WO2000020425A1 - Silanes and polyorganosiloxanes with boronate function(s) - Google Patents
Silanes and polyorganosiloxanes with boronate function(s) Download PDFInfo
- Publication number
- WO2000020425A1 WO2000020425A1 PCT/FR1999/002362 FR9902362W WO0020425A1 WO 2000020425 A1 WO2000020425 A1 WO 2000020425A1 FR 9902362 W FR9902362 W FR 9902362W WO 0020425 A1 WO0020425 A1 WO 0020425A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- chosen
- silane
- radicals
- gold
- Prior art date
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- 150000004756 silanes Chemical class 0.000 title claims abstract description 17
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical group OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 125000005621 boronate group Chemical group 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 19
- -1 methoxy, ethoxy Chemical group 0.000 claims description 18
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 239000010931 gold Substances 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 238000006197 hydroboration reaction Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000012764 mineral filler Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000002280 amphoteric surfactant Substances 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 230000005661 hydrophobic surface Effects 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 2
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- PROLJSIXZFYNRY-UHFFFAOYSA-N dibutoxy(prop-2-enyl)borane Chemical compound CCCCOB(CC=C)OCCCC PROLJSIXZFYNRY-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 3
- ULHDSMBBOXGDRG-UHFFFAOYSA-N tris(prop-2-enyl)borane Chemical compound C=CCB(CC=C)CC=C ULHDSMBBOXGDRG-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 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 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229920005565 cyclic polymer Polymers 0.000 description 2
- 150000004759 cyclic silanes Chemical class 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical class CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 0 C*CCCN(*)O Chemical compound C*CCCN(*)O 0.000 description 1
- XDYHPCWDKWSHGT-UHFFFAOYSA-N CB(C)c1ccc(CC[Si](C)(OC)OC)cc1 Chemical compound CB(C)c1ccc(CC[Si](C)(OC)OC)cc1 XDYHPCWDKWSHGT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DKJLZAZNYAZWOZ-UHFFFAOYSA-N [SiH4].OBO Chemical class [SiH4].OBO DKJLZAZNYAZWOZ-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- DNAJDTIOMGISDS-UHFFFAOYSA-N prop-2-enylsilane Chemical compound [SiH3]CC=C DNAJDTIOMGISDS-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000001957 sucroglyceride Substances 0.000 description 1
- 235000010964 sucroglyceride Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
Definitions
- the present invention relates to new functionalized silanes and polyorganosiloxanes, as well as to compositions comprising as base polymer a polyorganosiloxane of this type, capable of crosslinking into an elastomer in the presence of air humidity without the aid of a catalyst. crosslinking. It also relates to the processes for preparing these silanes and polyorganosiloxanes.
- Monocomponent silicone compositions capable of hardening or crosslinking by polycondensation reaction by exposure at room temperature to air humidity are well known in the art. 'skilled in the art and are described in many patent documents.
- a tin-based catalyst is generally used which can generate degradation reactions of the elastomer formed during the aging of the latter.
- the main objective of the invention is to provide a silicone composition based on polyorganosiloxanes which is stable on storage in the absence of moisture and which is curable by the action of atmospheric humidity without the aid of a catalyst. of crosslinking, for the production of thin layers and thick layers.
- the present invention relates to the silanes which are used to make the polyorganosiloxanes according to the invention and which correspond to formula (1):
- R 1 is chosen from a monovalent hydrocarbon group, optionally substituted by halogen atoms, - X is a hydrolyzable group,
- - b is chosen from 0, 1 and 2
- . c and d are integers ranging from 0 to 18
- . e is chosen from 0 and 1.
- the R 2 groups which may be identical or different, are chosen from a hydrogen atom, a linear or branched C1-C20 alkyl radical, preferably 01 -06, C5-C8 cycloalkyl, C6-C12 aryl, or can form with the boron and oxygen atoms a heterocyle comprising from 5 to 8 elements (atoms in the heterocyle), preferably from 5 to 6, the carbons being possibly substituted,
- silane excluded by disclaimer, was disclosed by M. Glad et al., J. Ohromato., 1985, 347: 1 1-23. It is used to produce a polysiloxane coating on porous silica to allow the taking of molecular fingerprints or for the fixation of enzymes, in the field of chromatography.
- Z is a phenylene group
- R 2 linear or branched alkyl groups at 01 -04 and / or H.
- the radicals R 1 identical or different, are hydrocarbon radicals at 01 to 010, substituted or not by halogen atoms.
- radicals include in particular: - alkyl and haloalkyl radicals in C -C10, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethyl hexyl, octyl, decyl, 3,3,3-trifluoro radicals propyl, trifluoro-4,4,4 butyl, pentafluoro-4,4,4, 3,3 butyl, the cycloalkyl and halocycloalkyl radicals in C3-C10, preferably C5-C8, such as the cyclopentyie, cyclohexyl, methylcyclohexyl radicals, propylcyclohexyl, 2,3-difluoro-cyclobutyl, 3,4-difluoro-5-methyl-cycloheptyl, C2-C4 alkenyl radicals, such as vinyl, allyl, but
- the hydrolyzable radicals X which are identical or different, are more specifically chosen from a halogen atom (preferably chlorine) and from the substituted amino-N, substituted amido-N, aminoxy-N, disubstituted N, ketiminoxy, aldiminoxy radicals, alkoxy, alkoxyalkylene-oxy, enoxy, acyloxy.
- a halogen atom preferably chlorine
- substituted amino-N substituted amido-N, aminoxy-N, disubstituted N
- ketiminoxy aldiminoxy radicals
- alkoxy alkoxyalkylene-oxy
- enoxy acyloxy
- silanes particularly suitable are methoxy, ethoxy and acetoxy. Mention may be made, as preferred silanes, of the following:
- the silanes can be prepared by a hydrosilylation reaction between a silane of formula (3)
- . c and d are integers ranging from 0 to 18
- . c + d is at most equal to 18
- R 2 , Z and e have the same meanings as above.
- This reaction is carried out in the presence of a conventional hydrosilylation catalyst such as rhodium, platinum, optionally in the presence of an inert solvent such as toluene or cyclohexane, at a temperature between room temperature and 120 ° C.
- a conventional hydrosilylation catalyst such as rhodium, platinum
- an inert solvent such as toluene or cyclohexane
- silanes can also be prepared by a hydroboration reaction by reacting together:
- R 2 is as above, and:
- This reaction is carried out with or without a catalyst, optionally in the presence of a solvent such as cyclohexane, at a temperature ranging from -50 ° C. to + 100 ° C.
- these alkoxy groups are preferably methox ' y, ethoxy, propyloxy, butyloxy, pentyloxy or hexyloxy groups.
- the present invention also relates to polyfunctional polyorganosiloxanes having per molecule at least one unit corresponding to the general formula (7):
- - f is chosen from 0, 1 or 2
- g is chosen from 0, 1 or 2
- the polyfunctional polyorganosiloxane can have, on the one hand, at least one motif (7) taken without its disclaimer, and, on the other hand, other siloxy units corresponding to formula (8):
- - R 1 has the same meaning as in formula (1) - h is chosen from 0, 1, 2 and 3.
- R 1 is chosen from methyl, phenyl and vinyl radicals, 80% by number of the radicals R 1 being methyl.
- the polyorganosiloxanes according to the invention can therefore have a linear, cyclic or branched structure.
- Linear or cyclic polyorganosiloxanes are preferred having, per molecule, at least one unit of formula (7) where f + g is other than zero, and optionally at least one unit of formula (8) where h is 2 or 3.
- the present invention relates in particular to the polyfunctional polyorganosiloxanes of formula (9): R ' R 1 R 1 R
- R 1 , X and Y have the same meaning as in the formula (1
- X ' chosen from the radicals Y, R, hydroxyl and hydrogen atom
- the radicals R 5 identical or different, are chosen from the radicals R 1 and X i is an integer between 0 and 1000
- the invention also relates to those of formula (10):
- R 1 and Y have the meaning given to the formula ( ⁇ C ⁇
- - k is an integer between 0 and 9 inclusive
- k + I is an integer between 1 and 9 inclusive
- k + I is between 3 and 10 inclusive.
- These polyfunctional polyorganosiloxanes can be prepared according to different methods.
- a first method consists in carrying out a hydrosilylation reaction between:
- Certain polyorganosiloxanes can be prepared by a hydroboration reaction between the compound of formula (5), and:
- reaction mixture comprising cyclic polymers of formula (10) and / or linear polymers of formula (9) blocked at each of their ends by a hydroxyl group or by the unit :
- the polycondensation can also be stopped by adding, at the end of the reaction, an organosilicon compound capable of reacting with the terminal hydroxyls of the polymer of formula (9) formed, this organosilicon compound being able to correspond to the formulas: R 1 3 SiCI, R 1 3 SiNHSiR 1 3 and R 1 3 SiOSiR 1 3 .
- the duration of the hydrolysis can be between a few seconds and several hours.
- the aqueous phase is separated from the siloxane phase by any suitable physical means, generally by decantation and / or extraction with an organic solvent such as isopropyl ether or toluene.
- an organic solvent such as isopropyl ether or toluene.
- the polyfunctional polyorganosiloxanes of the invention crosslink to form boroxins very stable to UV and to temperature. They can also be dissolved in water in the form of stable boronic acid, crosslinkable into boroxin by elimination of the water.
- These polydiorganosiloxanes can be used pure to form, for example, coatings after crosslinking, in the absence of catalyst, in the presence of moisture or by elimination of water as the case may be.
- They are more particularly usable as basic diorganopolysiloxane polymers, within a silicone composition crosslinkable into an elastomer, in the absence of catalyst, by exposure to atmospheric humidity or by elimination of water, as the case may be.
- silicone compositions can be packaged in a single package and are stable on storage.
- the present invention therefore relates to an organopolysiloxane composition, stable on storage in the absence of moisture and capable of crosslinking by exposure to moisture in the absence of crosslinking catalyst, comprising: (A) - 100 parts by weight of at least one polymer of formula (7) taken without its disclaimer, with possibly motifs (8), or of formula (9) or (10), in accordance with the invention (B ) - from 0 to 250 parts by weight of a mineral filler. It also relates to an aqueous organopolysiloxane composition, stable in storage and capable of crosslinking by elimination of water, in the absence of crosslinking catalyst, comprising:
- (C) - from 0.5 to 50, preferably from 3 to 20 parts by weight of water
- the mineral fillers (B) are used in an amount of 0 to 250 parts, preferably 20 to 200 parts, per 100 parts of polymer (A).
- fillers can be in the form of very finely divided products, the average particle diameter of which is less than 0.1 micrometer.
- these fillers are combustion silicas and precipitation silicas; their BET specific surface area is generally greater than 40 m 2 / g.
- These fillers can also be in the form of more roughly divided products, with an average particle diameter greater than 0.1 micrometer.
- Examples of such fillers include ground quartz, diatomic silicas, calcium carbonate, calcined clay, titanium oxide of the rutile type, iron, zinc, chromium, zirconium oxides. , magnesium, the different forms of alumina (hydrated or not), boron nitride, barium metaborate, glass microbeads; their specific surface is generally less than 30 m 2 / g.
- These fillers (B) may have been modified at the surface by treatment with the various organosilicon compounds usually used for this use.
- these organosilicon compounds can be organochlorosilanes, diorganocyclopolysiloxanes, hexaorganodisiloxanes, hexaorganodisilazanes or diorganocyclopolysiloxanes (French patents FR-A-1,126,884, FR-A-1,136,885, FR-A-1,236,505; English patent GB -A-1 024 234).
- the treated fillers contain, in most cases, from 3 to 30% of their weight of organosilicon compounds.
- the fillers (B) can consist of a mixture of several types of fillers of different particle size.
- the surfactants (D) which may be used can be nonionic with an HLB greater than 10, preferably of the order of 10 to 20, anionic, cationic, zwitterionic or amphoteric with an HLB greater than 10.
- the nonionic surfactants can be chosen from alkoxylated fatty acids, polyalkoxylated alkyphenols, polyalkoxylated fatty alcohols, polyalkoxylated or polyglycerolated fatty amides, polyglycerolated alcohols and alphadiols, ethylene oxide block polymers propylene, as well as alkylglucosides, alkylpolyglucosides, sucroethers, sucroesters, sucroglycerides, sorbitan esters, and ethoxylated compounds of these sugar derivatives, having an HLB of at least 10.
