical Zj_, as defined above; * Z2, Z3, Rf, h, g, j &k are also defined more 5 arri a; * with the proviso that if h = 0, then g = 1 &Z2 becomes an olefinic precursor Z2p; G) - and / or with at least one olefinic precursor Ep of E; 10 D) - in the presence of an effective amount of metal bridging catalyst, preferably a platinum base. Preferably, the Gfp precursor of Gf is at least one of the following formulas: 15 - > (ip)
ff C_R with: Ra, R9 independently = H or lower alkyl, linear or branched l 'Cg', preferably CH3; -25 R10, R11 independently = OH alkoxy C- ^ - Cg, linear or branched, or Z3-Rf; i = 0 to 10, preferably 0 to 3, and still more preferably i = 1; (üp) 23
OR
with Ra, R9, R10, R11 & i as defined above; - > (ülp) i5
with 20 R, R10, R11 & i as defined above; the hexyl ring may optionally be substituted. These olefinic Gfp precursors of the bifid Gf grafts have one or two perfluorinated R?, R11 groups (R10 and / or R1: 1 = Z3Rf) and are obtained by setting them in reaction according to a transesterification mechanism: - > at least one alcohol constituted by the hydrogenated radical Z3Rf, that is H-Z3Rf, is: H-0-qua2n ^ x ^ x = O or l 'according to the foregoing; > with starting products formed by
compounds of formula (ip), (II) or (iiip), as defined above, and in which at least one of the radicals R10, R ^, is a linear or branched alkoxy in C - ^ - Cg. For the olefinic precursors Ep of the 10 bifid E grafts, each of them is preferably of at least one of the formulas (iep), (iiep) and (iiiep), and corresponds respectively to the formulas (ip), (üp) Y (iüp). which are given in the foregoing GFp, with the small difference that R10, R- ^ 15 are the same or different and correspond only to OH, C ^ -C, linear or branched alkoxy. The subject of the present invention is also novel synthons (reaction intermediates) of the process described above. Each synthon
characterizes what is at least one of the following formulas:
-25 (ip)
ff c _R "
with: Ra, R9 independently = H or lower alkyl,
C ^ -Cg, linear or branched, preferably CH3; at least one of the radicals R10, R11 - corresponds to a linear or branched C - ^ - Cg alkoxy, methoxy and ethoxy, with propyl being preferred; - > (üp) 5
with 0 R9, Ra, R10, R11 & i as defined above; - > (iüp)
-5 with R9, R u, RH & i as defined above; the hexyl ring may optionally be substituted.
One of the major advantages arising from the use of this type of perfluorinated or unsaturated compounds (Zlp, Z2p, Gfp, Ep), consists in the possibility of putting into operation an industrial catalyst that is selected among the compounds based on of Ni, Pd or
pt preferably based on Pt. For example, this may be a catalyst of KARSTEDT, advantageously employed in a small amount, ie of the order of 10 to 50 ppm in relation to the POS that is considered before hydrosilylation (Si oil). -H) The methodology determined by the method according to the invention is particularly simple. The kinetics of hydrosilization is fast. The yield and the conversion rate of the SiH are particularly high. It is a procedure of good behavior and
economic. According to a preferred embodiment of the invention, the POS of motifs ----------- SiH, is progressively placed in the presence of halogenated Gfp olefin (s) and olefinic precursors Ep of the E-grafts. catalyst is
_25 contained in one and / or in the other of those three constituents POS, Gfp and Ep of the reaction medium. In practice, hydrosilylation proceeds in as many phases as there are different olefinic reagents. The reaction medium is placed under stirring and is brought to a temperature between 50 ° C and 150 ° C. The reaction develops at atmospheric pressure and over a period of several hours, generally. Rate
transformation of the SiH motifs is greater than 99% in number. - In the case of other functionalities E described above, and which can be carried by the silicons of the POS according to the invention, its grafting can take place before, during or after grafting of the perfluorinated alkyl residues by Rf. Among the POS that can be used as starting materials of the process according to the invention, examples that may be mentioned are: * linear POS such as polymethyl-hydrogenosiloxanes, especially those of the type:. Me3 SiO (SiMeH0) s if Me3, with s = 10 to 100, preferably 50; . or Me3SiO (SiMeHO) sl (If Me20) s2, with B 1 = 10 to 100, 5 and s2 = 0 to 50;
* cyclic POS, such as tetramethylcyclosiloxane D'4. By way of examples of POS that can be perhalogenated, preferably perfluorinated, thanks to the method according to the invention, the following can be mentioned:. Me3 SiO (SiMe20) _8 (Si Me20) "4 If Me3; . Me3 SiO (SiMeHO) _50 SiMe3; It has already been indicated above, that the POS (I) or (II) at least bifunctional replaced by grafts Gf and 10 E, can be presented in the form of oils. According to a variant of presentation, the POS mentioned above, can be emulsified with water. Thus, the present invention also has for its object, an aqueous dispersion characterized in that it contains: - at least one POS that is defined above or those that are obtained csn the process as defined above; - Water; - and at least one surfactant. Therefore, the oils of the invention can be emulsified without addition of solvent for the application. In addition, the behaviors in terms of oleophobic and hydrophobic, can be improved by the addition of -25 selected surfactants.
The fluoro silicones according to the invention can be combined with conventional acrylate backbone fluoropolymers, which synthesis process naturally leads to an emulsion. Other ionic compounds, such as the styrene / maleic anhydride copolymer salts, can be used in addition to the fluorinated POS of the invention. In the case in which the fluorinated POS comprise? 0 salivable specific E-functions, this allows to ensure the emulsification, thanks to the salification
- partial or complete with a base (-COOH functions-) or the quaternization of amines functions. In other cases, it is necessary to formulate an emulsion. 5 Different solvents can then be used
(alcohol, ketone, fluorinated solvents, ethyl acetate, etc ...), for an initial solution of the product. The surfactants which are used for the emulsification are ionic or non-ionic with a high hydrophilic / hydrophobic balance. Generally, they are selected from the following compounds: ethoxylated fatty alcohols, ethoxylated alkyl phenols, -25 ethoxylated alkylamine salts, ethoxylated polyalcohols, alkyl ammonium salt, etc. According to another of these aspects, the invention relates to the application of the perhalogenated (perfluorinated) silicon compounds per se, as described above or those obtained by the halogenation process disclosed above, by way of: lubricant 10 - agent for lowering surface tension; - anti-dirt agent -_-adherent agent; - anti-foam; - oleophobic and / or hydrophobic agent; 15 - raw material to make elastomers that resist chemical aggressions and solvents. - Raw materials for preparing films and / or coatings endowed with at least one of the properties mentioned above. With reference to the particular properties of perfluorinated bifid grafted GF grafts (mono but especially bi-perfluoro grafts), the present invention also has an anti-dirt composition, characterized in that it comprises: -25 - at least one POS such as is defined above; - and / or at least one emulsion as defined above; 5 - the POS (s) mentioned above, which are put into operation, are preferably POS carriers: * of bifunctional Gf grafts bifunctionalized by perhalogenated, perfluorinated radicals, as defined above; 10 * of other E grafts functionalized by functions other than the bi- or mono- -halohalogenated / perfluorinated functions, as defined above; * and possibly Gf bifid mono-? 5 grafts functionalized by perhalogenated, perfluorinated radicals, also defined above. By way of illustration, it can be indicated that for perfluorinated POS applications as antifouling agents in the textile industry, one can have as an example: * E =
COOH CH ^ 3? NCH, -COOH -25 For example, perfluorinated POS that can be used as anti-adherent agents on paper or other supports, of which especially stone (anti-graffiti), are those in which it is found: * E =
