WO2004063266A1 - Procédé de préparation d'une suspension de silice dans une matiere silicone eventuellement réticulable - Google Patents
Procédé de préparation d'une suspension de silice dans une matiere silicone eventuellement réticulable Download PDFInfo
- Publication number
- WO2004063266A1 WO2004063266A1 PCT/FR2003/003817 FR0303817W WO2004063266A1 WO 2004063266 A1 WO2004063266 A1 WO 2004063266A1 FR 0303817 W FR0303817 W FR 0303817W WO 2004063266 A1 WO2004063266 A1 WO 2004063266A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pos
- functions
- silica
- crosslinking
- suspension
- Prior art date
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 266
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 123
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000725 suspension Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 94
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 46
- 238000002360 preparation method Methods 0.000 claims abstract description 40
- 229920002545 silicone oil Polymers 0.000 claims abstract description 36
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 56
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 54
- 238000004132 cross linking Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000003921 oil Substances 0.000 claims description 47
- -1 siloxanes Chemical class 0.000 claims description 44
- 239000000945 filler Substances 0.000 claims description 35
- 239000008346 aqueous phase Substances 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 102100039659 Adenylate cyclase type 3 Human genes 0.000 claims description 23
- 101710194150 Adenylate cyclase type 3 Proteins 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000003381 stabilizer Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 230000003014 reinforcing effect Effects 0.000 claims description 13
- 239000012763 reinforcing filler Substances 0.000 claims description 13
- 150000004756 silanes Chemical class 0.000 claims description 13
- 239000002518 antifoaming agent Substances 0.000 claims description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 239000007900 aqueous suspension Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002318 adhesion promoter Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 150000003973 alkyl amines Chemical class 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000003093 cationic surfactant Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000006254 rheological additive Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 230000036961 partial effect Effects 0.000 claims description 7
- 239000004971 Cross linker Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 230000007717 exclusion Effects 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 5
- 239000005046 Chlorosilane Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- WKWOFMSUGVVZIV-UHFFFAOYSA-N n-bis(ethenyl)silyl-n-trimethylsilylmethanamine Chemical compound C[Si](C)(C)N(C)[SiH](C=C)C=C WKWOFMSUGVVZIV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims 2
- 150000002431 hydrogen Chemical group 0.000 claims 2
- 239000000969 carrier Substances 0.000 claims 1
- 230000037361 pathway Effects 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 25
- 239000000806 elastomer Substances 0.000 abstract description 25
- 239000000843 powder Substances 0.000 abstract description 18
- 229920002379 silicone rubber Polymers 0.000 abstract description 11
- 238000000518 rheometry Methods 0.000 abstract description 7
- 238000010348 incorporation Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 239000012429 reaction media Substances 0.000 abstract description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 abstract 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000005051 trimethylchlorosilane Substances 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 29
- 125000000217 alkyl group Chemical group 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229940073561 hexamethyldisiloxane Drugs 0.000 description 4
- 238000005360 mashing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012053 oil suspension Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012632 extractable Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical group CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SPSGYTWOIGAABK-DQEYMECFSA-N [4-[(2s)-2-acetamido-3-[[(5s)-3-carbamoyl-2-(cyclohexylmethoxy)-6,7,8,9-tetrahydro-5h-benzo[7]annulen-5-yl]amino]-3-oxopropyl]-2-phosphonophenyl]phosphonic acid Chemical compound C([C@H](NC(=O)C)C(=O)N[C@@H]1C2=CC(=C(OCC3CCCCC3)C=C2CCCC1)C(N)=O)C1=CC=C(P(O)(O)=O)C(P(O)(O)=O)=C1 SPSGYTWOIGAABK-DQEYMECFSA-N 0.000 description 1
- KVKVYYGLSLKKNR-UHFFFAOYSA-N [diacetyloxy(2-cyanoethyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)CCC#N KVKVYYGLSLKKNR-UHFFFAOYSA-N 0.000 description 1
- DRWYONGJPZHQOD-UHFFFAOYSA-N [diacetyloxy(3,3,3-trifluoropropyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)CCC(F)(F)F DRWYONGJPZHQOD-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- LGWCCQIZIJQENG-UHFFFAOYSA-N chloro-hex-1-enyl-dimethylsilane Chemical compound CCCCC=C[Si](C)(C)Cl LGWCCQIZIJQENG-UHFFFAOYSA-N 0.000 description 1
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000007822 coupling agent 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 238000000265 homogenisation Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000765 intermetallic 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
- 238000004898 kneading Methods 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PULCKIYKBGOTTG-UHFFFAOYSA-N n-(2,4-dimethylpentan-3-ylidene)hydroxylamine Chemical compound CC(C)C(=NO)C(C)C PULCKIYKBGOTTG-UHFFFAOYSA-N 0.000 description 1
- ODCQZCNSWWLGCQ-UHFFFAOYSA-N n-(2-chlorocyclohexylidene)hydroxylamine Chemical compound ON=C1CCCCC1Cl ODCQZCNSWWLGCQ-UHFFFAOYSA-N 0.000 description 1
- DNYZBFWKVMKMRM-UHFFFAOYSA-N n-benzhydrylidenehydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1=CC=CC=C1 DNYZBFWKVMKMRM-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 125000005447 octyloxy 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])O* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920006294 polydialkylsiloxane Polymers 0.000 description 1
- 235000021395 porridge Nutrition 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OLTVTFUBQOLTND-UHFFFAOYSA-N tris(2-methoxyethoxy)-methylsilane Chemical compound COCCO[Si](C)(OCCOC)OCCOC OLTVTFUBQOLTND-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- 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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- 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
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- 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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Definitions
- the field of the invention is that of charged silicones and in particular silicone elastomers crosslinkable by polyaddition or polycondensation and silicone anti-foam compositions.