- the anionic surfactants can be chosen from alkylbenzene sulfonates, alkysulfates, alkylethersulfates, alkylarylethersulfates, dialkylsulfosuccinates, alkylphosphates, etherphosphates, of alkali metals having an HLB of at least 10.
- surfactants cationic there may be mentioned aliphatic or aromatic fatty amines, aliphatic fatty amides, quaternary ammonium derivatives, having an HLB of at least 10.
- betaines and their derivatives there may be mentioned betaines and their derivatives, sultaines and their derivatives, lecithins, imidazoline derivatives, glycinates and their derivatives, aminopropionates, fatty amine oxides having an HLB of at least 10.
- the polyorganosiloxanes with boronate functions according to the invention can be used in the pure state or in the form of compositions of the type of those mentioned above, for example in the field of packaging of textile materials and in the field of coating of metals, natural stones or various construction articles based on cement, to give them non-stick and / or hydrophobic surface properties.
- the invention therefore also relates to this use as well as the method of treatment of these different materials or substrates, in which these substrates are coated with the polyorganosiloxanes or the compositions according to the invention, so as to confer on these substrates, after crosslinking , the adherent and / or hydrophobic properties.
- Example 2 Hydrosilylation of an Si-H oil with the allyl dibutoxy borane obtained in Example 1:
- the allyl dibutoxy borane and the catalyst are introduced into a flask (100 ml three-necked flask with mechanical stirrer). The oil is slowly poured over the alkene. The reaction medium is then heated to around 70-75 ° C for 2 hours.
- IR spectrometry makes it possible to follow the evolution of the reaction by monitoring the disappearance of the SiH band (around 2100 cm ⁇ 1 ).
- the unreacted reagents are removed by heating under vacuum (13.3 10 2 Pa.) around 110-120 ° C.
- the polyorganosiloxane obtained corresponds to the following formula:
- Example 5 Hydrosilylation of allyldibutoxyborane according to Example 1 with the cyclic polysiloxane of Example 4 to obtain 1, 3,5,7-tetra- (3- (dibutoxyboronate) propyl) -1, 3,5,7 - tetramethyl-cyclotetrasiloxane:
- allyldibutoxyborane (1.8 g, 9.1 mmol) and Karstedt catalyst (1.10 "4 mole of platinum per mole of allyldibutoxyborane) are mixed and heated to 70 ° C. , the cyclic silane (0.5 ml, 2.1 mmol) is added. The solution is then heated at 70 ° C for 4 h. The solvent is evaporated off under reduced pressure and the volatile by-products and the excess of allyldibutoxyborane are extracted by distillation on Kugeirohr (100 ° C / 0.2 mm Hg, ie 26.6 Pa). 1.6 g of the desired product having the formula:
- Example 7 Hydrosilylation of an Si-H Oil with the Allyl Diisopropyloxy Borane Obtained in Example 6:
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Abstract
The invention concerns silanes of formula (1) wherein Y is a boronate group of formula (2), wherein: c and d are integers ranging from 0 to 18; c + d = 0 to 18; e is selected between 0 and 1; Z is a divalent heterocarbon group comprising one or several heteroatoms such as O, S, and/or N. The invention also concerns the corresponding polyorganosiloxanes, the methods for preparing them and compositions containing them.
Description
Silanes et polyorganosiloxanes à foτιction(s) boronate Boronate silanes and polyorganosiloxanes
La présente invention concerne de nouveaux silanes et polyorganosiloxanes fonctionnalisés, ainsi que les compositions comportant comme polymère de base un polyorganosiloxane de ce type, capable de réticuler en un élastomère en présence de l'humidité de l'air sans le concours d'un catalyseur de réticulation. Elle a aussi pour objet les procédés de préparation de ces silanes et polyorganosiloxanes.The present invention relates to new functionalized silanes and polyorganosiloxanes, as well as to compositions comprising as base polymer a polyorganosiloxane of this type, capable of crosslinking into an elastomer in the presence of air humidity without the aid of a catalyst. crosslinking. It also relates to the processes for preparing these silanes and polyorganosiloxanes.
Des compositions silicones monocomposantes (c'est-à-dire se présentant sous la forme d'un seul emballage) capables de durcir ou réticuler par réaction de polycondensation par exposition à température ambiante à l'humidité de l'air sont bien connues de l'homme du métier et sont décrites dans de nombreux documents brevets. On utilise généralement dans ce cadre un catalyseur à base d'étain qui peut générer des réactions de dégradation de Pélastomère formé au cours du vieillissement de ce dernier.Monocomponent silicone compositions (that is to say being presented in the form of a single package) capable of hardening or crosslinking by polycondensation reaction by exposure at room temperature to air humidity are well known in the art. 'skilled in the art and are described in many patent documents. In this context, a tin-based catalyst is generally used which can generate degradation reactions of the elastomer formed during the aging of the latter.
L'objectif principal de l'invention est de proposer une composition silicone à base de polyorganosiloxanes qui soit stable au stockage en l'absence d'humidité et qui soit durcissable par l'action de l'humidité atmosphérique sans le concours d'un catalyseur de réticulation, pour la réalisation de couches minces et de couches épaisses.The main objective of the invention is to provide a silicone composition based on polyorganosiloxanes which is stable on storage in the absence of moisture and which is curable by the action of atmospheric humidity without the aid of a catalyst. of crosslinking, for the production of thin layers and thick layers.
Dans un premier objet, la présente invention vise les silanes qui servent à faire les polyorganosiloxanes selon l'invention et qui répondent à la formule (1 ) :In a first object, the present invention relates to the silanes which are used to make the polyorganosiloxanes according to the invention and which correspond to formula (1):
YY
dans laquelle :in which :
R1 est choisi parmi un groupe hydrocarboné monovalent, éventuellement substitué par des atomes d'halogènes, - X est un groupe hydrolysable,R 1 is chosen from a monovalent hydrocarbon group, optionally substituted by halogen atoms, - X is a hydrolyzable group,
- a est choisi parmi 1 , 2 et 3,- a is chosen from 1, 2 and 3,
- b est choisi parmi 0, 1 et 2,- b is chosen from 0, 1 and 2,
- a + b = 3
Y est un groupe boronate de formule (2)- a + b = 3 Y is a boronate group of formula (2)
ORGOLD
CH, CH (CH2 2)1 C (CH2 2)' r BCH, CH (CH 2 2) 1 C (CH 2 2) 'r B
ORGOLD
dans laquelle :in which :
. c et d sont des entiers allant de 0 à 18. c and d are integers ranging from 0 to 18
. c + d = 0 à 18. c + d = 0 to 18
. e est choisi parmi 0 et 1.. e is chosen from 0 and 1.
. Z est un groupe divalent hétérocarboné comportant un ou plusieurs hétéroatomes comme O, S et/ou N ; conviennent bien : -O-, -CO-, -COO-, phénylène, -NR'- avec R' =. Z is a divalent heterocarbon group having one or more heteroatoms such as O, S and / or N; are suitable: -O-, -CO-, -COO-, phenylene, -NR'- with R '=
H ou alkyle linéaire ou ramifié en C1 -C4, -S-H or linear or branched C1-C4 alkyl, -S-
. les groupements R2, qui peuvent être identiques ou différents, sont choisis parmi atome d'hydrogène, radical alkyle linéaire ou ramifié en C1 -C20, de préférence 01 -06, cycloalkyle en C5-C8, aryle en C6-C12, ou peuvent former avec les atomes de bore et d'oxygène un hétérocyle comportant de 5 à 8 éléments (atomes dans l'hétérocyle), de préférence de 5 à 6, les carbones pouvant être éventuellement substitués,. the R 2 groups, which may be identical or different, are chosen from a hydrogen atom, a linear or branched C1-C20 alkyl radical, preferably 01 -06, C5-C8 cycloalkyl, C6-C12 aryl, or can form with the boron and oxygen atoms a heterocyle comprising from 5 to 8 elements (atoms in the heterocyle), preferably from 5 to 6, the carbons being possibly substituted,
étant exclu le silane de formulebeing excluded the silane of formula
Ce silane particulier, exclu par disclaimer, a été divulgué par M. Glad et al., J. Ohromato., 1985, 347 : 1 1-23. Il sert à produire un revêtement polysiloxane sur de la silice poreuse pour permettre la prise d'empreintes moléculaires ou pour la fixation d'enzymes, dans le domaine de la chromatographie.This particular silane, excluded by disclaimer, was disclosed by M. Glad et al., J. Ohromato., 1985, 347: 1 1-23. It is used to produce a polysiloxane coating on porous silica to allow the taking of molecular fingerprints or for the fixation of enzymes, in the field of chromatography.
De préférence, dans la formule (2), on choisira : soit : . c + d = 0 ou 1Preferably, in formula (2), we will choose: either:. c + d = 0 or 1
. e = 0
. R2 = groupements alkyles linéaires ou ramifiés en C1 -C4 et/ou H, soit : . c = 0 ou 1 . d = 0 . e = 1 . Z est un groupe phénylène. e = 0 . R 2 = linear or branched C1-C4 and / or H alkyl groups, ie:. c = 0 or 1. d = 0. e = 1. Z is a phenylene group
. R2 = groupements alkyles linéaires ou ramifiés en 01 -04 et/ou H. De préférence, dans la formule (1 ), les radicaux R1, identiques ou différents, sont des radicaux hydrocarbonés en 01 à 010, substitués ou non par des atomes d'halogènes. Ces radicaux englobent notamment : - les radicaux alkyles et halogénoalkyies en d -C10, tels que les radicaux méthyle, éthyle, propyle, isopropyle, butyle, pentyle, hexyle, éthyl-2 hexyle, octyle, décyle, trifluoro-3,3,3 propyle, trifIuoro-4,4,4 butyle, pentafluoro-4,4,4, 3,3 butyle, les radicaux cycloalkyles et halogénocycloalkyles en C3-C10, de préférence C5-C8, tels que les radicaux cyclopentyie, cyclohexyle, méthylcyclohexyle, propylcyclohexyle, difluoro-2,3 cyclobutyle, difluoro-3,4 méthyl-5 cycloheptyle, les radicaux alcényles en C2-C4, tels que les radicaux vinyle, allyle, butène-2 yle, les radicaux aryles et halogénoaryles mononucléaires en C6-C10, tels que les radicaux phényle, tolyle, xylyle, chlorophényle, dichlorophényle, trichlorophényle. Les radicaux méthyle, phényle, vinyle et trifluoro-3,3,3 propyle sont les radicaux • préférés.. R 2 = linear or branched alkyl groups at 01 -04 and / or H. Preferably, in formula (1), the radicals R 1 , identical or different, are hydrocarbon radicals at 01 to 010, substituted or not by halogen atoms. These radicals include in particular: - alkyl and haloalkyl radicals in C -C10, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethyl hexyl, octyl, decyl, 3,3,3-trifluoro radicals propyl, trifluoro-4,4,4 butyl, pentafluoro-4,4,4, 3,3 butyl, the cycloalkyl and halocycloalkyl radicals in C3-C10, preferably C5-C8, such as the cyclopentyie, cyclohexyl, methylcyclohexyl radicals, propylcyclohexyl, 2,3-difluoro-cyclobutyl, 3,4-difluoro-5-methyl-cycloheptyl, C2-C4 alkenyl radicals, such as vinyl, allyl, butene-2 yl radicals, C6-C10 mononuclear aryl and haloaryl radicals , such as phenyl, tolyl, xylyl, chlorophenyl, dichlorophenyl, trichlorophenyl radicals. The methyl, phenyl, vinyl and 3,3,3-trifluoropropyl radicals are the preferred radicals.
Les radicaux hydrolysables X, identiques ou différents, sont plus spécifiquement choisis parmi un atome d'halogène (de préférence le chlore) et parmi les radicaux amino- N substitués, amido-N substitué, aminoxy-N,N disubstitué, cétiminoxy, aldiminoxy, alcoxy, alcoxyalkylène-oxy, enoxy, acyloxy. Pour plus de détails concernant les radicaux X utilisables, l'homme du métier pourra se reporter à EP-B1 -430 826.The hydrolyzable radicals X, which are identical or different, are more specifically chosen from a halogen atom (preferably chlorine) and from the substituted amino-N, substituted amido-N, aminoxy-N, disubstituted N, ketiminoxy, aldiminoxy radicals, alkoxy, alkoxyalkylene-oxy, enoxy, acyloxy. For more details concerning the radicals X which can be used, a person skilled in the art can refer to EP-B1 -430 826.