or E =
fifteen
twenty
-25 E J E M P L O S
EXAMPLE I: Synthesis of perfluorinated silicone oils 5 thanks to Rf motifs comprising two types of ball joints Gf = alsuylene v Gf2 = alkylcarbonyl v also comprising EII grafts- Synthesis This synthesis is operated in 2 phases: 10 - Phase 1: preparation of the oil Grafted POS with perfluorinated GF1 motifs and with acid and anhydride E motifs. Stage 2: esterification of the anhydrous functions of the phase 1 oil. Phase 1: In a 150 ml four-neck reactor provided with a central mechanical stirring, with a thermometer, with a vertical ball cooler and with a septum, 20-90.8 ml of dry toluene (dried over molecular sieve) are introduced. The medium is placed under agitation, which is inerted with nitrogen and brought to a temperature of 90 ° C. The following are then introduced through the septum: • 25 - 4.8 μl of a solution in divinyltetra ethyl disiloxane from a platinum complex to 11% by weight of platinum bound with divinyltetramethyldisiloxane (KARSTEDT catalyst). Then, a period of 90 minutes is poured progressively and simultaneously over a period of 90 minutes: - 17.21 g (0.0273 mol of Si-H functions) of a polymethylhydrogensiloxane oil of structure (CH3) 3SiO- (SiOCH3H) 50-Si (CH3) 3 to 1585 milliequivalents (Meq.) / YES-H / 100 g of oil [RHODORSILR H68 from RHONE-POULENC) and - 50.1 g (0.139 mol) of 3-perfluorohexyl
1-propene 24 hours after the beginning of the reaction, the rate of transformation of the SiH functions are only 44% (for a maximum of 50), and 3.2 μl of the same KARSTEDT platinum solution is added. 2 hours 30 after that addition, the transformation rate of the SiH functions is 49.5%. Then, they are cast over a period of 90 minutes: - 25.13 g (0.179 mol) of alkylated succinic anhydride. Twice (43 and 50 hours after the beginning of the first casting), add: - 2 x 3.2 of the same KARSTEDT platinum solution. 72 hours after the start of the first casting, the transformation rate of the SiH functions is 99%. Then, a devolatilization is carried out to remove the solvent, excess reagents, heating up to 120 ° C under vacuum (0.01 mbar). 86.8 g of an oil of structure are obtained:
MßjSiO (SiMej 10
\ Gf, E, ac 15 Phase 2: In a 150 ml four-neck reactor equipped with a central mechanical stirrer, a thermometer, a vertical ball cooler and a septum, enter: 20 - 7.03 g of the oil which is described in the phase
1, partially hydrolyzed and structured:
-25 '_ J V. ~ 1 1 Gf, E, ae E, ae
- 5 24 f (0. 0113 mol) of 1-perfluoro-octyl 2-hydroxy ethane, -12.6 g of 1,1-trifluorotrichloroethane, The medium is placed under stirring, is inerted with nitrogen and then introduced: 0.15 g of pyridine through the septum and the temperature of the medium is brought to 50 ° C 8 hours later, a devolatilization is carried out to remove the solvent and the excess of alcohol that did not react, heating up to 110 ° C under vacuum. Then, 10.35 g of structure oil are obtained:
_25 1 Gf, E, ac G?
An infrared spectrum that is carried out on this
- "oil, shows that there is total disappearance of anhydride functions (there is no band at 1780 and 1860 cm- 1). NMR analyzes confirm the structure of this
functionalized silicone oil. 1.2.- Application of the bi-functional POS oil obtained in I.1: * Fat resistance test: The oil resistance of the example oil
1.1, it is evaluated on a mat of polyamide-6 (PA.G) that is treated with this oil by means of the test of the
AATCC (American Association of Textile Chemist and
Colorist) No. 118-1983, which consists of depositing drops of normal liquids (maximum eight) of polarity
--25 decreasing on the mat and measuring the time during which the drop remains on the surface before entering the mat (and the following is noted) Each number corresponds to a number and perfluorinated oil is given a quotation that corresponds to the highest number of liquid that remains at least 30 seconds on the surface of the mat. * Mat treatment: KP 307 oil is deposited in different quantities, on a mat of polyamide-6 from a solution in 1, 1 , 2-trifluorotrichloroethane, first place the mat in an oven at 30 ° C, and then place it in an oven for 6 minutes at 80 ° C and 4 minutes at 140 ° C. * Results: TABLE 1
The composition of the normal contribution liquids used was as follows: liquid 1: (liquid paraffin) liquid 2: NUJOL / n-hexadecane 65/35 by volume at 21 ° C liquid 3: n-hexadecane liquid 4: n -tetradecane liquid 5: n-dodecane In this way the oil of 1.1 corresponds to a price of 2 to 700 ppm of fluorine, 3 to 1400 and 42000 ppm of fluorine and 4 to 2800, 5600 and 7000 ppm of fluorine.
EXAMPLE II: Synthesis of a silicone oil
In a 1000 ml four-neck reactor equipped with a central mechanical stirrer, a thermometer, a vertical ball cooler and a septum, introduce: - 262.5 g of a perfluorohexyl isopentyl 1- and 2-ene mixture (CgF13CH2CH2C ( CH3) = CH2 and (C6F13CH2CH = C (CH3) 2) in a proportion of 20% and 80% respectively, be 0.135 and 0.541 mol, respectively 7.75 g of a polymethylhydrogen-siloxane polymer (either 0.122 mol of Si-H functions ) whose characteristics are the following: * Mn = 3160 g, * 1,585 equivalents Si-H per 100 g, * medium structure CH I 5 (CH3) 3 SiO- (Si-0) 5 0-Si (CH3) 3 H The medium is placed under stirring, is inerted with nitrogen and brought to a temperature of 100 ° C. It is then introduced through the septum: XQ - 13 μl (be 100 ppm / total mass of the Si-H oil) of a solution in diveniltetramethyldisiloxane of a
-_, platinum complex at 11.9% by weight of platinum agglutinated by diveniltetramethyldisiloxane (catalyst
KARSTEDT); i5 30 minutes later, when the rate of transformation of the Si-H that was introduced is 70%, they sneak simultaneously and in 80 minutes: 262.5 g of a mixture of perfluorohexyl isopentyl 1- and 1-ene 20 y (C6F13CH2CH = C (CH3) 2) in a proportion of 20% and 80% respectively, are 0.135 and 0.541 mol, respectively; - 7.75 g of the same polymethylhydrogensiloxane
(be 0.122 mol of Si-H functions). 3 hours 15 minutes after the beginning of the
The reaction, when the conversion rate of all the Si-H introduced, is 76%, is introduced: - 13 μl KARSTEDT catalyst. 22 hours after the beginning of the reaction, 5 when the transformation rate of the. all of the Si-H that were introduced, is 88.6%, are introduced through the septum: - 7 g (either 0.056 mol or 2 equivalents / Si-H remaining) of vinylcyclohexene; 10 - and 6.5 μl of KARSTEDT catalyst. 12 hours after these last additions, the TT
- of the Si-H functions is 99.9%, and devolatilization is carried out under vacuum (110 ° C under 1 mm Hg during
2 hours) to remove the perfluorohexyl isopropylpentyl 2-ene and j-5 the excesses of perfluorohexyl isopylethyl 1-ene vinylcyclohexene, and 90 g of an oil of structure are obtained:
E |? E Gf \
-25 EXAMPLE III: Synthesis of another bifunctional perfluorinated silicone oil Gf- | __y_E gamae: In a 1000 ml four-neck reactor provided with a central mechanical stirring, with a thermometer, 5 with a vertical ball cooler and with a septum , introduce: - 17.3 g of perfluorshexyl butylene (CgF13CH2CH2CH = CH2 (either 0.0462 mol), - and 5.7 g of vinylcyclohexene (either 0.0462 mol) 10. The medium is placed under stirring, is inerted with nitrogen and brought to a temperature of 100 ° C. It is then introduced, through the septum - 17 μl (be 50 ppm / total of the Si-H oil) of a solution in diveniltetramethyldisiloxane of a
. Platinum complex 11.9% by weight of platinum bound by divinyltetramethyldisiloxane (KARSTEDT catalyst); Then, over a period of 80 minutes are introduced: - 40 g (be 0.084 equivalent Si-H) of a 20 poly- (dimethyl, methylhydrosgenosiloxane) oil whose characteristics are the following: * Mn = 3160 g, * 1,585 Si equivalents H per 100 g, * medium structure. -25 CH CH II (CH3) 3SYO- (YES-0) 8- (Si?) 4 2 -YES (CH3) 3 H CH3 At the end of the introduction, the transformation rate of the Si-H functions is 98.6% and goes to 99.9%, 40 minutes later. Devolatilization is carried out under vacuum (100 ° C under 1 mm HG for
1 hour 30) to eliminate the excesses of the two reagents and obtain 59.1 g of structure oil:
Example Gfj
graduating at 0.065 equivalent per 100 g of oil (perchloric dosage).