- the present invention relates to the preparation of an intermediate product useful for obtaining these elastomers and these anti-foam silicone compositions.
- This intermediate product consists of a fine charge suspension (as defined below):
- Si-OH Si-OH
- the fillers considered are reinforcing fillers, to be distinguished from non-reinforcing fillers.
- the most commonly used reinforcing fillers are preferably fumed silicas having a BET surface area> 50 m 2 / g. They owe their reinforcing effect on the one hand, to their morphology and on the other hand, to the hydrogen bonds which form between the silanol groups on the surface of the silicas and the polyorganosiloxane chains. These interactions between the filler and the polymer increase the viscosity and modify the behavior of the polymer in the vicinity of the solid surface of the fillers.
- connections between polymer and filler improve the mechanical properties but can also cause a prejudicial premature hardening ("structuring") of the precursor compositions of the elastomers.
- the non-reinforcing fillers have an extremely weak interaction with the silicone polymer. These include, for example, chalk, quartz powder, diatomaceous earth, mica, kaolin, aluminas or iron oxides. Their effect is often to increase the viscosity of the unvulcanized precursors of the elastomers, as well as the Shore hardness and the elastic modulus of the latter.
- the silicone elastomers can also contain, inter alia, catalysts, inhibitors, crosslinkers, pigments, non-stick agents, plasticizers and adhesion promoters. These elastomers which can be crosslinked by polyaddition or polycondensation, are shaped before crosslinking by casting, extrusion, calendering, coating, with a brush or with a gun, or by compression molding, injection or transfer.
- Cold-crosslinkable silicone compositions in elastomers are conventionally packaged in the form of two-component systems, that is to say comprising two parts packaged separately. and to be mixed at the time of use.
- one of the components comprises the catalyst for the polyaddition reaction.
- This catalyst is preferably platinum in nature. It may, for example, be a platinum complex such as that prepared from chloroplatinic acid and divinyl-1,3-tetramethyl-l-, l-, 3-, 3-disiloxane, according to the patent US-B-3,814,730 (Karstedt catalyst). Other platinum complexes are described in US Pat. Nos. 3,159,601, 3,159,662 and 3,220,972.
- This component comprising the catalyst generally also comprises a type A POS with Fa: Si-alkenyl, preferably Si-vinyl, crosslinking functions.
- the other component, without catalyst, comprises at least one type B POS with Eb: Si-H crosslinking functions.
- POS type A and POS type B comprise at least two groups Si-Vi and Si-H respectively per molecule, preferably in ⁇ , ⁇ for POS type A; at least one of the two must comprise at least three crosslinking functions per molecule.
- These two-component systems can also include a platinum inhibitor allowing the components to crosslink only when mixed together, possibly having been heated.
- inhibitors examples include polyorganosiloxanes, advantageously cyclic, substituted with at least one alkenyl, tetramethylvinyltetrasiloxane being particularly preferred, pyridine, phosphines and organic phosphites (Irgafos® P-PPQ, for example), unsaturated amides, alkylated maleates, and acetylenic alcohols, (Cf. FR-B-1 528 464 and FR-A-2 372 874).
- Such compositions can also be presented in the form of single-component systems which crosslink only after being heated.