Conviennent particulièrement les méthoxy, éthoxy et acétoxy. A titre de silanes préférés, on peut citer ceux qui suivent :Particularly suitable are methoxy, ethoxy and acetoxy. Mention may be made, as preferred silanes, of the following:
OEtAnd
• B. (B) • B. (B)
EtO- OEtEtO- OEt
OEtAnd
OMeOMe
MeMe
MeMe
Les silanes peuvent être préparés par une réaction d'hydrosilylation entre un silane de formule (3)The silanes can be prepared by a hydrosilylation reaction between a silane of formula (3)
X S i ( R ) b HX S i (R) b H
dans laquelle X, a, R1 et b ont les mêmes significations que ci-dessus, et - un alkyldialcoxyborane insaturé de formule (4)
ORin which X, a, R 1 and b have the same meanings as above, and - an unsaturated alkyldialcoxyborane of formula (4) GOLD
ORGOLD
dans laquelle :in which :
. c et d sont des entiers allant de 0 à 18. c and d are integers ranging from 0 to 18
. c + d est au plus égal à 18. c + d is at most equal to 18
. R2, Z et e ont les mêmes significations que ci-dessus.. R 2 , Z and e have the same meanings as above.
Cette réaction est menée en présence d'un catalyseur classique d'hydrosilylation tel que le rhodium, le platine, en présence éventuellement d'un solvant inerte tel que toluène ou cyclohexane, à température comprise entre la température ambiante et 120°C.This reaction is carried out in the presence of a conventional hydrosilylation catalyst such as rhodium, platinum, optionally in the presence of an inert solvent such as toluene or cyclohexane, at a temperature between room temperature and 120 ° C.
De préférence, l' alkyldialcoxyborane insaturé est tel que c = 0 ou 1 , e = d = 0.Preferably, the unsaturated alkyldialcoxyborane is such that c = 0 or 1, e = d = 0.
Certains silanes peuvent aussi être préparés par une réaction d'hydroboration en faisant réagir ensemble :Certain silanes can also be prepared by a hydroboration reaction by reacting together:
O RGOLD
H BH B
O RGOLD
(5),(5),
dans laquelle R2 est comme ci-dessus, et :in which R 2 is as above, and:
(6)(6)
Xa Si (R ) ,X a Si (R),
(CH2)C (CH2)d. CH = CH.(CH 2 ) C (CH 2 ) d . CH = CH.
dans laquelle :in which :
. c' = 2 à 18 . d' = 0 à 16 . c' + d' = 2 à 18 . R1, b, X, a, Z, e ont les mêmes significations que ci-dessus,
. avec la possibilité, lorsque e = 0, que c' = 0 et d' = 0 ou 1 (c' + d' = 0 ou 1).. c '= 2 to 18. from = 0 to 16. c '+ d' = 2 to 18. R 1 , b, X, a, Z, e have the same meanings as above, . with the possibility, when e = 0, that c '= 0 and d' = 0 or 1 (c '+ d' = 0 or 1).
Cette réaction est menée avec ou sans catalyseur, éventuellement en présence d'un solvant comme le cyclohexane, à une température allant de -50° C à + 100°C.This reaction is carried out with or without a catalyst, optionally in the presence of a solvent such as cyclohexane, at a temperature ranging from -50 ° C. to + 100 ° C.
A titre d'exemples préférés, des silanes fonctionnalisés selon l'invention peuvent être préparés par hydrosilylation d'un vinyidialcoxyborane (c = 0, formule (4)) ou d'un allyle dialcoxyborane (c = 1 , formule (4)), ou par hydroboration d'un vinylsilane (c' = d' = e = 0, formule (6)) ou d'un allylsilane (c' = 1 , e = d' = 0, formule (6)). On peut encore préciser que ces groupements alcoxy sont de préférence des groupements méthox'y, éthoxy, propyloxy, butyloxy, pentyloxy ou hexyloxy. On citera à titre d'exemple approprié, l'allyle dibutoxy borane, encore appelé allyle boronate de butyle, avec dans la formule (4) c = 1 , d = e = 0, R2 = butyle.As preferred examples, silanes functionalized according to the invention can be prepared by hydrosilylation of a vinyidialcoxyborane (c = 0, formula (4)) or of an allyl dialcoxyborane (c = 1, formula (4)), or by hydroboration of a vinylsilane (c '= d' = e = 0, formula (6)) or of an allylsilane (c '= 1, e = d' = 0, formula (6)). It can also be specified that these alkoxy groups are preferably methox ' y, ethoxy, propyloxy, butyloxy, pentyloxy or hexyloxy groups. As an appropriate example, mention will be made of allyl dibutoxy borane, also called allyl butyl boronate, with in formula (4) c = 1, d = e = 0, R 2 = butyl.
Les silanes fonctionnalisés de formule (1) peuvent être utilisés en tant que tels, notamment comme promoteurs d'adhérence dans des compositions élastomériques ou comme agent de réticulation dans des compositions silicones réticulant par des réactions de polycondensation (de préférence alors silanes (1) avec a = 2 ou 3).The functionalized silanes of formula (1) can be used as such, in particular as adhesion promoters in elastomeric compositions or as crosslinking agent in silicone compositions crosslinking by polycondensation reactions (preferably then silanes (1) with a = 2 or 3).
Dans son deuxième objet, la présente invention vise aussi les polyorganosiloxanes polyfonctionnels présentant par molécule au moins un motif répondant à la formule générale (7) :In its second object, the present invention also relates to polyfunctional polyorganosiloxanes having per molecule at least one unit corresponding to the general formula (7):
YY
dans laquelle :in which :
- R1, X et Y ont la même signification qu'à la formule (1) ,- R 1 , X and Y have the same meaning as in formula (1),
- f est choisi parmi 0, 1 ou 2 , g est choisi parmi 0, 1 ou 2,- f is chosen from 0, 1 or 2, g is chosen from 0, 1 or 2,
- f + g est au plus égal à 2, étant exclu le polyorganosiloxane dans lequel f + g = 0 et Y est tel que :
- f + g is at most equal to 2, being excluded the polyorganosiloxane in which f + g = 0 and Y is such that:
Le polyorganosiloxane polyfonctionnel peut présenter d'une part au moins un motif (7) pris sans son disclaimer et d'autre part d'autres motifs siloxyles répondant à la formule (8) :The polyfunctional polyorganosiloxane can have, on the one hand, at least one motif (7) taken without its disclaimer, and, on the other hand, other siloxy units corresponding to formula (8):
(R ) l (O)(R) l (O)
4 - h4 - h
dans laquelle :in which :
- R1 a la même signification qu'à la formule (1) - h est choisi parmi 0, 1 , 2 et 3.- R 1 has the same meaning as in formula (1) - h is chosen from 0, 1, 2 and 3.
De préférence, R1 est choisi parmi les radicaux méthyle, phényle et vinyle, 80 % en nombre des radicaux R1 étant méthyle.Preferably, R 1 is chosen from methyl, phenyl and vinyl radicals, 80% by number of the radicals R 1 being methyl.
Les polyorganosiloxanes selon l'invention peuvent donc présenter une structure linéaire, cyclique ou ramifiée. On préfère des polyorganosiloxanes linéaires ou cycliques présentant par molécule au moins un motif de formule (7) où f + g est différent de zéro, et éventuellement au moins un motif de formule (8) où h est égal à 2 ou 3.The polyorganosiloxanes according to the invention can therefore have a linear, cyclic or branched structure. Linear or cyclic polyorganosiloxanes are preferred having, per molecule, at least one unit of formula (7) where f + g is other than zero, and optionally at least one unit of formula (8) where h is 2 or 3.
De tels polymères linéaires ou cycliques peuvent éventuellement comprendre des motifs T de formule (7) où f + g = 0 et/ou des motifs T de formule (8) où h = 1 et/ou éventuellement des motifs Q de formule (8) où h = 0 dans la proportion d'au plus 2 % (cesSuch linear or cyclic polymers may optionally include T units of formula (7) where f + g = 0 and / or T units of formula (8) where h = 1 and / or optionally Q units of formula (8) where h = 0 in the proportion of at most 2% (these
% exprimant le nombre de motifs T et/ou Q pour 100 atomes de silicium).% expressing the number of T and / or Q units per 100 silicon atoms).
La présente invention vise notamment les polyorganosiloxanes polyfonctionnels de formule (9) :
R' R 1 R 1 RThe present invention relates in particular to the polyfunctional polyorganosiloxanes of formula (9): R ' R 1 R 1 R
X' - • Si O -Si • O -Si O- -Si X'X '- • If O -Si • O -Si O- -Si X'
R- R 1 Y R~ R- R 1 YR ~
dans laquelle :in which :
R1, X et Y ont la même signification que dans la formule (1
R 1 , X and Y have the same meaning as in the formula (1
X' est choisi parmi les radicaux Y, R, hydroxyle et atome d'hydrogène, les radicaux R5, identiques ou différents, sont choisis parmi les radicaux R1 et X i est un nombre entier compris entre 0 et 1000, j est un nombre entier compris entre 0 et 50, si j = 0, au moins 1 des radicaux X' est Y.X 'is chosen from the radicals Y, R, hydroxyl and hydrogen atom, the radicals R 5 , identical or different, are chosen from the radicals R 1 and X i is an integer between 0 and 1000, j is a integer between 0 and 50, if j = 0, at least 1 of the radicals X 'is Y.
L'invention vise aussi ceux de formule (10) :The invention also relates to those of formula (10):
R1 et Y ont la signification donnée à la formule (\\C~R 1 and Y have the meaning given to the formula (\\ C ~
- k est un nombre entier compris entre 0 et 9 inclus,- k is an integer between 0 and 9 inclusive,
- I est un nombre entier compris entre 1 et 9 inclus, k + I est compris entre 3 et 10 inclus.- I is an integer between 1 and 9 inclusive, k + I is between 3 and 10 inclusive.
Ces polyorganosiloxanes polyfonctionnels peuvent être préparés suivant différents procédés.These polyfunctional polyorganosiloxanes can be prepared according to different methods.
Un premier procédé consiste à effectuer une réaction d'hydrosilylation entre :A first method consists in carrying out a hydrosilylation reaction between:
- un polyorganosiloxane présentant par molécule au moins un motif de formule (11 ) :
Ha polyorganosiloxane having per molecule at least one unit of formula (11): H
(X) f Si — (O)(X) f Si - (O)
3 - (f + g)3 - (f + g)
(R ) g(R) g
dans laquelle X, f, R1, g ont les mêmes significations qu'à la formule (7) prise sans son disclaimer, et un alkyldialcoxy borane insaturé de formule (4) ci-dessus.in which X, f, R 1 , g have the same meanings as in formula (7) taken without its disclaimer, and an unsaturated alkyldialcoxy borane of formula (4) above.
De préférence, le composé de formule (4) est tel que c = 0 ou 1 et e = d = 0.Preferably, the compound of formula (4) is such that c = 0 or 1 and e = d = 0.
Certains polyorganosiloxanes peuvent être préparés par une réaction d'hydroboration entre le composé de formule (5), et :Certain polyorganosiloxanes can be prepared by a hydroboration reaction between the compound of formula (5), and:
(CH2 2)'C (CH, 2)>d' -CH = CH.(CH 2 2) 'C (CH, 2)>d' -CH = CH.
X< Si -OX <Si -O
-(f + g)- (f + g)
(12)(12)
(R )r(R) r
dans laquelle c' = 2 à 18 d' = 0 à 16 c' + d' = 2 à 18 formules (12) et (12') dans lesquelles X, f, R1, g, et Z, ont les mêmes significations que ci-dessus, avec la possibilité, lorsque e = 0, que c' = 0 et d' = 0 ou 1 (c' + d' = 0 ou 1).in which c '= 2 to 18 d' = 0 to 16 c '+ d' = 2 to 18 formulas (12) and (12 ') in which X, f, R 1 , g, and Z, have the same meanings as above, with the possibility, when e = 0, that c '= 0 and d' = 0 or 1 (c '+ d' = 0 or 1).