EXAMPLE IV: Synthesis of another bifunctional perfluorinated silicone oil Gfj ^ v ^? ? f c: In a 50 ml four-nozzle reactor equipped with a central mechanical stirrer, - with a thermometer, vertical ball cooler and septum, introduce: - 7.36 g of perfluorooctylethylene (either 0.0165 mol); - and 30 g (either 0.033 equivalent Si-H) of a poly (dimethyl, methylhydrogensiloxane) oil, whose characteristics are the following: * Mn = 3806 g, * 0.11 equivalent Si-H per 100 g of oil, * medium structure . CH CH
I I (CH3) 3SYO- (YES -?) 4- (YES) 4 6-YES (CH3) 3 H CH3 The medium is placed under stirring, is inerted with nitrogen and left at room temperature. Then, it is introduced: - 0.075 g of dicobaltoctocarbonil stabilized with hexane (be 0.25% mass / to the oil Si-H). The exotherm of the reaction increases the temperature of 10 ° C for a short period, 10 hours after the beginning of the reaction, the transformation rate of the Si-H functions reached 48.5%. Then, it is transferred in an ampoule to decant and three washes are carried out with 3 times 30 ml of methanol. The methanol, which is still contained in the silicone phase, is removed by devolatilization under vacuum at 80 [deg.] C. for 2 hours, then a thermometer and a vertical refrigerant are placed in a 50 ml flask fitted with mechanical stirring. balls: 25.23 g (either 0.01 equivalent Si-H) of the partially grafted oil that is graduated to 0.037 equivalent SiH for 100 g; . and 1.54 g (0.011 mol) of alkylated succinic anhydride. The medium is placed under stirring, is inerted with nitrogen and brought to a temperature of 100 ° C. The following is then introduced by the septum: 10.6 μl (50 pp / loop of Si-H oil) of a solution of divinyl tetramethyldisiloxane from a platinum complex to 11.9% by weight of platinum bound with divinyltetramethyldisiloxane (KARSTEDT catalyst). 10 hours after the addition of platinum, the transformation rate of the Si-H functions is 71.5%; then added: - 10.6 μl of KARSTEDT catalyst. 24 hours later, the transformation rate of the Si-H functions is 97%; then a -25 devslatilization is carried out under vacuum to remove the excess of alkylated succinic anhydride and 26.51 g of structure oil are obtained:
E] ae Gf \
EXAMPLE V: Synthesis of a perfluorinated silicone oil
bifunctional Gf- | _ v E6: In a 1000 ml four-neck reactor provided with a central mechanical stirring, with a thermometer, with a vertical ball cooler and with a septum, enter: 20 - 10 g of toluene. The medium is placed under stirring, is inerted with nitrogen and brought to a temperature of 85 ° C. • Enter: - 2 μl (be 40 ppm / loop of Si-H oil) of
-25 a solution in divinyltetramethyldisiloxane of a platinum complex to 11.9% by weight of platinum bound with divinyltetramethyldisiloxane (KARSTEDT catalyst). It is then introduced, simultaneously, over a period of 1 hour by the septum, on the one hand: - 20 g of perfluorooctylptopylene (C6F13CH2CH2CH = CH2 (either 0.0435 mol), and on the other hand: - 5.18 g of a polymethylhydrogensiloxane (either 0.122 mol of functions Si-H), whose characteristics are the following: i * -. * Mn = 3160 g, * 1,585 equivalent Si-H per 100 g, * medium structure 15 CH3 I (CH3) 3SÍO- (Si- 0) 5 0-YES (CH3) 3 H 2 hours 40 later, when the transformation rate of the Si-H functions is 54%,
introduce, over a period of 30 minutes: - 8.27 g of 1-allyl, 3-methyl, 5-t-butyl phenol (either 0.0405 mol). 11 hours later, the conversion rate of the si-H functions is total and a devolatilization is carried out under vacuum (2 hours at 70 ° C under 1 mbar) to remove the toluene and the excess of perfluorooctyl-propylene and obtain 31.71 g of structure oil:
EXAMPLE V: Synthesis of a silicone oil
Bifunctional perfluorinated Gf- ^ and E13: In a three-neck 100 ml reactor provided with a central mechanical stirring, with a thermometer, with a vertical ball cooler, introduce: - 30 g of toluene. The medium is placed under stirring, is inerted with nitrogen and brought to a temperature of 85 ° C, and then introduced: - 2.1 μl (be 20 ppm / mass of Si-H oil) of a solution in divinyltetramethyldisiloxane of a
-25 platinum complex at 9.5% by weight of platinum bound with divinyltetramethyldisiloxane (KARSTEDT catalyst). It is then poured, simultaneously, over a period of 1 hour 30 minutes, on the one hand: 5 - 28.4 g of perfluorooctylptopylene (either 0.0435 mol); and on the other hand: - 9.74 g of a polymethylhydrogensiloxane (either 0.154 mol of Si-H functions), whose characteristics are
the following: * Mn = 3160 g, - - * 1,585 equivalent Si-H per 100 g, * medium structure.