- the silicone compositions which can be crosslinked or curable into elastomers by polycondensation at room temperature or at higher temperatures are conventionally packaged in the form of single-component systems (that is to say comprising a single package) or two-component systems (that is to say comprising two parts packed separately and which must be mixed at the time of use).
- one of the components comprises in particular a type C POS having reactive ends Fc, in particular hydroxydimethylsiloxy, the other component comprising the catalyst of the polycondensation reaction.
- This catalyst can be a metallic compound, such as for example an organic tin compound.
- This component comprising the catalyst can also comprise a crosslinking agent D carrying Fd functions capable of reacting with the reactive functions Fc of POS C.
- compositions can also be presented in the form of single-component systems which crosslink at room temperature, in the presence of moisture.
- the fillers used are particulate fillers of the type of those mentioned above for the elastomeric compositions. These charges act through their non-deformable nature, their geometry and their dimensions as well as through the interactions they exchange with the surrounding environment.
- the preparation of concentrated suspensions (mashings) of reinforcing particulate fillers in reactive or non-reactive silicone oils, intended to produce crosslinkable elastomers or anti-foam silicone compositions is a step in the processes for preparing elastomeric compositions widely used in the field.
- silicone elastomers The best known reinforcing particulate fillers are based on pyrogenic silica, but substances such as precipitation silica, titanium oxide, for example, can also be used in certain cases.
- These charges have a BET specific surface of at least 1 m 2 / g up to generally 400 m 2 / g.
- These are ultra-fine powders that can be dispersed in silicone oils. This dispersion poses problems of mixing the powdery charge with the oil and particular care must be taken to obtain a uniform distribution of the charge in the suspension.
- compatibilizers There are mainly two types of compatibilizers:
- This compatibilization treatment can take place before and / or during and / or after the incorporation of the filler (e.g. silica) in the polyorganosiloxane oils.
- the filler e.g. silica
- French patent application FR-A-2 320 324 describes a homogeneous distribution process in polyorganosiloxane oils, of a filler based on highly dispersed pyrogenic silica and with a BET specific surface of at least 50 m 2 / g .
- This process is characterized in that the filler is treated during the incorporation, in the presence of water, with a compatibilizing agent (hexamethyldisilazane).
- This accounting treatment of the silica with the silicone oil can be described as "early" since the HMDZ is present as soon as the reinforcing combustion silica is brought into contact with this silicone oil.
- EP-A-0 462 032 describes a process for preparing a pasting which can be used in particular in compositions which can be crosslinked by polyaddition reaction.
- the compatibilization treatment using hexamethyldisilazane takes place after the incorporation of the silica into the silicone oil. This processing method is here called "late”.
- PCT patent application WO-A-02/44259 discloses the preparation of a suspension of precipitation silica in a silicone oil, this suspension being usable for producing crosslinkable silicones by polyaddition or by polycondensation (RTV elastomers).
- the precipitated silica is treated using hexamethyldisilazane (HMDZ) introduced in two fractions (15 and 85%) in a crosslinkable silicone oil. The first fraction is first brought into contact with the precipitation silica and water.
- HMDZ hexamethyldisilazane
- Isopropyl alcohol, THexaMethylDiSiloxane (HDMS or M 2 ) or toluene are also part of the reagents in addition to the aqueous silica slurry.
- the temperature is also increased (65 ° C).
- HDMS can be replaced by Me 2 SiCl 2 .
- one of the essential objectives of the present invention is to provide an economical process for preparing a suspension of a particulate charge treated with a compatibilizing agent based on aminosilanes or of halosilanes, in a silicone oil, this suspension which can be useful as a raw material for the preparation of: two-component or even single-component silicone compositions, crosslinkable in particular by polyaddition, polycondensation or dehydrogenocondensation, in silicone elastomers,> or anti-silicone compositions foam.
- This process must meet the following specifications: coupling in a single production sequence of the silica compatibilization treatment in particular using aminosilanes or halosilanes and mixing the silica with a polysiloxane silicone material capable of being used directly as a raw material for the preparation of crosslinkable silicone compositions, standardization and homogenization of the distribution of the filler in the silicone oil, optimization of the dispersion, viscosity suitable for the handling and transformation of the suspension,
- Another essential objective of the invention is to provide a process for the preparation of a reinforcing filler / silicone oil suspension for elastomers, which is suitable for silicone materials (oils) having a long chain length (for example having at least 100 patterns D -cf nomenclature infra-) and therefore viscous and difficult to mix even in high power mixers.