Un autre procédé encore consiste à produire le polyorganosiloxane par des réactions d'hydrolyse et/ou de redistribution à partir d'un silane fonctionnalisé de formule (1 ) conforme à l'invention avec un polysiloxane cyclique ou linéaire comprenant des motifs de formule (8) dans laquelle h = 2 ou 3, ou avec un silane hydrolysable répondant à la formule (13) :Yet another process consists in producing the polyorganosiloxane by hydrolysis and / or redistribution reactions from a functionalized silane of formula (1) according to the invention with a cyclic or linear polysiloxane comprising units of formula (8) ) in which h = 2 or 3, or with a hydrolyzable silane corresponding to formula (13):
Rm X n SiR m X n Si
dans laquelle :in which :
- R1 a la même signification qu'à la formule 1 ,
WO 00/20425 10 - R 1 has the same meaning as in formula 1, WO 00/20425 10
- m = 2 ou 3 m + n = 4- m = 2 or 3 m + n = 4
- X tel que décrit à la formule (1 ).- X as described in formula (1).
Dans le cas où l'on arrête la polycondensation par simple neutralisation on obtient un mélange réactionnel comportant des polymères cycliques de formule (10) et/ou linéaires de formule (9) bloquée à chacune de leurs extrémités par un groupe hydroxyle ou par le motif :In the case where polycondensation is stopped by simple neutralization, a reaction mixture is obtained comprising cyclic polymers of formula (10) and / or linear polymers of formula (9) blocked at each of their ends by a hydroxyl group or by the unit :
R1 2YSiO0,5 si l'on utilise au départ en outre le silane R1 2YSiCI ou le disiloxane correspondant. On peut également arrêter la polycondensation en ajoutant, en fin de réaction, un composé organosilicié susceptible de réagir avec les hydroxyles terminaux du polymère de formule (9) formé, ce composé organosilicié pouvant répondre aux formules : R1 3SiCI, R1 3SiNHSiR1 3 et R1 3SiOSiR1 3.R 1 2 YSiO 0.5 if the silane R 1 2 YSiCI or the corresponding disiloxane is also used at the start. The polycondensation can also be stopped by adding, at the end of the reaction, an organosilicon compound capable of reacting with the terminal hydroxyls of the polymer of formula (9) formed, this organosilicon compound being able to correspond to the formulas: R 1 3 SiCI, R 1 3 SiNHSiR 1 3 and R 1 3 SiOSiR 1 3 .
La durée de l'hydrolyse peut être comprise entre quelques secondes et plusieurs heures.The duration of the hydrolysis can be between a few seconds and several hours.
Après hydrolyse, la phase aqueuse est séparée de la phase siloxane par tout moyen physique approprié, généralement par décantation et/ou extraction par un solvant organique comme I'éther isopropylique ou le toluène. En présence d'humidité, les polyorganosiloxanes polyfonctionnels de l'invention réticulent pour former des boroxines très stables aux UV et à la température. Ils peuvent aussi être mis en solution dans de l'eau sous forme d'acide boronique stable, réticulable en boroxine par élimination de l'eau.After hydrolysis, the aqueous phase is separated from the siloxane phase by any suitable physical means, generally by decantation and / or extraction with an organic solvent such as isopropyl ether or toluene. In the presence of moisture, the polyfunctional polyorganosiloxanes of the invention crosslink to form boroxins very stable to UV and to temperature. They can also be dissolved in water in the form of stable boronic acid, crosslinkable into boroxin by elimination of the water.
Ces polydiorganosiloxanes peuvent être utilisés purs pour former par exemple des revêtements après réticulation, en l'absence de catalyseur, en présence d'humidité ou par élimination d'eau selon le cas.These polydiorganosiloxanes can be used pure to form, for example, coatings after crosslinking, in the absence of catalyst, in the presence of moisture or by elimination of water as the case may be.
Ils sont plus particulièrement utilisables comme polymères diorganopolysiloxanes de base, au sein d'une composition silicone réticulable en un élastomère, en l'absence de catalyseur, par exposition à l'humidité atmosphérique ou par élimination d'eau, selon le cas.They are more particularly usable as basic diorganopolysiloxane polymers, within a silicone composition crosslinkable into an elastomer, in the absence of catalyst, by exposure to atmospheric humidity or by elimination of water, as the case may be.
Ces compositions silicones peuvent être conditionnées en un seul emballage et sont stables au stockage.These silicone compositions can be packaged in a single package and are stable on storage.
Dans un troisième objet, la présente invention concerne donc une composition organopolysiloxane, stable au stockage en l'absence d'humidité et pouvant réticuler par exposition à l'humidité en l'absence de catalyseur de réticulation, comprenant :
(A) - 100 parties en poids d'au moins un polymère de formule (7) prise sans son disclaimer, avec éventuellement des motifs (8), ou de formule (9) ou (10), conforme à l'invention (B) - de 0 à 250 parties en poids d'une charge minérale. Elle concerne aussi une composition organopolysiloxane aqueuse, stable au stockage et pouvant réticuler par élimination d'eau, en l'absence de catalyseur de réticulation, comprenant :In a third object, the present invention therefore relates to an organopolysiloxane composition, stable on storage in the absence of moisture and capable of crosslinking by exposure to moisture in the absence of crosslinking catalyst, comprising: (A) - 100 parts by weight of at least one polymer of formula (7) taken without its disclaimer, with possibly motifs (8), or of formula (9) or (10), in accordance with the invention (B ) - from 0 to 250 parts by weight of a mineral filler. It also relates to an aqueous organopolysiloxane composition, stable in storage and capable of crosslinking by elimination of water, in the absence of crosslinking catalyst, comprising:
(A) - 100 parties en poids d'au moins un polymère, un polymère de formule (7) prise sans son disclaimer, avec éventuellement dès motifs (8), ou de formule (9) ou (10), conforme à l'invention(A) - 100 parts by weight of at least one polymer, a polymer of formula (7) taken without its disclaimer, possibly with grounds (8), or of formula (9) or (10), in accordance with invention
(B) - de 0 à 250 parties en poids d'une charge minérale,(B) - from 0 to 250 parts by weight of a mineral filler,
(C) - de 0,5 à 50, de préférence de 3 à 20 parties en poids d'eau(C) - from 0.5 to 50, preferably from 3 to 20 parts by weight of water
(D) - éventuellement un tensioactif non ionique, anionique, cationique ou amphotère. Les charges minérales (B) sont utilisées à raison de 0 à 250 parties, de préférence 20 à 200 parties, pour 100 parties de polymère (A).(D) - optionally a nonionic, anionic, cationic or amphoteric surfactant. The mineral fillers (B) are used in an amount of 0 to 250 parts, preferably 20 to 200 parts, per 100 parts of polymer (A).
Ces charges peuvent se présenter sous la forme de produits très finement divisés dont le diamètre particulaire moyen est inférieur à 0,1 micromètre. Parmi ces charges figurent les silices de combustion et les silices de précipitation ; leur surface spécifique BET est généralement supérieure à 40 m2/g. Ces charges peuvent également se présenter sous la forme de produits plus grossièrement divisés, de diamètre particulaire moyen supérieur à 0,1 micromètre. Comme exemples de telles charges, on peut citer le quartz broyé, les silices de diatomées, le carbonate de calcium, l'argile calcinée, l'oxyde de titane du type rutile, les oxydes de fer, de zinc, de chrome, de zirconium, de magnésium, les différentes formes d'alumine (hydratée ou non), le nitrure de bore, le métaborate de baryum, les microbilles de verre ; leur surface spécifique est généralement inférieure à 30 m2/g.These fillers can be in the form of very finely divided products, the average particle diameter of which is less than 0.1 micrometer. Among these fillers are combustion silicas and precipitation silicas; their BET specific surface area is generally greater than 40 m 2 / g. These fillers can also be in the form of more roughly divided products, with an average particle diameter greater than 0.1 micrometer. Examples of such fillers include ground quartz, diatomic silicas, calcium carbonate, calcined clay, titanium oxide of the rutile type, iron, zinc, chromium, zirconium oxides. , magnesium, the different forms of alumina (hydrated or not), boron nitride, barium metaborate, glass microbeads; their specific surface is generally less than 30 m 2 / g.
Ces charges (B) peuvent avoir été modifiées en surface par traitement avec les divers composés organosiliciques habituellement employés pour cet usage. Ainsi ces composés organosiliciques peuvent être des organochlorosilanes, des diorganocyclopolysiloxanes, des hexaorganodisiloxanes, des hexaorganodisilazanes ou des diorganocyclopolysiloxanes (brevets français FR-A-1 126 884, FR-A-1 136 885, FR- A-1 236 505 ; brevet anglais GB-A-1 024 234). Les charges traitées renferment, dans la plupart des cas, de 3 à 30 % de leur poids de composés organosiliciques.These fillers (B) may have been modified at the surface by treatment with the various organosilicon compounds usually used for this use. Thus these organosilicon compounds can be organochlorosilanes, diorganocyclopolysiloxanes, hexaorganodisiloxanes, hexaorganodisilazanes or diorganocyclopolysiloxanes (French patents FR-A-1,126,884, FR-A-1,136,885, FR-A-1,236,505; English patent GB -A-1 024 234). The treated fillers contain, in most cases, from 3 to 30% of their weight of organosilicon compounds.
Les charges (B) peuvent être constituées d'un mélange de plusieurs types de charges de granulométrie différente.
Les agents tensio-actifs (D) éventuellement mis en œuvre peuvent être non-ioniques de HLB supérieur à 10, de préférence de l'ordre de 10 à 20, anioniques, cationiques, zwitterioniques ou amphotères de HLB supérieur à 10.The fillers (B) can consist of a mixture of several types of fillers of different particle size. The surfactants (D) which may be used can be nonionic with an HLB greater than 10, preferably of the order of 10 to 20, anionic, cationic, zwitterionic or amphoteric with an HLB greater than 10.
Les agents tensio-actifs non-ioniques peuvent être choisis parmi les acides gras alcoxylés, les alkyphénols polyalcoxylés, les alcools gras polyalcoxylés, les amides gras polyalcoxylés ou polyglycérolés, les alcools et les alphadiols polyglycérolés, les polymères blocs oxyde d'éthylène-oxyde de propylène, ainsi que les alkylglucosides, les alkylpolyglucosides, les sucroéthers, les sucroesters, les sucroglycérides, les esters de sorbitan, et les composés éthoxylés de ces dérivés de sucres, présentant un HLB d'au moins 10.The nonionic surfactants can be chosen from alkoxylated fatty acids, polyalkoxylated alkyphenols, polyalkoxylated fatty alcohols, polyalkoxylated or polyglycerolated fatty amides, polyglycerolated alcohols and alphadiols, ethylene oxide block polymers propylene, as well as alkylglucosides, alkylpolyglucosides, sucroethers, sucroesters, sucroglycerides, sorbitan esters, and ethoxylated compounds of these sugar derivatives, having an HLB of at least 10.
Les agents tensio-actifs anioniques peuvent être choisis parmi les alkylbenzène sulfonates, les alkysulfates, les alkyléthersulfates, les alkylaryléthersulfates, les dialkylsulfosuccinates, les alkylphosphates, les étherphosphates, de métaux alcalins présentant un HLB d'au moins 10. Parmi les agents tensio-actifs cationiques on peut citer les aminés grasses aliphatiques ou aromatiques, les amides gras aliphatiques, les dérivés d'ammonium quaternaire, présentant un HLB d'au moins 10.The anionic surfactants can be chosen from alkylbenzene sulfonates, alkysulfates, alkylethersulfates, alkylarylethersulfates, dialkylsulfosuccinates, alkylphosphates, etherphosphates, of alkali metals having an HLB of at least 10. Among surfactants cationic there may be mentioned aliphatic or aromatic fatty amines, aliphatic fatty amides, quaternary ammonium derivatives, having an HLB of at least 10.
Parmi les agents tensio-actifs zwitterioniques ou amphotères, on peut citer les bétaïnes et leurs dérivés, les sultaïnes et leurs dérivés, les lécithines, les dérivés d'imidazolines, les glycinates et leurs dérivés, les aminopropionates, les oxydes d'aminés grasses présentant un HLB d'au moins 10.Among the zwitterionic or amphoteric surfactants, there may be mentioned betaines and their derivatives, sultaines and their derivatives, lecithins, imidazoline derivatives, glycinates and their derivatives, aminopropionates, fatty amine oxides having an HLB of at least 10.