H 4 hours 40 minutes after the beginning of the reaction, the transformation rate of the Si-H functions is 32%, and then 20 - 2 μl of KARSTEDT catalyst is added. 1 hour 50 minutes after that addition, the TT of the SiH functions is 48.7%, and they are filtered in 25 minutes: - 10.2 g of allyloxyethanol (either 0.1 mol). 1 hour after this second pouring, the TT of the -25 Si-H is 87.7%, and then: - 4 μl of KARSTEDT catalyst is added. 14 hours later the SiH is 96.5%, and devolatilization is carried out under vacuum (75 ° C, for 1 hour under 5 mm Hg), to eliminate the toluene and 34.3 g of an oil of structure are obtained:
Gfi Ei3
EXAMPLE VTI: Synthesis of another trifunctional grafted silicone oil Gf ^. % igama c. = 3: In a 100 ml three-neck reactor equipped with a central mechanical stirrer, with a thermometer, with a vertical ball cooler, introduce: - 12 g of polyfluorooctylethylene C6F17CH = CH2
(be 0.0275 mol), - and 50 g (be 0.055 equivalent Si-H) of a poly (dimethyl, methylhydrogensiloxane) oil, whose characteristics are the following: * Mn = 3806 g, * 0.11 equivalent SiH per 100 g of oil , * median structure: CH- CH-- 5 (CH3) 3SÍ0- (YES-O) 4- (YES0) 4 g-YES (CH3) 3 H CH3 The medium is put under stirring, is inerted with nitrogen and heated at 50 ° C. Then, it is introduced: - 0.049 g of dicobaltoctocarbonil stabilized with hexane (be 0.1% mass / to the oil Si-H). - 10 hours and 30 minutes after the beginning of the reaction, the transformation rate of the Si-H functions reached 34%; then added: - 0.049 g of dicobaltoctocarbonil stabilized with hexane. 1 hour later, the TT of the SiH reached 48.5%. The transvase medium is then placed in a decoupling vial and three washes are carried out with 3 times 50 ml of methanol. The remaining oil, partially emulsified by methanol, is solubilized in 1,1,1-trifluorotrichloroethane, and then the whole is devolatilized at 90 ° C under atmospheric pressure.
-25 They are then placed in a 50 ml three-necked flask provided with a central mechanical stirring, with a thermometer and with a vertical ball cooler: - 53.3 g (or 0.017 equivalent Si-H) of the partially grafted oil that is graduated to 0.032 equivalent Si-H / 100 g. - 5 μl of a solution in divinyltetramethyldisiloxane of a platinum complex at 10.0% by weight of platinum bound with divinyltetramethyldisiloxane
(KARSTEDT catalyst). - and 6 g of vinylcyclohexene (0.0484 mol).
- The temperature of the medium is brought to 70 ° C in 1 hour
minutes later. The TT of loe Si-H is total. A devolatilization is then carried out under vacuum (135 ° C,
for 2 hours under 6-water), to eliminate the excesses of perfluorooctylethylene and vinylcyclohexene and 49.67 g of an oil of structure are obtained:
i (CH,),
I I I I I I Gf] Ex ee E3
-25 that are graduated at 0.0359 epoxy equivalent per 100 g of an oil (dosage with perchloric acid).
EXAMPLE VIII: Synthesis of another trifunctional silicone oil G ^. Bj ^ gamae. «_ E3: In a 1000 ml four-nozzle reactor equipped with a central mechanical stirrer, with a thermometer, with a vertical ball cooler, introduce: - 271.6 g of per-fluorooctylethylene CQ F17CH = CH2 10 ( be 0.609 mol), - and 400 g (be 1.16 equivalent Si-H) of a - poly (dimethyl, methylhydrogensiloxane) oil, whose characteristics are as follows: * Mn = 6200 g, 15 * 0.29 equivalent SiH per 100 g of oil, * medium structure: CH CH
I I (CH3) 3SYO- (YES-0) 18- (YES-0) g 7-YES (CH3) 3 20 H CH3 The medium is placed under stirring, is inerted with nitrogen and heated to 50 ° C. Then, it is introduced: - 0.7944 g of dicobaltoctocarbonil stabilized -25 with hexane (be 0.2% ~ mass / to the oil Si-H).
8 hours 15 minutes after the beginning of the reaction, the transformation rate of the Si-H functions reaches 30.4%; Then add: 5 - 0.03972 g of dicobaltoctocarbonil stabilized with hexane (total 0.3% mass / SiH oil). 1 hour later, the TT of the SiH reaches 49.7%. The medium is then transferred to a decantation vial and washed four times with 175 g.
of methanol. The remaining oil, partially emulsified by methanol, is devolatilized at 90 ° C under 6 mm Hg
- for 45 minutes. It is then introduced into a 1000 ml three-neck flask fitted with a central mechanical stirrer, with 5 5 a thermometer and with a vertical ball cooler: - 597.1 g (or 0.211 Si-H equivalent) of the grafted partially graded oil to 0.353 equivalent Si-H / 100 g. - 30 μl of a solution in divinyltetramethyl disyl siloxane of a platinum complex at 9.5 wt% of platinum bound with divinyltetramethyldisiloxane (KARSTEDT catalyst). - and 30.4 g of vinylcyclohexene (either 0.245 mol). The temperature of the medium is brought to 80 ° C and 1 hour
-23 later, the TT in functions SlrH is 94.4%.
They are added then. - 30 μl of KARSTEDT catalyst. 8 hours later the transformation rate of the Si-H functions is total. A devolatilization is then carried out under vacuum (135 ° C, for 2 hours under 6 mbar), to eliminate the excesses of perfluorooctylethylene and vinylcyclohexene and 591.6 g of structure oil are obtained:
J L J L 15 Gf \ Example E3
which are graduated at 0.0213 epoxy equivalent per 100 g of oil (dosage with perchloric acid). EXAMPLE IX: Synthesis of POS mono-v bis-perfluoroalguyl monomers = Gfp precursors of bifid Gf and E grafts:
_25 Reaction: (BRD 1776)
i5 In a 5-liter reactor, 2018 g (10.09 mol) of allyldiethylmalonate, 2340 g (5.04 mol) of C8 alcohol Fj.7CH2CH2OH, 3.8 g (0.016 mol = of Ti- (0Et) 4 and 1000 are introduced under nitrogen, 2018 g (10.09 mol). g of dry toluene.
brings the reaction mass to 95 ° C. The reaction is carried out under partial vacuum (approximately 500 mm Hg), to favor the elimination of ethanol. After 5 hours of reaction, 7.3 g (0.032 mol of Ti- (OEt) 4 are added again, and it is left to react for 120 hours 5 An analysis by gas chromatography indicates that the conversion rate of the perfluorinated alcohol is 100%. of neutral alumina (50-200 μm) and filtered on cardboard, the light ones are devolatilized under vacuum pump (5 mm Hg, 3 hours 40 minutes), then a vacuum distillation is carried out which allows to separate the two mono- and bis-perfluoroalkyls.
The IR and NMR analyzes confirm the structure of two monomers.
EXAMPLE X: Synthesis of POS replaced by biofluorinated Gf (beta) bifido grafts and by functions E- ^ Jbefcae = pre-formula Gf: In a 1000 ml reactor, 217.3 g of dry toluene are introduced under nitrogenous, which is brought to 98 ° C. Then, 2.2 μl of KARSTEDT catalyst (11.5% by weight of Pt) is added. 24.6 g of a silicone oil of Si-H motifs of structure Me3SiO (SiMe2) 25 (SiMeHO) 70SiMe3 are simultaneously cast (Graduation Si-H: 11.27
J_Q moles Si-H / kg, be 0.277 mol Si-H) and 230.2 g (0.222 moles) of the fused bi-perfluoroalkyl monomer (about 70 ° C) as described in example No. 1. Pouring time: 2 15 minutes. It is left to react at 98 ° C for 21 hours 40 minutes. The rate of
± 5 transformation of the Si-H motifs is 79.3%. Then 50.6 g (0.361 mol) of the allyl of the succinic anhydride and 2.2 μl of the KARSTEDT catalyst are added. It is left to react at 98 ° C for 50 hours. The rate of transformation of the Si-H motifs is almost complete. The
reactional mass is heterogeneous. It is left to decant at 25 ° C and a net separation of the two phases is obtained. Filter over BUCHNER and wash with toluene. A white solid is obtained. Water (approximately 100 ml) is added and left to react for 17 hours at 25 ° C. 5 toluene is added to remove the free monomials. Decant, take the toluene phase and then, the solid is filtered and dried under vacuum at 25 ° C under 5 mm Hg. 465 g of a white solid are recovered. The IR and NMR analyzes make up the structure of this silicone oil. The melting point is close to 65 ° C and the elemental analysis in fluorine gives a content percentage of 53.8%.