- Another essential objective of the invention is to provide a process for the preparation of a reinforcing filler / silicone oil suspension for elastomers, which is simple to implement and applicable on an industrial scale.
- Another essential objective of the invention is to provide an efficient and direct process for obtaining a suspension of reinforcing filler in a silicone oil for elastomers, this process being of the type of that aimed for in the abovementioned objectives.
- Another essential objective of the invention is to provide a process for obtaining a silicone composition, crosslinkable by polyaddition or polycondensation or even dehydrogenocondensation, to form an elastomer and comprising as a constituent element the suspension as obtained by the process referred to below. -above.
- Another essential objective of the invention is to provide a process for obtaining a silicone anti-foam composition and comprising as a constituent element the suspension as obtained by the process referred to above.
- this suspension being, in particular, usable for producing crosslinkable compositions by polyaddition and / or by polycondensation and / or by dehydrogenocondensation or anti-foam silicone compositions;
- This process being of the kind in which an aqueous suspension of silica particulate filler is made hydrophobic by treatment using at least one halogenated reagent, this treatment comprising a transfer of the silica rendered hydrophobic in a nonaqueous phase and at least one step of at least partial removal of the water;
- AC compatibilization agent
- Way I either selected from silazanes, taken alone or as a mixture between them, preferably from disilazanes, Phexamethyldisilazane (HMDZ) associated or not with divinyl - tetramethyldisilazane being particularly preferred
- the particulate charge is selected from the group of precipitation silicas,
- an aqueous suspension of silica is prepared or used comprising:> silica,
- siloxane resins (iii) silanes; (iv) and their mixtures;
- amines such as, for example, alkylamines (such as diethylamine) and / or silylamines: "and of surfactants and more particularly cationic surfactants.
- the compatibilization agent (AC III) is chosen from the group comprising:
- siloxanes with hydroxyl terminations of low molecular weight are “siloxanes with hydroxyl terminations of low molecular weight (advantageously less than 100 g / mole) di or mono functional;
- amines such as, for example, alkylamines (such as diethylamine) and / or silylamines; 1 and surfactants and more particularly cationic surfactants.
- the compatibilization agent (AC III) is chosen from the group comprising:
- siloxane resins (ii) siloxane resins; (iii) silanes; (iv) and their mixtures;
- AC I AC I
- any compatibilization agent selected from silazanes, taken alone or as a mixture between them, in particular the disilazanes such as the associated hexamethyldisilazane (HMDZ) or not with divinyltetramethyldisilazane;
- amines such as, for example, alkylamines (such as diethylamine) and / or silylamines:" and surfactants and more particularly cationic surfactants.
- the compatibilization agent (AC III) is chosen from the group comprising: (i) the POSs carrying, in and / or at the ends of their chains, compatibilization functions OR 111 ′ in which R IIh independently corresponds to hydrogen or to a radical corresponding to the same definition as that given above for R c ; (ii) siloxane resins;
- This compatibilization agent (AC III) is associated with at least one condensation catalyst preferably selected from:
- strong bases and more preferably still in the subgroup comprising: KOH, LiOH, NaOH and their mixtures;
- metal salts and more preferably still in the subgroup comprising: tin salts, salts of titanium and their mixtures; "the salts of triflic acid;
- amines such as, for example, alkylamines (such as diethylamine) and / or silylamines;” and surfactants and more particularly cationic surfactants.
- the advantages of this new process for the preparation of silicic suspensions are in particular: * significant reduction in cost; easy implementation; obtaining suspensions endowed with suitable rheological qualities and viscoelastic behavior (no or low flow threshold with a viscosity added as a function of the silica content and the viscosity of the oils used); in particular, they have a fluidity stable over time and suitable for handling and processing operations, such as pumping, conveying, mixing, shaping, molding, extrusion, etc., and this including for long silicone oils and therefore already viscous in themselves; implementation -develling- facilitated for the elastomeric compositions prepared from these suspensions; and in addition, improved transparency of the elastomeric compositions prepared from these suspensions.
- step Ile For an elastomeric silicone composition, step Ile) is mandatory and it is even completed by devolatilization (distillation) to completely eliminate volatiles, including water;
- an anti-foam silicone composition it is optionally possible to dispense with eliminating the volatile species including water, with a view to subsequent emulsification.