Les polyorganosiloxanes à fonctions boronates selon l'invention peuvent être utilisés à l'état pur ou sous forme de compositions du type de celles précitées, par exemple dans le domaine du conditionnement de matières textiles et dans le domaine du revêtement de métaux, de pierres naturelles ou d'articles de construction divers à base de ciment, pour leur conférer des propriétés de surface anti-adhérentes et/ou hydrophobantes.The polyorganosiloxanes with boronate functions according to the invention can be used in the pure state or in the form of compositions of the type of those mentioned above, for example in the field of packaging of textile materials and in the field of coating of metals, natural stones or various construction articles based on cement, to give them non-stick and / or hydrophobic surface properties.
L'invention a donc également pour objet cette utilisation ainsi que la méthode de traitement de ces différentes matières ou substrats, dans laquelle on enduit ces substrats avec les polyorganosiloxanes ou les compositions selon l'invention, de façon à conférer à ces substrats, après réticulation, les propriétés adhérentes et/ou hydrophobantes.The invention therefore also relates to this use as well as the method of treatment of these different materials or substrates, in which these substrates are coated with the polyorganosiloxanes or the compositions according to the invention, so as to confer on these substrates, after crosslinking , the adherent and / or hydrophobic properties.
L'invention va être maintenant décrite plus en détail à l'aide de modes de réalisation pris à titre d'exemples non limitatifs.The invention will now be described in more detail using embodiments taken by way of nonlimiting examples.
Les silanes et vinylsilanes sont des produits industriels et commerciaux. Les méthodes de préparation des hydrures de bore sont connues. On peut citer Jeffers P. .
„„„„„«. ι o PCT/FR99/02362Silanes and vinylsilanes are industrial and commercial products. The methods for preparing boron hydrides are known. We can quote Jeffers P.. „„ „„ „ “ . ι o PCT / FR99 / 02362
WO 00/20425 13WO 00/20425 13
et al., Inorg. Chem., 1981 , 20 : 1698 pour la préparation de HB(OMe)2. La synthèse d'allyle dibutoxy borane est décrite ci-après.et al., Inorg. Chem., 1981, 20: 1698 for the preparation of HB (OMe) 2 . The synthesis of allyl dibutoxy borane is described below.
EXEMPLESEXAMPLES
Exemple 1 : synthèse d'allyle dibutoxy borane :Example 1: Synthesis of allyl dibutoxy borane:
Dans un tricol d'1 litre équipé d'une agitation mécanique, d'un réfrigérant ascendant, d'une ampoule isobare de 100 ml, d'une valve à N2 (le tout séché à la flamme sous N2), on introduit le Mg 0,5 mole, puis l'ethérate de BF3 fraîchement distillé et 350 ml d'éther anhydre distillé sur Na.Into a 1 liter three-necked flask equipped with mechanical stirring, an ascending cooler, an isobaric bulb of 100 ml, a valve with N 2 (all flame-dried under N 2 ), the following is introduced 0.5 mg Mg, then the freshly distilled BF 3 etherate and 350 ml of anhydrous ether distilled over Na.
Sous forte agitation à température ambiante, on additionne gouttte à goutte une solution de 28,62 g de chlorure d'allyle dans 50 ml d'éther anhydre. La réaction est amorcée par introduction directe de 4 cm3 (sur les 28,60 g) de chlorure d'allyle dans le réacteur.With vigorous stirring at room temperature, a solution of 28.62 g of allyl chloride in 50 ml of anhydrous ether is added dropwise. The reaction is initiated by direct introduction of 4 cm 3 (out of 28.60 g) of allyl chloride into the reactor.
Il y a rapidement un reflux d'éther, qui une fois redevenu à un niveau raisonnable est entretenu par addition de solution de chlorure d'alllyle, sous vive agitation.There is quickly a reflux of ether, which once returned to a reasonable level is maintained by the addition of alllyl chloride solution, with vigorous stirring.
Après 1 h 30 d'addition, on iaisse 2 h à température ambiante sous vive agitation. Après décantation, le surnageant est transféré sous N2 dans un ballon de 1 h dégazé et sec.After 1 hour 30 minutes of addition, it is left for 2 hours at room temperature with vigorous stirring. After decantation, the supernatant is transferred under N 2 into a 1-hour degassed and dry flask.
On ajoute 3 x 200 ml d'éther anhydre sur le précipité sous agitation pour en extraire le maximum de produit. Les surnageants rassemblés, l'éther est distillé à pression atmosphérique. Après transfert sous N2 du produit restant dans un ballon de 100 ml, le triallylborane est distillé à 60 °C pendant 20 min. Rendement : 67 %.3 x 200 ml of anhydrous ether are added to the precipitate with stirring to extract the maximum amount of product. The supernatants collected, the ether is distilled at atmospheric pressure. After transfer under N 2 of the product remaining in a 100 ml flask, the triallylborane is distilled at 60 ° C for 20 min. Yield: 67%.
Dans un ballon de 100 ml bicol, muni d'une agitation magnétique et d'un réfrigérant + valve, le tout séché à la flamme sous Argon, on introduit 9 g de triallylborane fraîchement distillé.9 g of freshly distilled triallylborane are introduced into a 100 ml two-necked flask, fitted with a magnetic stirrer and a condenser + valve, all dried in a flame under Argon.
On ajoute goutte à goutte un excès de 1-butanol fraîchement distillé sous N2. La réaction est exothermique. On assure éventuellement un refroidissement par bain d'eau àAn excess of freshly distilled 1-butanol under N 2 is added dropwise. The reaction is exothermic. A water bath cooling is optionally provided
30-35° C.30-35 ° C.
On laisse une nuit à température ambiante. On distille ensuite l'excès de 1-butanol sous vide de 40 mm Hg (5320 Pa), puis le produit attendu sous 0,2 à 0,4 mm Hg (26,6 àIt is left overnight at room temperature. The excess 1-butanol is then distilled under vacuum of 40 mm Hg (5320 Pa), then the expected product under 0.2 to 0.4 mm Hg (26.6 to
53,2 Pa) à 58-62° C ; 12,2 g d'un liquide incolore sont obtenus. Il reste un léger culot. Le culot et le liquide sont rassemblés et redistillés sur une colonne Vigreux de 13 cm de
hauteur. Le produit attendu (allyle dibutoxy borane) est récupéré à 50° C - 52° C sous 0,1 mm Hg (13,3 Pa).53.2 Pa) at 58-62 ° C; 12.2 g of a colorless liquid are obtained. There remains a light base. The pellet and the liquid are combined and redistilled on a Vigreux column of 13 cm in height. The expected product (allyl dibutoxy borane) is recovered at 50 ° C - 52 ° C under 0.1 mm Hg (13.3 Pa).
Remarque : il est possible de ne pas purifier l'intermédiaire triallyle borane et d'effectuer directement l'ajout de butanol.Note: it is possible not to purify the triallyl borane intermediate and to directly add butanol.
Exemple 2 : hydrosilylation d'une huile Si-H par l'allyle dibutoxy borane obtenu à l'exemple 1 :Example 2: Hydrosilylation of an Si-H oil with the allyl dibutoxy borane obtained in Example 1:
Réactifs : - 7,18 g d'huile polyhydrogénosiloxanique (MD9D'4M [où M = (CH3)3Si01 2, D =Reagents: - 7.18 g of polyhydrogenosiloxane oil (MD 9 D ' 4 M [where M = (CH 3 ) 3 Si0 1 2 , D =
(CH3)2Si02/2 et D' = H(CH3)Siθ2/2] ayant 384 millimoles de motifs SiH pour 100 g d'huile et de viscosité 12 mPa.s à 25° C (viscosimètre Brookfield) 6,55 g d'allyle dibutoxy borane (0,033 mmole) - 10 ppm de catalyseur au platine de type Karstedt : solution dans le divinyltetraméthyldisiloxane d'un complexe de platine à environ 11 % en poids de platine zéro ligandé par du divinyltetraméthyldisiloxane : les quantités de ce catalyseur sont exprimées en ppm de Pt métal apporté par la solution dans le mélange réactionnel. Mode opératoire : L'huile est chargée dans une ampoule de coulée isobare. On introduit l'allyle dibutoxy borane et le catalyseur dans un ballon (tricol de 100 ml avec agitateur mécanique). On coule lentement l'huile sur l'alcène. On chauffe ensuite le milieu réactionnel vers 70-75° C pendant 2 heures.(CH 3) 2 Si0 2/2 and D '= H (CH 3) SiO 2/2] with 384 millimoles of SiH units per 100 g of oil and viscosity 12 mPa.s at 25 ° C (Brookfield) 6.55 g of allyl dibutoxy borane (0.033 mmol) - 10 ppm of Karstedt-type platinum catalyst: solution in divinyltetramethyldisiloxane of a platinum complex of approximately 11% by weight of zero platinum liganded by divinyltetramethyldisiloxane: the amounts of this catalyst are expressed in ppm of Pt metal supplied by the solution in the reaction mixture. Procedure: The oil is loaded into an isobaric dropping funnel. The allyl dibutoxy borane and the catalyst are introduced into a flask (100 ml three-necked flask with mechanical stirrer). The oil is slowly poured over the alkene. The reaction medium is then heated to around 70-75 ° C for 2 hours.
La spectrométrie IR permet de suivre l'évolution de la réaction par le suivi de la disparition de la bande SiH (Vers 2100 cm"1). En fin de réaction, on procède à l'élimination des réactifs n'ayant pas réagi par chauffage sous vide (13,3 102 Pa.) vers 110-120 ° C.IR spectrometry makes it possible to follow the evolution of the reaction by monitoring the disappearance of the SiH band (around 2100 cm −1 ). At the end of the reaction, the unreacted reagents are removed by heating under vacuum (13.3 10 2 Pa.) around 110-120 ° C.
Le polyorganosiloxane obtenu répond à la formule suivante :
The polyorganosiloxane obtained corresponds to the following formula:
dans laquelle les fonctions boronates sont constituées essentiellement par un mélange des fonctions :in which the boronate functions consist essentially of a mixture of the functions:
B B BB B B
BuO OBu BuO OH HO OHBuO OBu BuO OH HO OH
où les fonctions a sont largement majoritaires en nombre.where the functions a are largely in number.
Exemple 3 : Hydrosilylation du triéthoxysilane par l'allyle dibutoxyborane obtenu à l'exemple 1 :Example 3 Hydrosilylation of the Triethoxysilane by the Allyl Dibutoxyborane Obtained in Example 1:
Charαe des produits :Product characteristics:
Allyldibutoxy borane 22,30 g 0,094 mol 1 ,1 éq.Allyldibutoxy borane 22.30 g 0.094 mol 1.1 eq.
Triéthoxysilane 14,20 g 0,086 mol 1 éq.Triethoxysilane 14.20 g 0.086 mol 1 eq.
Catalyseur 0,0009 gCatalyst 0.0009 g
Mode opératoire :
Dans un tricol (sec et sous argon), on introduit l'allyboronate de butyle et le platine de Karstedt. On coule sur ce mélange le triéthoxysilane distillé. Quand la coulée est terminée, on chauffe à 100°C et on suit l'évolution de la réaction par dosage Si-H.Procedure: In a three-necked flask (dry and under argon), the butyl allyboronate and the Karstedt platinum are introduced. The distilled triethoxysilane is poured onto this mixture. When the pouring is finished, the mixture is heated to 100 ° C. and the progress of the reaction is monitored by Si-H assay.
Un dosage Si-H réalisé après 24 h de réaction indique que celle-ci n'est pas terminée. On rajoute du catalyseur et on continue le chauffage. La réaction est suivie par dosages Si-H. Au bout de 48 heures, un quatrième dosage indique que le taux de transformation est de 95 %.An Si-H assay carried out after 24 h of reaction indicates that the latter is not complete. Catalyst is added and heating is continued. The reaction is followed by Si-H assays. After 48 hours, a fourth dosage indicates that the transformation rate is 95%.