EXAMPLE XI: Synthesis of POS substituted by monofluorinated bifido grafts Gf by functions E ^ betae = pre-formula Gf: In a 1000 ml reactor, 145.2 g of dry toluene are introduced under nitrogen and the medium is brought to 94 ° C. 5 μl of KARSTEDT catalyst (11.5% by weight of Pt) is added. Then, a mixture consisting of 578.5 g (0.936 mol) of the monoperfluorinated monomer described in Example VIII and 105.6 g of a silicone oil of Si-H motifs of structure Me3SiO (SiMe2) 25 (SiMeHO) 70SiMe3 ( Si-H graduation: 11.27 moles si-H / kg, be 1.19 mol Si-H). The duration of the laundry is 2 hours. Allow to react at 94 ° C for 28 hours 30 minutes. The transformation rate is 53%. Then 5 μl of KARSTEDT catalyst (11.5% by weight of Pt) is added and a total of 69 hours 30 minutes is allowed to react. The conversion rate of Si-H motifs is 73%. Then, 96.2 g (0.925 mol) of the allyl of the succinic anhydride are introduced. It is left to react for 128 hours. The transformation rate of the Si-H motifs is 96.5%. Approximately 100 ml of water are added and the mixture is stirred for 15 hours at 25 ° C. It is left to decant. The organic phase is devolatilized (5 hours at 120 ° C under 2 mm Hg) and 1330 g of a viscous oil are recovered. The IR and NMR analyzes confirm the structure of this silicone oil and the elemental analysis in fluorine gives a content percentage of 41%.
(PHO 128) EXAMPLE XII: Synthesis of POS substituted by monofluorinated bifid Gf grafts and by functions E- ^ betae = pretula Gf: In a 1000 ml reactor, 775 g of dry toluene and 0.2944 g of PtCl2 (PhCN) 2 are introduced. (Catalytic solution: 0.0169 g of catalyst of 1.8429 g of CH2cl2 in CH2Cl2) in the CH2Cl2. It is brought to 80 ° C and a solution of 134.9 g (1.5209 equivalent of Si-H motifs) of a silicone oil of structure Me3SiO (SiMe? 2) 23 (SiMeHO) 75SiMe3 is cast. It is left to react at 80 ° C for 24 hours by adding twice 0.15 g of the catalytic solution of Pt. The conversion rate of the SiH motifs is 69.79%. Then, 106 g of the allyl of the succinic anhydride and 59 μl of a catalyst solution of KARSTEDT (Graduation in Pt 11.5%) are added at 80 ° C. It is left to react for 24 hours. The transformation rate is 96%. The reaction mass is devolatilized (120 ° C, 5 mm Hg). The oil obtained is washed 6 times with 250 ml of water. It is devolatilized again and 852.5 g of a viscous oil are obtained. The IR and NMR analyzes confirm the structure of this silicone oil.
EXAMPLE XIII: Synthesis of POS substituted by biofluorinated Gf (beta) bifido grafts v by functions E-betae = pre-formula Gf: In a 5-liter reactor, 50 mg of toluene and 12.5 mg of Pt are introduced under nitrogen in the form of KARSTEDT catalyst. The reaction mass is brought to 85 ° C and a mixture consisting of 400 g of dry toluene, 874.94 g (0.864 mol) of the bis-perfluoroalkyl monomer described in example No. 625.06 g of a silicone oil of the same type is cast. Si-H structure
Me3SiO (SiMeO2) 200 (SiMeHO) 45SiMe3 U-55 m ° of Si-H motifs). The duration of casting is 3 hours. It is left to react for 4 hours at that temperature. The transformation rate of the Si-H motifs is 55%. 1901 g of a lipid oil are recovered.
In a 2000 ml reactor, 95.6 g (0.682 mol) of allyl of succinic anhydride and 0.1653 g of a KARSTEDT catalyst solution (11.5% of Pt) are introduced. The reaction mass is brought to 105 ° C and 950.6 g of the silicon oil of the above-mentioned SiH motifs are poured (3.412 moles of Si-H motifs). It is left to react at this temperature for 4 hours. The transformation rate of the Si-H motifs is 96.3%. Then, 500 ml of water are added. It is allowed to react for 7 hours at reflux. It is cooled and devolatilized under 3 mm Hg at 110 ° C for 4 hours. 781.6 g of a viscous oil are recovered. The IR and NMR analyzes confirm the structure of this silicone oil.
EXAMPLE XIV: Synthesis of POS substituted by bi-perfluorinated Gf (beta) bifido grafts v by E2 functions (hals) = Prefilm Gf: In a 2000 ml reactor, 93.01 g (0.442 mol) of allyloxy-HAi5 are introduced under nitrogen and 0.1651 g of a KARSTEDT catalyst solution (11.5% Pt). It is brought to 95-98 ° C. Then, 949.6 g of the silicone oil of SiH motifs of Example 6 are filtered in 2 hours, functionalized to 55% by the bis-perfluoroalkyl motif monomer described in Example No. 1. It is allowed to react for 2 hours to 100 hours. ° C The transformation rate of the Si-H motifs is complete. Allow to cool and add 50 ml of toluene. It is devolatilized for 5 hours at 110-140 ° C under 5 mm Hg. 755.5 g of a very viscous oil are recovered. The IR and NMR analyzes confirm the structure of this silicone oil.
E2 (hals) (BRD 1785) EXAMPLE XV: Synthesis of POS substituted by bi-perfluorinated Gf (beta) bifido grafts v by functions E2 (als) = pre-formula Gf: In a 250 ml reactor, 5 g dry toluene are introduced and 1.2 mg of Pt in the form of the KARSTEDT catalyst (11.45% Pt). The reaction mass is brought to 95 ° C and a mixture consisting of 20.24 g (0.02 mol) of the bis-perfluoroalkyl monomer described in example No. 69.15 g of a silicone oil of Si-based motifs is cast for 1 hour. -H of structure following Me3Si? (SiMe? 23) 220 (SiMeHO) 25SiMe3 (0.1 mole of Si-H motifs). 25 g of toluene are added and it is allowed to react for 1 hour 10 minutes at that temperature. The transformation rate of the Si-H motifs is 25.8%. In a 2000 ml reactor, 18.99 g (0.963 mol) of allyoxi-Hfti-S and 20.76 mg of a KARSTEDT catalyst solution (11.5% Pt) are introduced under nitrogen. It is brought to 98 ° C. Then, 119.39 g (0.0715 mol SiH) of the SiH motif oil functionalized at 25.8% are filtered in 1 hour, by the bis-perfluoroalkyl monomer described in example No. 1. It is allowed to react for 1 hour at 100 °. c. The transformation rate of the Si-H motifs is complete. Let it cool. It is devolatilized under 3 mm Hg at 140 ° C for 6 hours. 86.1 g of a very viscous liquid are recovered. The IR and NMR analyzes confirm the structure of this silicone oil.