On dévolatilise le milieu sous pression "réduite pour éliminer l'excès d'allyboronate de butyle. On récupère 22 g de produit correspondant à la formule suivante :Is devolatilized the pressurized medium "reduced to remove excess allyboronate butyl were recovered 22 g of product corresponding to the following formula.:
Exemple 4 : Hydrosilylation d'allylpinacolboronate avec un polyorganosiloxane cyclique pour produire du 1 ,3,5,7-tétra-(3-(pinacolboronate)propyl)-1 ,3,5,7-tétraméthyl- cyclotétrasiloxane :Example 4 Hydrosilylation of allylpinacolboronate with a cyclic polyorganosiloxane to produce 1, 3,5,7-tetra- (3- (pinacolboronate) propyl) -1,3,5,7-tetramethylcyclotetrasiloxane:
Composés de départ :
polyorganosiloxane cycliqueStarting compounds: cyclic polyorganosiloxane
Me allylpinacolboronate :Me allylpinacolboronate:
ce composé est préparé selon la méthode décrite dans R. W. Hoffmann et al., Liebigs Ann. Chem. 1986, 1823-1836 ou dans W.R. Roush et al., J. Am. Chem. Soc. 1986, 108,this compound is prepared according to the method described in R. W. Hoffmann et al., Liebigs Ann. Chem. 1986, 1823-1836 or in W.R. Roush et al., J. Am. Chem. Soc. 1986, 108,
3422-3434. catalyseur de Karstedt3422-3434. karstedt catalyst
Mode opératoire : Sous argon, on mélange et chauffe jusqu'à 60° C de l'allylpinacolboronate (1 ,5 ml,Procedure: Under argon, allylpinacolboronate (1.5 ml,
9,1 mmoles) et du catalyseur de Karstedt (1.10"4 mole de platine par mole d'allylpinacolboronate) dans du toluène (5 ml). Après agitation, on ajoute le silane cyclique (0,5 ml, 2,1 mmoles). On chauffe ensuite la solution à 60° C pendant 4 h. Le solvant est évaporé sous pression réduite et l'on extrait les sous-produits volatiles et les excès d'allylpinacolboronate par distillation sur Kugelrohr (90% C, 0,2 mm Hg, soit 26,6 Pa).9.1 mmol) and Karstedt catalyst (1.10 "4 mole platinum per mole of allylpinacolboronate) in toluene (5 ml). After stirring, the cyclic silane (0.5 ml, 2.1 mmol) is added. The solution is then heated at 60 ° C. for 4 h. The solvent is evaporated off under reduced pressure and the volatile by-products and the excess of allylpinacolboronate are extracted by distillation on Kugelrohr (90% C, 0.2 mm Hg, i.e. 26.6 Pa).
On obtient 1 ,31 g du produit recherché.1.31 g of the desired product are obtained.
1H RMN : δ = 0,02 ppm (12H, Si-CH3), 0.51-0.58 (8H, m, Si-CH2), 0,74-0,82 (m, 8H, -CH2), 1 ,19 (s,48H, C-CH3), 1 ,41-1.51 (m, 8H, CH2). 1 H NMR: δ = 0.02 ppm (12H, Si-CH 3 ), 0.51-0.58 (8H, m, Si-CH 2 ), 0.74-0.82 (m, 8H, -CH 2 ), 1, 19 (s, 48H, C-CH 3 ), 1, 41-1.51 (m, 8H, CH 2 ).
13C RMN : δ = - 0,66 ppm (Si-CH3), 17,53 (Si-CH2), 19,97 (B-CH2), 20,24 (CH2), 24,79 (C-CH3), 82,73 (C ). 13 C NMR: δ = - 0.66 ppm (Si-CH 3 ), 17.53 (Si-CH 2 ), 19.97 (B-CH 2 ), 20.24 (CH 2 ), 24.79 ( C-CH 3 ), 82.73 (C).
Exemple 5 : Hydrosilylation d'allyldibutoxyborane selon l'exemple 1 avec le polysiloxane cyclique de l'exemple 4 pour obtenir du 1 ,3,5,7-tétra-(3-(dibutoxyboronate)propyl)-1 ,3,5,7- tétraméthyl-cyclotétrasiloxane :Example 5 Hydrosilylation of allyldibutoxyborane according to Example 1 with the cyclic polysiloxane of Example 4 to obtain 1, 3,5,7-tetra- (3- (dibutoxyboronate) propyl) -1, 3,5,7 - tetramethyl-cyclotetrasiloxane:
Sous argon, on mélange et on chauffe jusqu'à 70 °C de l'allyldibutoxyborane (1 ,8 g, 9,1 mmoles) et du catalyseur de Karstedt (1.10"4 mole de platine par mole d'allyldibutoxyborane). Après agitation, on ajoute le silane cyclique (0,5 ml, 2,1 mmoles).
On chauffe ensuite la solution à 70° C pendant 4 h. Le solvant est évaporé sous pression réduite et l'on extrait les sous-produits volatiles et les excès d'allyldibutoxyborane par distillation sur Kugeirohr (100° C/0,2 mm Hg, soit 26,6 Pa). On obtient 1 ,6 g du produit recherché ayant la formule :Under argon, allyldibutoxyborane (1.8 g, 9.1 mmol) and Karstedt catalyst (1.10 "4 mole of platinum per mole of allyldibutoxyborane) are mixed and heated to 70 ° C. , the cyclic silane (0.5 ml, 2.1 mmol) is added. The solution is then heated at 70 ° C for 4 h. The solvent is evaporated off under reduced pressure and the volatile by-products and the excess of allyldibutoxyborane are extracted by distillation on Kugeirohr (100 ° C / 0.2 mm Hg, ie 26.6 Pa). 1.6 g of the desired product having the formula:
BB
#θ' OR2 # θ ' OR 2
dans laquelle les fonctions boronates sont constituées essentiellement par un mélange des fonctions :in which the boronate functions consist essentially of a mixture of the functions:
B B BB B B
BuO OBu BuO OH HO OHBuO OBu BuO OH HO OH
où les fonctions a_sont largement majoritaires en nombre.where the functions a_are largely in number.
1H RMN : δ = 0,03 ppm (12H, Si-CH3), 0,48-0,57 (8H, m, Si-CH2J, 0,73-0,81 (m, 8H, B- 1 H NMR: δ = 0.03 ppm (12H, Si-CH 3 ), 0.48-0.57 (8H, m, Si-CH 2 J, 0.73-0.81 (m, 8H, B -
CH2), 0,85-0,92 (m, 24H, CH2-CH3), 1 ,24-1 ,56 (s, 40H,
Si-CH2-CH2)), 3,72-CH 2 ), 0.85-0.92 (m, 24H, CH 2 -CH 3 ), 1, 24-1, 56 (s, 40H, Si-CH 2 -CH 2 )), 3.72-
3,79 (m, 16H, 0-CH2).3.79 (m, 16H, 0-CH 2 ).
13C RMN : δ = -0,65 ppm (Si-CH3), 13,85 (CH2-CH3), 17,71 (Si-CH2), 19,06, 20,53 (CH3- 13 C NMR: δ = -0.65 ppm (Si-CH 3 ), 13.85 (CH 2 -CH 3 ), 17.71 (Si-CH 2 ), 19.06, 20.53 (CH 3 -
CH2, Si-CH2-CH2), 33,81 (0-CH2-CH2), 62,92 (0-CH2).CH 2 , Si-CH 2 -CH 2 ), 33.81 (0-CH 2 -CH 2 ), 62.92 (0-CH 2 ).
29Si RMN : δ = -13,80, -20,79, -20,81 , -20,87, -20,88, -20,94, -21 ,00 ppm 29 If NMR: δ = -13.80, -20.79, -20.81, -20.87, -20.88, -20.94, -21.00 ppm
11B RMN : δ = 31 ,16 ppm
Exemple 6 : synthèse d'allyle diisopropyloxy borane 11 B NMR: δ = 31, 16 ppm EXAMPLE 6 Synthesis of Allyl Diisopropyloxy Borane
Dans un réacteur de 500 ml sous azote, on introduit 12 g (0,493 mole) de Mg, 170 ml d'éther anhydre et 20 g (0,141 mole) de BF3-EtOEt. On introduit ensuite en 1 h une solution de 32,4 g (0,423 mole) de chlorure d'allyle et 50 ml d'éther sec. On démarre la préparation du magnésien par l'introduction d'un cristal d'iode. La réaction est exothermique et entraîne le reflux de l'éther. On laisse ensuite réagir 4 h à la température ambiante. On porte la masse réactionnelle à 0°C à l'aide d'un bain de glace. On rajoute ensuite en 1 h, 16,1 g (0,268 mole) d'isσpropanol anhydre. On laisse réagir 35 h à la température ambiante. On filtre sur terre de diatoméë. On évapore le filtrat et on récupère une masse réactionnelle qui est distillée sous vide. On récupère 13,3 g de H2C=CH- CH2B(OiPr)2 (Rendement isolé 55 %) ; Température d'ébullition : ~ 37°C /760 mm d'Hg (1010,8 102 Pa). Les analyses RMN et IR confirment la structure de ce dérivé.12 g (0.493 mole) of Mg, 170 ml of anhydrous ether and 20 g (0.141 mole) of BF 3 -EtOEt are introduced into a 500 ml reactor under nitrogen. Then a solution of 32.4 g (0.423 mole) of allyl chloride and 50 ml of dry ether is introduced over 1 hour. We start the preparation of the magnesian by the introduction of an iodine crystal. The reaction is exothermic and causes the reflux of the ether. Then allowed to react for 4 h at room temperature. The reaction mass is brought to 0 ° C. using an ice bath. Then added in 1 hour, 16.1 g (0.268 mole) of anhydrous isσpropanol. It is left to react for 35 h at room temperature. We filter on diatomaceous earth. The filtrate is evaporated and a reaction mass is recovered which is distilled under vacuum. 13.3 g of H 2 C = CH-CH 2 B (OiPr) 2 are recovered (isolated yield 55%); Boiling temperature: ~ 37 ° C / 760 mm Hg (1010.8 10 2 Pa). NMR and IR analyzes confirm the structure of this derivative.
Exemple 7 : hydrosilylation d'une huile Si-H par l'allyle diisopropyloxy borane obtenu à l'exemple 6 :Example 7: Hydrosilylation of an Si-H Oil with the Allyl Diisopropyloxy Borane Obtained in Example 6:
Dans un réacteur de 250 ml sous azote, on introduit 30 ml de toluène sec et 3,7 g (0,020 mole) de H2C=CH-CH2B(OiPr)2. On rajoute ensuite 0,0314 g de la solution de catalyseur de Karstedt (soit 104 ppm de Pt métal). On porte la masse réactionnelle à 70°C et on coule en 1 h l'huile silicone MD20oD'7M (30 g soit 0,0137 mole de motifs SiH). Au bout de 24h de réaction à 80°C, le taux de transformation des motifs SiH est de 100 %. On rajoute ensuite 2g de Noir de carbone et on laisse 1 h à 60°C. On filtre sous azote et par dévolatilisation (100°C, 1 -2 bar, soit de 100 à 200 Pa), on récupère 35,4 g d'une huile très visqueuse dont les analyses RMN et IR confirment la structure suivante :30 ml of dry toluene and 3.7 g (0.020 mole) of H 2 C = CH-CH 2 B (OiPr) 2 are introduced into a 250 ml reactor under nitrogen. 0.0314 g of the Karstedt catalyst solution is then added (ie 104 ppm of Pt metal). The reaction mass is brought to 70 ° C. and the silicone oil MD 20 oD ' 7 M is poured in within 1 h (30 g, ie 0.0137 mole of SiH units). After 24 hours of reaction at 80 ° C., the degree of conversion of the SiH units is 100%. 2 g of carbon black are then added and the mixture is left for 1 hour at 60 ° C. Filtered under nitrogen and by devolatilization (100 ° C., 1-2 bars, ie from 100 to 200 Pa), 35.4 g of a very viscous oil are recovered, the NMR and IR analyzes confirm the following structure:
B. B BB. B B
PriO OiPr PriO OH HO OHPriO OiPr PriO OH HO OH
où les fonctions a sont largement majoritaires en nombre.
where the functions a are largely in number.