EXAMPLE XVI: Synthesis of POS replaced by bi-perfluorinated Gf (beta) bifido grafts v by functions E (hals) = reroll Gf: In a 250 ml reactor, under nitrogen, 120 g of bisphosphate monomer 2 are introduced. perfluoroalkyl which is described in Example IX and 3.5 IU to a catalyst solution of KARSTEDT (11.45% Pt). The reaction mass is brought to 90 ° C. After, a silicone oil of Si-H motifs of following structure is introduced in 1 hour 30 minutes, Me3SiO (SiMe02) 220"(SiMeH?) 25SiMe3 (0.105 mole of Si-H motifs) It is left to react for 46 hours at 90 ° C. The transformation rate of the Si-H motifs is 96.4%, it is devolatilized for 2 hours at 200 ° C under 3 mm Hg, 127.6 g of a viscous limpid oil are recovered, IR and NMR analyzes. confirm the structure of this silicone oil.
Gfß (PHO 118)
EXAMPLE XVII: Determination of the crystallinity rate:
Table I below shows the crystallinity rate measured by RX on certain functionalized monomers and silicones. These results reveal the organization resulting from the particular structure of monomer 2 of bis-perfluoroalkyl motifs described in Example IX.
The differential thermal analysis that was performed on the same products, also shows a peak of crystallization. TABLE 1
EXAMPLE XVIII Synthesis - Application of emulsion and application of POS to mono-perfluorinated Gf bifid grafts and E (betae) grafts: XVIII. 1 . The oils of the following structures were synthesized following the operative protocol as set forth in Examples IX, X, XI, and XII above.
TABLE 2
X and R samples
PHO 105 15 55 C2H5
PHO 107 55 15 C2H5
PHO 127 15 55 CH 2CH2C8F17
PHO 128 15 - 55 C2H5 XVIII. 2 Put into emulsion PHO 105 The following ingredients are mixed: PHO 105: 6 g AD33: 0.5 g GENAPOL X080: 0.1 g C13OEt fatty alcohol Water is added progressively and mixed manually. Then, 7 g H20 are added and emulsified with the help of a SILVERSTON mixer. A white emulsion is obtained (dry extract = 46.3%, average granulometry = 7.965 μm). PHO 107 The following ingredients are mixed: PHO 100 2.5 g AD33 0.5 g Butyldigol 0.25 g BRIG 72 0.5 g Water is added progressively and mixed manually. Then, 10 g H20 is added and emulsified with the help of a SILVERSTON mixer. A light brown emulsion is obtained (dry extract =
31%).
XVIII. In addition to the fluorinated POS according to the invention, commercial perfluorinated polyacrylates are also tested: the FC 396 of 3 M and the AG 850 of ASAHI. The characteristics of the products tested are given in Table 3 below.
* calculated ** dosed Table No. 3: Global characteristics of synthesized oils and commercial products.
XVIII. 4 Two series of tests are carried out: application in solvent. 700 ppm deposit of fluorine (impregnation of a 15 g polyamide PA round mat) from solutions diluted to 1% in trichlorofluoroethane. Those fluorinated POS that are put into work are: PHO 105, 107, 127, 128. FC 396 and AG 850 are also used in solution. Dried 6 minutes at 80 ° C and then thermal 4 minutes at 140 ° C. application in emulsion. 700 ppm deposit of fluorine (spray applied to a 15 g PA round mat) from the emulsions described above: PHO 105 and PHO 107. FC 396 and AG 850 emulsion are also tested. Dried 6 minutes at 80 ° C and then thermal 4 minutes at 140 ° C. The properties of hydrophobicity and oleofsbia are evaluated, by penetration or not of decreasing surface tension liquids (on three drops of liquid). The corresponding number is attributed to the smallest surface tension liquid that does not penetrate after 30 seconds for the oleophobic test and 3 minutes for the hydrophobic test.
TABLE 4: IPA / H20 composition hydrophobicity index
0 0/100 1 10/90 _ 2 20/80 3 30/70 4 40/60 5 50/50 6 60/40 7 70/30 8 80/20 9 90/10 10 100/0
TABLE 5: Oleophobic index Composition 1 Nujol 2 Nujol (65) / n-hexadecane (35)
3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-sctane 8 n-heptane
The compositions are given in volume at 20 ° C.
Results TABLE 6: hydrophobic oleophobia index index
FC 396 (emulsion) 4 4 FC 396 (solvent) 4 3 AG 850 (emulsion) 5 3 AG 850 (solvent) 5 2 PHO 105 (emulsion) 4 2 PHO 105 (solvent) 4 1 PHO 107 (solvent) 4 1 PHO 107 (emulsion) 6 3 PHO 128 (solvent) 4 - 1 XVIII. 5 _ Physico-chemical study 5.1.- Humidification of deposits The transcription of the use value "antisuciedad" in terms of physical-chemical properties, can be summarized with the behavior of the deposit in relation to liquids (humidification) and its behavior in the time in contact with a liquid. 5.2.- Methodology of the study The physical-chemical study put in its place, is as follows: 1 * Deposit of the treatment polymer by means of a winder from 0.25% polymer solutions. The FC 369 (Scotchguard), reference treatment, was also studied. On this basis, 6 families of samples were studied. The sample "as is" or initial and an annealed sample at 140 ° C for 4 minutes. These 2 samples are taken again and submitted: "either to a" wash "test consisting of dropping for 10 minutes, a few drops of water falling from a height of 1 meter (initial and washing, annealing and washing );
either a tempering test in demineralized water for 30 minutes (initial and tempered, annealed and tempered). Obviously, these two tests are intended to know 5 the persistence of the treatment. 2 * Measurement of the angle and its evolution over time (from 0 to 60 seconds) in contact with reference liquids (water and CH2I2). The experiments were carried out on the following products: PHP105, PHO107, PH0127, FC96 and the non-treated polyamide PA66 control. 5.1.2.- Results In Table No. 7, the angles that X5 obtained after 60 seconds were reported.
twenty
TABLE 7
Table No. 7: Evolution of the angles of liquid tests on the treated surfaces or not. The conclusions are the following: * The PHO 127 presents a very strong oleophobic and hydrophobic and remains little sensitive to annealing and washing. * In general, the fluorinated POS products according to the invention (PHO, 105, 107, 127, 128) have a better washing behavior than FC 396. * It is not necessary to "overdose" in perfluorinated groups, to obtain the properties of hydrophobic and oleophobic. The PHO107, for which y = 15, presents comparable results, after annealing, to the other functionalized silicones of the perfluorinated monoester group.
EXAMPLE XIX: Synthesis of new bifunctional silicones in the limbs for epoxies and perfluoroalkyls of the following general formula: Rf Epoxide \ SiMe20 (SiMe20) xSiMe / with preferably x = 0. This type of silicones bifunctionalized for epoxy reasons, could be useful to hydrophobize and oleophobize surfaces (wood, paper) or silicone type matrices. Preparation of:
-SiMe2OSiMe2 / - "P
(a) In a 1 liter flask under nitrogen, introduce: 300 g of Vi-C8F17 (0.647 mol), 250 g of
HSiMe2OSiMe2SiH (1866 mol) and 150 g of M2. Then, 2 g of C02COQ (2857 ppm / total mass) are added. It is left to react for 48 hours at 25 ° C. A CPG analysis shows that the transformation rate of Vi-CQF17 is close to 100%. It is filtered on paper and the M2-c and M'2 are evaporated in excess (100 ° C / 50 mm Hg). The reaction mass is distilled under vacuum and 289 g of a colorless liquid are recovered (T boiling: 93 ° C / 6 mm Hg). Purity is > 98% (GPG). The NMR and IR analyzes confirm the structure of the product. Si-H rate: 1,715 equivalent
lens / kg (Teo: 1673 equivalent / kg). Isolated yield: 77%. obtain: F17c8- \ SiMe20SÍMe2 H (b) In a 100 ml flask under nitrogen, introduce: 23 g of the venilcyclohexene epoxide (0.185 5 mol), 200 g of the preceding product (GPE 1218) (0.34 mol) and 50 g of dry toluene. Then, 10 ppm of platinum / total mass is added in the form of the KARSTEDT catalyst. It is brought to 90 ° C for 24 hours. The transformation rate of the Si-H motifs is close to 100%. The solvent and VCMX are evaporated in excess. 225 g of a slightly yellow oil are recovered whose NMR and IR analysis confirm the structure. Purity is > 98%. The alpha-perfluorinated and omega-perfluorinated dimethyldisiloxane whose formula is given above is obtained.
Claims (19)
1 and Rftal as defined above; * E is a monovalent functional moiety, different from Gf that is defined above, of identical or different nature in the e and e 'siloxyl motifs D and / or the two siloxyl motifs M where it is present and selected, preferably among the groups that 20 present at least one of the following functionalities E- ^ a E13 / _ \ Ei = ^ ™ * (Z,) b - ^, _ U ~ ¡) tM > , I _ 25 in which: * Zj has the same definition as that given above for the definition of Gf, with m greater than or equal to 2; * Z2 corresponds to: ae. OR II / c II O with at least one of the free valences of a carbonyl, attached to an OH, or then also those two valences are both bound to the same oxygen atom; -ße. / CO -CH CO- with the two free valencies of the carbonyls, each linked to an alkoxy in linear or branched C ^ -C; ye »W O Se - -N = C = 0 ou - -NHj ee. Or the free valence of the carbonyl is attached to a linear or branched C-^ - C8 alkoxy, or then also to an OH; with at least one of the free valences of a carbonyl, attached to an OH, to a linear or branched Cj-Cg alkoxy, or then also those two free valences are both bonded to the same oxygen atom; * one and / or the other of the two free valences different from the valence - », is (are) joined to -Z3Rf, & in the case where only one of the aforementioned free valencies is linked to -Z3Rf, and in the case that only one of these two valences is linked to -Z3Rf, then the other valency is attached to OH or to an alkoxy, in which 'linear or branched; R, b ° _ = H or lower alkyl in C? _C6, linear or branched; methyl is preferred; * Z-y, z2 are identical or different from their corresponding ones that intervene in Gf and are described above; * W is as defined above for Gf; / _ \ E2 = amine; E3 = alkoxy; E4 = acyl; E5 = alkoxy; Eg = hydroxy, E7 = trialkoxysilyl; Eg = amide; Eg = ester; E10 = phenol; E-j ^ = arylalkoxy; E12 = aryloxy; E13 = ether-hydroxy.
2. - POS according to clause 1, characterized in that they are of the following formula (1-1): sj) * Gf corresponds to the definition according to clause 1, with h = g = l or h = l & g = 0; * E = E to E13; R, R2, are as defined in clause 1, preferably methyl, propyl or butyl; * C-L + d-L = 3, preferably c-j ^ = 2, d-j ^ = 1; * c2 + d2 = 3, preferably c2 = 2, d2 = 1; * 1 less than or equal to Z less than or equal to 90, preferably 1 less than or equal to Z less than or equal to 50; * 1 less than or equal to and less than or equal to 100, preferably 1 less than or equal to e, less than or equal to 60; * 0 less than or equal to y- ^ less than or equal to 10, preferably 0 less than or equal to y- ^ less than or equal to 5; * 0 less than or equal to and less than or equal to 50, preferably 0 less than or equal to and less than or equal to 25;
3. - POS according to clause 2, characterized in that they are of the following formula (1-1.1): with and, Y? , z, e, Gf & E as defined in clause 1 or 2 and Ralfa, identical or different represent: H or alkyl in C ^ -Cg.
4. - POS according to clause 1, characterized in that they are of the following formula (1-1.2): ¡bl bl (R ^ ÍO ,, "^ R fefS'O ^ - j (R * > £ ¡, ^ '); Gf) b2SiO.; Jy (1.1.2) in which: 5 + Gf is as defined in clause 1; + R1 identical or different from its similar ones of - same index = R, as defined in clause 1, or then also corresponds to a functionality (E) as defined in clause 1, of i0 preference an epoxy-functional radical; + R2 identical or different from its similar ones of the same index, has the same definition as that which is given in clause 1; + a1 + b1 = a2 + b2 = 3 15 a 1 '2 = 2 ° 3' k1 'b2 = 0 or 1; 10 less than or equal to, less than or equal to 100, preferably 0 less than or equal to, less than or equal to 10; 0 less than or equal to less than or equal to 50, 20 preferably 0 less than or equal to p less than or equal to 5; - > the formula in which R1 = CH3, b ^ = 1, b2 = 0: COR10 / G1: - (CHj), - CH 25 \ CORp with R10, R11 equal or different and representing OH alkoxy - ^ - Cg or Z3Rf according to the above, at least one of the radicals R10, R11 = Z3Rf, = 0, y = 0 or 1; - > the formula in which R = CH3, b = b2 = 0: CO R10 / y = 0, p = 1 to 10, preferably 1; - > they are particularly preferred.
5. - POS according to any of clauses 1 to 4, characterized in that they comprise at least one species (I) and / or (II) substituted by at least one perhalogenated Gf residue, preferably perfluorinated, selected in the subgroup of the following radicals: - > (i) with: Ra, R9 independently = H or lower alkyl, Cj-C8, linear or branched, preferably CH3; R10, R11 independently = OH-alkoxy J-Cg, linear or branched, or Z3Rf; one at least of the radicals R ^ °, R11 represents -Z3Rf; i = 0 to 10, preferably 0 to 3, and still more preferably i = 1; - > (ü) 10 - CHR9 (CH ^ SÍR * 5 with Ra, R9, R10, R11 & i as defined above; - > (iü) with R9, R10, R11 & i as defined above; the hexyl ring may optionally be substituted. -_- 25 - > the mixtures of the radicals that precede.
6. POS according to clause 5, characterized in that they comprise at least one species (I) and / or (II) substituted by: - at least one perhalogenated Gf residue, preferably perfluorinated, of formula (i), (ii) or ( iii), according to clause 5; - the radicals R10, R11 of the formula considered to correspond to Z3Rf; preferably to: , 0-CaH¿-CqFarCF, (q = O) - possibly by at least one residue Gf (i), (ii) or (iii), in which one of the radicals R10, R11 is Z3Rf; - the other of these radicals R10, R11 is different from Z3Rf and advantageously corresponds to: OHalkoxyl Cj ^ -C, linear or branched.
7. - POS according to any of clauses 1 to 6, characterized in that they comprise at least one species (I) and / or (II) substituted by at least one residue E selected in the subgroup of the radicals E (ie), (ue ^ ° (ü e) cue correspond to the radicals Gf (i), ( ii) or (iii), respectively according to clause 5, with the small difference that R10, R11 are the same or are not equal &correspond only to OH-alkoxy in C- ^ - Cg, linear or branched.