Claims
1. Silane de formule (1 )1. Silane of formula (1)
YY
dans laquelle :in which :
R1 est choisi parmi un groupe hydroearboné monovalent, éventuellement substitué par des atomes d'halogènes,R 1 is chosen from a monovalent hydro-carbon group, optionally substituted by halogen atoms,
X est un groupe hydrolysable, a est choisi parmi 1 , 2 et 3, - b est choisi parmi 0, 1 et 2,X is a hydrolyzable group, a is chosen from 1, 2 and 3, - b is chosen from 0, 1 and 2,
- a + b = 3- a + b = 3
Y est un groupe boronate de formule (2)Y is a boronate group of formula (2)
// OR2 CH2 CH2 (CH2)C Ze (CH2) d B ' // OR 2 CH 2 CH 2 (CH 2 ) C Z e (CH 2 ) d B '
\ 2 OR\ 2 OR
dans laquelle : . c et d sont des entiers allant de 0 à 18in which : . c and d are integers ranging from 0 to 18
. c + d = 0 à 18. c + d = 0 to 18
. e est choisi parmi 0 et 1. e is chosen from 0 and 1
. Z est un groupe divalent hétérocarboné comprenant un ou plusieurs hétéroatomes comme O, S et/ou N . les groupements R2, qui peuvent être identiques ou différents, sont choisis parmi atome d'hydrogène, radical alkyle linéaire ou ramifié en C1-C20, de préférence C1-C6, cycloalkyle en C5-C8, aryle en C6-C12, ou peuvent former avec les atomes de bore et d'oxygène un hétérocycle comportant de 5 à 8 éléments (atomes dans l'hétérocycle), de préférence de 5 à 6, les carbones pouvant être éventuellement substitués,. Z is a divalent heterocarbon group comprising one or more heteroatoms such as O, S and / or N. the groups R 2 , which may be identical or different, are chosen from a hydrogen atom, a linear or branched C1-C20 alkyl radical, preferably C1-C6, C5-C8 cycloalkyl, C6-C12 aryl, or can forming with the boron and oxygen atoms a heterocycle comprising from 5 to 8 elements (atoms in the heterocycle), preferably from 5 to 6, the carbons being possibly substituted,
étant exclu le silane de formule / OCHgCHgCHabeing excluded the silane of formula / OCH g CH g CHa
OH BOH B
\ OCH2CH2CH3 \ OCH 2 CH 2 CH 3
(CH3CH2CH2O)3SiCH2CH2CH2OCH2CH-CH2-NH(CH 3 CH 2 CH 2 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CH-CH 2 -NH
2. Silane selon la revendication 1 , caractérisé en ce que, dans la formule (2), . c + d = 0 ou 12. Silane according to claim 1, characterized in that, in formula (2),. c + d = 0 or 1
. e = 0. e = 0
. R2 sont des groupements alkyles linéaires ou ramifiés en C1-C4 et/ou H.. R 2 are linear or branched C1-C4 and / or H alkyl groups.
3. Silane selon la revendication 1 , caractérisé en ce que, dans la formule (2), . c = 0 ou 13. Silane according to claim 1, characterized in that, in formula (2),. c = 0 or 1
. d = 0. d = 0
. e = 1. e = 1
. Z est un groupe phénylène. Z is a phenylene group
. R2 sont des groupements alkyles linéaires ou ramifiés en C1-C4 et/ou H.. R 2 are linear or branched C1-C4 and / or H alkyl groups.
4. Silane selon la revendication 1 , caractérisé en ce que, dans la formule (2), Z est choisi parmi : - O-, -CO-, -COO-, phénylène, -NR'- avec R' = H ou alkyle linéaire ou ramifié en C1 -C4, -S-.4. Silane according to claim 1, characterized in that, in formula (2), Z is chosen from: - O-, -CO-, -COO-, phenylene, -NR'- with R '= H or alkyl linear or branched in C1 -C4, -S-.
5. Silane selon l'une quelconque des revendications 1 à 4, caractérisé en ce que, dans la formule (1 ), les radicaux R1, identiques ou différents, sont choisis parmi :5. Silane according to any one of claims 1 to 4, characterized in that, in formula (1), the radicals R 1 , identical or different, are chosen from:
- les radicaux alkyle et halogénoalkyles linéaires ou ramifiés en C3-C10, de préférence C1 -C6, - les radicaux cycloalkyles et halogénocycloalkyles en C1 -C10, de préférence C5-C8, les radicaux alcényles en C2-C4,- linear or branched C3-C10 alkyl and haloalkyl radicals, preferably C1 -C6, - C1 -C10 cycloalkyl and halocycloalkyl radicals, preferably C5-C8, C2-C4 alkenyl radicals,
- les radicaux aryles et halogénoaryies en C6-C10.- C6-C10 aryl and haloaryry radicals.
6. Silane selon la revendication 5, caractérisé en ce que, dans la formule (1 ), les radicaux R1, identiques ou différents, sont choisis parmi méthyle, phényle, vinyle et trifluoro-3,3,3 propyle. 6. Silane according to claim 5, characterized in that, in formula (1), the radicals R 1 , identical or different, are chosen from methyl, phenyl, vinyl and trifluoro-3,3,3 propyl.
7. Silane selon l'une quelconque des revendications 1 à 6, caractérisé en ce que, dans la formule (1 ), le radical X est choisi parmi les atomes d'halogène, les radicaux amino-N substitués, amido-N substitués, amino-N, N disubstitués, cétiminoxy, aldiminoxy, alcoxy, alcoxyalkylène-oxy, enoxy, acyloxy.7. Silane according to any one of claims 1 to 6, characterized in that, in formula (1), the radical X is chosen from halogen atoms, substituted amino-N, substituted amido-N radicals, amino-N, disubstituted N, ketiminoxy, aldiminoxy, alkoxy, alkoxyalkylene-oxy, enoxy, acyloxy.
8. Silane selon la revendication 7, caractérisé en ce que le radical X est choisi parmi les groupements méthoxy, éthoxy et acétoxy.8. Silane according to claim 7, characterized in that the radical X is chosen from methoxy, ethoxy and acetoxy groups.
9. Silane selon la revendication 2, de formule :9. Silane according to claim 2, of formula:
OBuOBu
OMeOMe
10. Silane selon la revendication 2, de formule10. Silane according to claim 2, of formula
MeMe
OEtAnd
B.B.
(B)(B)
EtO- Si - OEtEtO- Si - OEt
OEtAnd
11. Silane selon la revendication 3, de formule :11. Silane according to claim 3, of formula:
OMe OMe
12. Silane selon la revendication 3, de formule :12. Silane according to claim 3, of formula:
MeMe
MeMe
13. Polyorganosiloxane présentant par molécule au moins un motif répondant à la formule générale (7) :13. Polyorganosiloxane having at least one unit per molecule corresponding to the general formula (7):
YY
X< Si "(O)X <If "(O)
(f + g)(f + g)
(R ) g(R) g
dans laquelle :in which :
- R1 et X ont les mêmes significations qu'aux revendications 1 à 12,- R 1 and X have the same meanings as in claims 1 to 12,
- f est choisi parmi 0, 1 ou 2,- f is chosen from 0, 1 or 2,
- g est choisi parmi 0, 1 ou 2,- g is chosen from 0, 1 or 2,
- f + g est au plus égal à 2- f + g is at most equal to 2
- Y est un groupe boronate de formule (2)- Y is a boronate group of formula (2)
ORGOLD
CH2 CH2 (CH2)C Ze (CH2) d B.CH 2 CH 2 (CH 2 ) C Z e (CH 2 ) d B.
ORGOLD
dans laquelle c, Z, e, d et R2 ont les mêmes significations qu'aux revendications 1 à 12, étant exclu le polyorganosiloxane dans lequel f + g = 0 et Y est tel que :in which c, Z, e, d and R 2 have the same meanings as in claims 1 to 12, being excluded the polyorganosiloxane in which f + g = 0 and Y is such that:
CH, CH. CH. OCH. 
CH, CH. CH. OCH.
14. Polyorganosiloxane présentant par molécule d'une part au moins un motif répondant à la formule générale (7)14. Polyorganosiloxane having, per molecule on the one hand, at least one motif corresponding to the general formula (7)
YY
X Si -(O)X Si - (O)
(f + g)(f + g)
(R )(R)
dans laquelle :in which :
R1 et X ont les mêmes significations qu'aux revendications 1 à 12, - f est choisi parmi 0, 1 ou 2, g est choisi parmi 0, 1 ou 2,R 1 and X have the same meanings as in claims 1 to 12, - f is chosen from 0, 1 or 2, g is chosen from 0, 1 or 2,
- f + g est au plus égal à 2- f + g is at most equal to 2
- Y est un groupe boronate de formule (2)- Y is a boronate group of formula (2)
ORGOLD
CH. CH, (CH2 2)C (CH 22) d BCH. CH, (CH 2 2) C (CH 2 2 ) d B
ORGOLD
dans laquelle c, Z, e, d et R2 ont les mêmes significations qu'aux revendications 1 prise son son disclaimer et 2 à 12, et d'autre part des motifs répondant à la formule (8)in which c, Z, e, d and R 2 have the same meanings as in claims 1 taken its disclaimer and 2 to 12, and on the other hand grounds corresponding to the formula (8)
(R ) , (O)(R), (O)
4 - h dans laquelle :4 - h in which :
R1 a la même signification qu'aux revendications 1 à 12 h est choisi parmi 0, 1 , 2 et 3.R 1 has the same meaning as in claims 1 to 12 h is chosen from 0, 1, 2 and 3.
15. Polyorganosiloxane selon la revendication 13 prise sans son disclaimer ou 14, caractérisé en ce qu'il répond à la formule (9)15. Polyorganosiloxane according to claim 13 taken without its disclaimer or 14, characterized in that it corresponds to formula (9)
dans laquelle :in which :
R1, X et Y ont les mêmes significations qu'aux revendications 13 prise sans son disclaimer et 14,R 1 , X and Y have the same meanings as in claims 13 taken without its disclaimer and 14,
- X' est choisi parmi les radicaux Y, R', hydroxyle et atome d'hydrogène,- X 'is chosen from the radicals Y, R', hydroxyl and hydrogen atom,
- les radicaux R5, identiques ou différents, sont choisis parmi les radicaux R1 et X, - i est un nombre entier compris entre 0 et 1000,the radicals R 5 , which are identical or different, are chosen from the radicals R 1 and X, - i is an integer between 0 and 1000,
- j est un nombre entier compris entre 0 et 50, si j = 0, au moins 1 des radicaux X' est Y.- j is an integer between 0 and 50, if j = 0, at least 1 of the radicals X 'is Y.
16. Polyorganosiloxane selon la revendication 13 prise sans son disclaimer ou 14, caractérisé en ce qu'il répond à la formule (10)16. Polyorganosiloxane according to claim 13 taken without its disclaimer or 14, characterized in that it corresponds to formula (10)
dans laquelle : R1 et Y ont les mêmes significations qu'aux revendications 13 prise sans son disclaimer et 14, k est un nombre entier compris entre 0 et 9 inclus,in which : R 1 and Y have the same meanings as in claims 13 taken without its disclaimer and 14, k is an integer between 0 and 9 inclusive,
I est un nombre entier compris entre 1 et 9 inclus, k + I est compris entre 3 et 10 inclus.I is an integer between 1 and 9 inclusive, k + I is between 3 and 10 inclusive.
17. Procédé de préparation d'un silane selon l'une des revendications 1 à 12, caractérisé en ce que l'on effectue une réaction d' hydrosilylation entre : - un silane de formule (3)17. Process for the preparation of a silane according to one of claims 1 to 12, characterized in that a hydrosilylation reaction is carried out between: - a silane of formula (3)
Xa Si (R ) b X a Si (R) b
H et un alkyldialcoxyborane insaturé de formule (4)H and an unsaturated alkyldialcoxyborane of formula (4)
22
ORGOLD
CH = CH (CH2 2)> Ç, (CH2 2)/ d B,CH = CH (CH 2 2)> Ç, (CH 2 2) / d B,
ORGOLD
formules (3) et (4) dans lesquelles R1, X, a, b, c, d, Z, e, R2 ont les mêmes significations qu'aux revendications 1 à 12.formulas (3) and (4) in which R 1 , X, a, b, c, d, Z, e, R 2 have the same meanings as in claims 1 to 12.
18. Procédé de préparation de silanes selon l'une des revendications 1 à 12, caractérisé en ce que l'on effectue une réaction d'hydroboration entre :18. Process for the preparation of silanes according to one of claims 1 to 12, characterized in that a hydroboration reaction is carried out between:
22
ORGOLD
H BH B
22
ORGOLD
(5)(5)
et χa si (R ) b and χ a if (R) b
(CH2)C 2e (CH2)y. CH = CH2 (CH 2 ) C 2e (CH 2 ) y. C H = CH 2
(6) dans laquelle : . c' = 2 à 18 . d' = 0 à 16 . c' + d" = 2 à 18 formules (5) et (6) dans lesquelles R2, X, a, R1, b, Z ont les mêmes significations qu'aux revendications 1 à 12, . avec la possibilité, lorsque e = 0, que c' = 0 et d' = 0 ou 1 (c' + d' = 0 ou 1).(6) in which:. c '= 2 to 18. from = 0 to 16. c '+ d "= 2 to 18 formulas (5) and (6) in which R 2 , X, a, R 1 , b, Z have the same meanings as in claims 1 to 12,. with the possibility, when e = 0, that c '= 0 and d' = 0 or 1 (c '+ d' = 0 or 1).