8. - POS according to any of clauses 1 to 7, characterized in that they also include: * siloxyl motifs: with the radicals R8 of the different motives identical or different from each other and having the same definition as that of R1, R2, Gf or E given above; * Eventually reasons: Q - (SÍO ^
9. - Process for preparing (per) halogenated POS, preferably (per) fluorinated, according to any of clauses 1 to 8, characterized in that it consists essentially of reacting: A) - at least one polyalkylhydrogen-siloxane oil, preferably polymethylhydrogensiloxane; B) - with at least one (per) halogenated, preferably (per) fluorinated olefin, precursor of Gf and of formula (Gfp) ZlpRf 5 in which: * Z-jn = olefinic precursor of Zj_; * Rf as defined in clause 1; C) - and / or with at least one olefin (per) halogenated, preferably (per) fluorinated, of the formula: zlpz2p - in which: * Zlp = olefinic precursor of Z ^ * Z2p = olefinic precursor of Z2; D) - in the presence of an effective amount of metal hydrosilylation catalyst, preferably based on platinum; the reaction product A + C is optionally placed in the presence of a reagent of the type Z3pRf with Z3p = precursor of Z3pRf with Z3p = precursor of Z3 and Rf as defined above, so that grafts Gf = Z- are obtained ^ Rf and / or = Z1Z2Z3Rf; E) - finally with an Ep reagent formed by an olefinic precursor of E; Ep can be hydrosylated with "25" = POS SiH in "presence of D.
10. - Process according to clause 9, characterized: * in which the precursor Ep is of the type: ZlpZ2p with Zlp, olefinic precursor of Z- ^ and Z2p precursor of Z2; Z ^, Z2, Zlp, Z2p are identical or different from their corresponding ones that intervene in Gf and that are described above; * and in which the radicals - ~ zlz2p grafted onto the POS are put in presence with at least one reactive compound carrying a group having at least one functionality E, so as to produce grafts: - Zj ^ E.
11. - Process according to clause 9 or 10, characterized: * in that at least a part of the precursors Z2p of Z2, grafted onto the oil (A), are acid anhydrides; * in which it undergoes at least a part of those anhydrous functions to a hydrolysis, in order to generate free carboxylic extremities; * and in which at least a part of these carboxylic extremities is esterified; ° either with the help of reagents of type Z3pRf; Z3p is a precursor of Z3; Z3 and Rf are as defined in clause 1; ° either with the aid of at least one reactive compound carrying a group having at least one E functionality.
12. - Process for preparing halogenated POS, preferably (perfluorinated), cyclic or linear, according to any of clauses 1 to 8, characterized in that it consists, essentially, in reacting: A) - at least one polyalkylhydrogen-siloxane oil, preferably polymethylhydrogensiloxane; F) - with at least one halogenated olefin, preferably (per) fluorinated, precursor of Gf and of formula (Gfp): in which: * Zlp is the olefinic precursor of radical Zj_, as defined above in clause 1; * Z2, Z3, Rf, h, g, j & k are also defined in clause 1; * with the condition according to which if h = 0, then g = 1 & Z2 becomes an olefinic precursor Z2p; G) - and / or with at least one olefinic precursor Rp of E; 5 D) - in the presence of an effective amount of metal hydrosilylation catalyst, preferably based on platinum.
13. - A method according to clause 12, characterized in that the precursor Gfp of Gf is at least one of the following formulas: with: 0 Ra. R9 independently = H or lower alkyl, C1-Cg, linear or branched, preferably CH3; R10, R11 independently = linear or branched C - ^ - Cg OH alkoxy, or Z3Rf; i = 0 to 10, preferably 0 to 3, and still more than 5 preference i = 1; , (üp) with Ra, R9, R10, R11 & i as defined above; 0 - > (üip) 5 C? N R9, R10, R11 & i as defined above; the hexyl ring may optionally be substituted.
14. - Procedure according to clause 13, or characterized in that the Gfp precursors of the grafts Gf showing one or two perfluorinated R10, R11 groups (R and / or R-j ^ = Z3Rf) and are obtained by putting into reaction according to a transesterification mechanism: > of at least one mobile hydrogen compound consisting of the hydrogenated radical Z3Rf, is desir H-Z3Rf, according to clause l; preferably an alcohol or a thiol; > they are starting products formed by formula blanks (ip). (üp) (iiip), such as are defined in clause 11, and in which at least one of the radicals R10, R i, is a linear or branched alkoxy in C - ^ - Cg.
15. - Process according to any of clauses 9 to 15, characterized in that the olefinic presurer Ep of the graft E is at least one of the formulas (iep), (iiep) and (iiigp), & corresponds respectively to the formulas (ip), (iip) and (iiip), which are given in clause 13 for GFp, with the small difference that R10, Rj are the same or different and correspond only to OH, C1-C6 alkoxy , linear or branched.
16. - Intermediary reaction (synthon) that can be put into work, especially in the procedure according to clauses 12, 13, 14 or 15, characterized in that it is at least one of the following formulas: - > (ip) are: Ra, R9 independently = H or lower alkyl, l "c6alne branched, preferensia CH3; with at least one of the radicals R10, R1 sorresponde to a linear or branched alsoxyl Cj-Cg, methoxyl and to ethoxy and propyl; - > dlp) R / CH2 = CR9 (CH ^ SiR * are R9, Ra, R10, R1 & These are defined above; - > (iüp) with: R9, R10, R11 & i as defined above; the hexyl cyclohexane may optionally be substituted.
17. - Saturated asuosa emulsion in which they are: - suando less a POS according to any of the provisions 1 to 8 or obtained by means of the prosedimiento according to any of the clauses 9 to 15; - in water; 0 - and suando less a tensoastivo.
18. - Application of POS according to any of the provisions 1 to 8 or obtained by means of proceeding according to any of the clauses 9 to 15, by title »J k - anti-foam; - lubricant; - adherent agent; - agent to lower the surface tension; 0 - anti-dirt agent; - oleophobic and / or hydrophobic agent; - raw material to make elastomers or films that resist chemical aggressions and solvents. 5
19. - Anti-fouling composition, in which the following appears: - minus one POS according to any of clauses 1 to 8 or obtained by means of the procedure according to any of clauses 9 to 15; and / or at least one emulsion according to clause 7; - those POS that are put into work, are preferably POS, carriers: 10 * of bifunctional Gf grafts bifunctionalized perhalogenated, perfluorinated radisals, such as are defined in clause 5; * of other E grafts funsionalized by functions other than bi- or monohalogenated perhalogenated / perfluorinated functions, such as are defined in clause 7. * and possibly of grafted bifid Gf grafts monophysicalized by perhalogenated / perfluorinated radisols , which are also defined, in clause 5. 20 EXTRACT The present invention relates to polyfunctional, chemically stable perfluorinated polyorganosiloxanes (POS) comprising, on the one hand, fluorinated side grafts resulting from the hydrosilylation of olefins perfluorinated by SiH and having alkyl and / or alkyl ester clamps, except ethers and, on the other hand, other non-perfluorinated functional E-motifs that can give them diverse and varied physical and chemical properties, which offers them outlets in the somersium for mushas applications. For example, those POS according to the invention are those of the following formula: J I I Gfi Ei? E E3 According to another of its aspects, the invention aims to improve the preparation of these polyfunctional perfluorinated POS. It is applied in the following processes: anti-foam; to lower the tension of superfisie; anti-ensusiado; anti-adherensia; lubrisante; oleophobization and / or hydrophobization; coatings; etc...
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9509268 | 1995-07-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA96002965A true MXPA96002965A (en) | 1999-05-31 |
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