19. Procédé de préparation d'un polyorganosiloxane selon l'une des revendications 13 à 16, caractérisé en ce que l'on effectue une réaction d'hydrosilylation entre : un polyorganosiloxane présentant par molécule au moins un motif de formule (11 )19. Process for the preparation of a polyorganosiloxane according to one of claims 13 to 16, characterized in that a hydrosilylation reaction is carried out between: a polyorganosiloxane having per molecule at least one unit of formula (11)
HH
X f Si (O)X f Si (O)
(f + g)(f + g)
(R )(R)
dans laquelle R1, g, X, f ont les mêmes significations qu'à la revendication 13 prise sans son disclaimer ou 14 etin which R 1 , g, X, f have the same meanings as in claim 13 taken without its disclaimer or 14 and
- un alkyldialcoxyborane insaturé de formule (4)- an unsaturated alkyldialcoxyborane of formula (4)
22
^/ OR CH2 = CH (CH2)C— Ze (CH2) d βv ^ / OR CH 2 = CH (CH 2 ) C - Z e (CH 2 ) d β v
OR dans laquelle R2, c, Z, e, d ont les mêmes significations qu'aux revendications 1 prise sans son disclaimer et 2 à 12 .GOLD in which R 2 , c, Z, e, d have the same meanings as in claims 1 taken without its disclaimer and 2 to 12.
20. Procédé de préparation d'un polyorganosiloxane selon l'une des revendications 6 à 9, caractérisé en ce que l'on effectue une réaction d'hydroboration en faisant réagir ensemble :20. Process for the preparation of a polyorganosiloxane according to one of claims 6 to 9, characterized in that a hydroboration reaction is carried out by reacting together:
ORGOLD
H BH B
ORGOLD
(5) et(5) and
(CH2 2)'C' (CH2)d, -CH = CH.(CH 2 2) 'C ' (CH 2 ) d , -CH = CH.
X, Si -OX, Si -O
-(f + g)- (f + g)
(12)(12)
(R ) ',g(R) ', g
dans laquelle c' = 2 à 18 d' = 0 à 16 c' + d' = 2 à 18 formules (5) et (12) dans lesquelles R2, X, f, R1, g, Z et e ont les mêmes significations qu'à la revendication 13 prise sans son disclaimer ou 14, . avec la possibilité, lorsque e = 0, que c' = 0 et d' = 0 ou 1 (c' + d' = 0 ou 1 ).in which c '= 2 to 18 d' = 0 to 16 c '+ d' = 2 to 18 formulas (5) and (12) in which R 2 , X, f, R 1 , g, Z and e have the same meanings as in claim 13 taken without its disclaimer or 14,. with the possibility, when e = 0, that c '= 0 and d' = 0 or 1 (c '+ d' = 0 or 1).
21. Procédé de préparation d'un polyorganosiloxane selon l'une des revendications 13 prise sans son disclaimer à 16, caractérisé en ce que l'on effectue l'hydrolyse et/ou la redistribution d'un silane selon l'une quelconque des revendications 1 à 12 avec un polysiloxane cyclique ou linéaire comprenant des motifs de formule (8) :21. Process for the preparation of a polyorganosiloxane according to one of claims 13 taken without its disclaimer at 16, characterized in that the hydrolysis and / or redistribution of a silane is carried out according to any one of the claims 1 to 12 with a cyclic or linear polysiloxane comprising units of formula (8):
(R ) , (O)(R), (O)
4 - h4 - h
dans laquelle : - h = 2 ou 3in which : - h = 2 or 3
R1 a la même signification qu'aux revendications 1 à 12.R 1 has the same meaning as in claims 1 to 12.
22. Procédé de préparation d'un polyorganosiloxane selon l'une des revendications 13 prise sans son disclaimer à 17, caractérisé en ce que l'on effectue l'hydrolyse et/ou la redistribution d'un silane selon l'une quelconque des revendications 1 à 12, avec un silane hydrolysable de formule (13)22. Process for the preparation of a polyorganosiloxane according to one of claims 13 taken without its disclaimer at 17, characterized in that the hydrolysis and / or redistribution of a silane is carried out according to any one of the claims 1 to 12, with a hydrolyzable silane of formula (13)
Rm X n SiR m X n Si
dans laquelle :in which :
- m = 2 ou 3 m + n = 4- m = 2 or 3 m + n = 4
- X et R1 ont les mêmes significations qu'aux revendications 1 à 12.- X and R 1 have the same meanings as in claims 1 to 12.
23. Composition organopolysiloxane, stable au stockage en l'absence d'humidité et pouvant réticuler par exposition à l'humidité en l'absence de catalyseur de réticulation, comprenant :23. Organopolysiloxane composition, stable on storage in the absence of moisture and capable of crosslinking by exposure to moisture in the absence of a crosslinking catalyst, comprising:
(A) - 100 parties en poids d'au moins un polydiorganosiloxane selon l'une quelconque des revendications 13 à 16, (B) - de 0 à 250 parties en poids d'une charge minérale.(A) - 100 parts by weight of at least one polydiorganosiloxane according to any one of claims 13 to 16, (B) - from 0 to 250 parts by weight of a mineral filler.
24. Composition organopolysiloxane aqueuse, stable au stockage et pouvant réticuler par élimination d'eau, en l'absence de catalyseur, comprenant :24. An aqueous organopolysiloxane composition, stable in storage and capable of crosslinking by elimination of water, in the absence of catalyst, comprising:
(A) - 100 parties en poids d'au moins un polydiorganosiloxane selon l'une quelconque des revendications 13 à 16,(A) - 100 parts by weight of at least one polydiorganosiloxane according to any one of claims 13 to 16,
(B) - de 0 à 250 parties en poids d'une charge minérale(B) - from 0 to 250 parts by weight of a mineral filler
(C) - de 0,5 à 20, de préférence de 3 à 15 parties en poids d'eau(C) - from 0.5 to 20, preferably from 3 to 15 parts by weight of water
(D) - éventuellement un tensioactif non ionique, anionique, cationique ou amphotère.(D) - optionally a nonionic, anionic, cationic or amphoteric surfactant.
25. Méthode pour conférer à un substrat des propriétés de surface anti-adhérentes et/ou hydrophobantes, dans laquelle on enduit un substrat, e.g. une matière textile, un métal, de la pierre ou un élément à base de ciment, avec un polyorganosiloxane selon l'une des revendications 13 à 16 ou avec une composition selon l'une des revendications 23 et 24. 25. Method for imparting non-stick and / or hydrophobic surface properties to a substrate, in which a substrate, eg a textile material, a metal, stone or a cement-based element, is coated with a polyorganosiloxane according to one of claims 13 to 16 or with a composition according to one of claims 23 and 24.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU59889/99A AU5988999A (en) | 1998-10-06 | 1999-10-04 | Silanes and polyorganosiloxanes with boronate function(s) |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR98/12636 | 1998-10-06 | ||
| FR9812636A FR2784679B1 (en) | 1998-10-06 | 1998-10-06 | BORONATE FUNCTION (S) SILANES AND POLYORGANOSILOXANES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2000020425A1 true WO2000020425A1 (en) | 2000-04-13 |
Family
ID=9531349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR1999/002362 WO2000020425A1 (en) | 1998-10-06 | 1999-10-04 | Silanes and polyorganosiloxanes with boronate function(s) |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU5988999A (en) |
| FR (1) | FR2784679B1 (en) |
| WO (1) | WO2000020425A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7790730B2 (en) | 2004-07-27 | 2010-09-07 | Gilead Sciences, Inc. | Imidazo[4,5-d]pyrimidines, their uses and methods of preparation |
| WO2011065144A1 (en) * | 2009-11-27 | 2011-06-03 | Jsr株式会社 | Composition, cured product, and electronic device |
| EP2332938A1 (en) | 2002-07-03 | 2011-06-15 | K.U. Leuven Research & Development | Viral inhibitors |
| JP2012006991A (en) * | 2010-06-22 | 2012-01-12 | Jsr Corp | Polymer, composition, cured product and electronic device |
| KR20190024379A (en) * | 2017-08-31 | 2019-03-08 | 오씨아이 주식회사 | Etching compositions and etching method using the same |
| CN109852318A (en) * | 2018-12-26 | 2019-06-07 | 广州市高士实业有限公司 | A kind of pair of plastics have the silane modified polyether seal glue of good bonding |
| CN116003802A (en) * | 2022-12-05 | 2023-04-25 | 东莞市唯纳孚润滑科技有限公司 | Boron-containing hybrid ester modified silicone oil, preparation method thereof and lubricating grease |
| CN116003802B (en) * | 2022-12-05 | 2024-06-11 | 东莞市唯纳孚润滑科技有限公司 | Boron-containing hybrid ester modified silicone oil, preparation method thereof and lubricating grease |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110607162A (en) * | 2019-09-29 | 2019-12-24 | 烟台德邦科技有限公司 | LED packaging silica gel with high adhesion and high refractive index and preparation method thereof |
-
1998
- 1998-10-06 FR FR9812636A patent/FR2784679B1/en not_active Expired - Fee Related
-
1999
- 1999-10-04 WO PCT/FR1999/002362 patent/WO2000020425A1/en active Application Filing
- 1999-10-04 AU AU59889/99A patent/AU5988999A/en not_active Abandoned
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 104, no. 7, 17 February 1986, Columbus, Ohio, US; abstract no. 48229, GLAD, MAGNUS ET AL: "Use of silane monomers for molecular imprinting and enzyme entrapment in polysiloxane-coated porous silica" XP002102383 * |
| J. CHROMATOGR. (1985), 347(1), 11-23 CODEN: JOCRAM;ISSN: 0021-9673, 1985 * |
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| EP2332938A1 (en) | 2002-07-03 | 2011-06-15 | K.U. Leuven Research & Development | Viral inhibitors |
| US7790730B2 (en) | 2004-07-27 | 2010-09-07 | Gilead Sciences, Inc. | Imidazo[4,5-d]pyrimidines, their uses and methods of preparation |
| JP5664874B2 (en) * | 2009-11-27 | 2015-02-04 | Jsr株式会社 | Moisture trapping composition, cured body and electronic device |
| WO2011065144A1 (en) * | 2009-11-27 | 2011-06-03 | Jsr株式会社 | Composition, cured product, and electronic device |
| CN102639642A (en) * | 2009-11-27 | 2012-08-15 | Jsr株式会社 | Composition, cured product, and electronic device |
| EP2505613A1 (en) * | 2009-11-27 | 2012-10-03 | JSR Corporation | Composition, cured product, and electronic device |
| EP2505613A4 (en) * | 2009-11-27 | 2012-12-12 | Jsr Corp | Composition, cured product, and electronic device |
| JPWO2011065144A1 (en) * | 2009-11-27 | 2013-04-11 | Jsr株式会社 | Composition, cured body and electronic device |
| JP2012006991A (en) * | 2010-06-22 | 2012-01-12 | Jsr Corp | Polymer, composition, cured product and electronic device |
| KR20190024379A (en) * | 2017-08-31 | 2019-03-08 | 오씨아이 주식회사 | Etching compositions and etching method using the same |
| KR102311335B1 (en) | 2017-08-31 | 2021-10-14 | 오씨아이 주식회사 | Etching compositions and etching method using the same |
| CN109852318A (en) * | 2018-12-26 | 2019-06-07 | 广州市高士实业有限公司 | A kind of pair of plastics have the silane modified polyether seal glue of good bonding |
| CN109852318B (en) * | 2018-12-26 | 2021-03-23 | 广州市高士实业有限公司 | Silane modified polyether sealant with good adhesion to plastics |
| CN116003802A (en) * | 2022-12-05 | 2023-04-25 | 东莞市唯纳孚润滑科技有限公司 | Boron-containing hybrid ester modified silicone oil, preparation method thereof and lubricating grease |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU5988999A (en) | 2000-04-26 |
| FR2784679A1 (en) | 2000-04-21 |
| FR2784679B1 (en) | 2001-03-30 |
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