- a silicone solvent eg hexane, cyclohexane, heptane, CC1, octane, dichloromethane, toluene, methyl ethyl ketone, methyl isobutyl ketone, white spirit, xylene
- a silicone solvent eg hexane, cyclohexane, heptane, CC1, octane, dichloromethane, toluene, methyl ethyl ketone, methyl isobutyl ketone, white spirit, xylene
- route II is that it may be advantageous to provide a pH, for example less than or equal to 2, preferably 1, at least during step Ha).
- the compatibilization agent AC III is incorporated after YAC I or VAC II, preferably after the withdrawal of all or part of the aqueous phase, provided that said withdrawal takes place.
- the ⁇ . ⁇ -dihydroxylated POSs more especially retained are the polydialkylsiloxanes ⁇ . ⁇ -bis (dialkylhydroxysiloxy), with short chains, for example of molecular weight less than or equal to 1 OOOg / mole.
- alkyl substituents of these POSs are preferably C1-C6 alkyls and even more preferably methyls.
- siloxane resin is meant within the meaning of the invention a resin comprising siloxy units Q and / or T and optionally siloxy units M and / or D and / or Q 0Rq and / or T 0Rt and / or M 0Rm and / or D 0Rd ' .
- Rq '- H or radical of the same definition as R m .
- siloxane resins AC III (iii) more especially retained are the resins MQ, MM 0RM Q, MQQ ORQ ' or MM 0RM' QQ 0RQ ' .
- AC III is added in an amount of 0.5 to 40% by weight, preferably 0.5 to 40% by weight relative to the amount of silica particulate filler used in the suspension.
- the invention also relates to a treatment intended to make the silica hydrophobic, which treatment being capable of being implemented in the process for the preparation of a suspension of a filler (eg silica) in a silicone.
- This process is characterized in that, according to the route II: Ha ′):
- an aqueous suspension of silica comprising 100 parts by dry weight of silica, optionally acidified using 20 to 60 (preferably 30 to 50) parts by weight of at least one acid, knowing that the pH of the non-aqueous phase is preferably ⁇ 2, and more preferably still ⁇ 1, "0 to 500 (preferably 0 to 300) parts by weight of a siloxane silicone resin precursor, preferably sodium silicate, "5 to 500 (preferably 10 to 200) parts by weight of a nonaqueous hydrogen bond stabilizer / initiator,” 5 to 500 (preferably from 10 to 200) parts by dry weight of at least one halosilane precursor of hydrophobic units formed by units -
- Si- (R c) ⁇ 3 with R c hydrogen, C1-C 30 alkenyl, C 2 -C 30, aryl, these groups R c being optionally substituted (preferably halogenated), "40-2000 ( preferably 50 to 800) parts by weight of silicone material
- Ilf ' optionally washing the residual acidity of the non-aqueous phase, Ilg') optionally removing the liquid from the non-aqueous phase to recover the hydrophobic silica in powder form.
- This succession of operations makes it possible to optimize the grafting of hydrophobic ⁇ Si-R c patterns on silica.
- At least one precursor of siloxane resins (in particular MQ) as defined above can be used during step Ha).
- This precursor is preferably a silicate, and more preferably still a sodium silicate.
- the precursor of such siloxane resins (preferably a sodium silicate) is transformed into polysilicic acid in the presence of acidified water at a pH preferably ⁇ 2.
- This acid forms a network of Q units which aggregate on the silica initially set artwork.
- the functionalization (“hydrophobation") of the network using AC II then occurs.
- a silicone phase is thus obtained containing siloxane resin with a large Q core.
- the aqueous phase is devoid of any trace of silica.
- the precursor of siloxane resins is used in an amount of 20 to 60, preferably 30 to 50% by weight relative to the particulate filler used.
- the precursor of siloxane resins can be in the form of an aqueous solution.
- siloxane resins are advantageously as follows: those in accordance with the technical content of patents US-B-2,676,182 and US-B-2,814,601.
- functional units other than hydrophobic units are grafted onto the silica, by placing the latter in the presence of halosilane precursors of these functional grafts.
- the functions that can be provided to silica by these motifs are for example the following: bactericidal, bacteriostatic, chromophore, fluorescence, "anti-fouling", refractive index modifier, coupling with the silicone network (eg haloalkoxy) -alkenyl-silane, ... and their associations.
- one or more precipitating silica preferably present essentially in the form of a slurry and whose BET specific surface is between 50 and 400 m 2 / g,
- a precipitation silica results from a succession of operations which can be for example: precipitation of the silica in the aqueous phase by acidification, by addition of acid on a silicate base stock or by simultaneous total or partial addition of acid and silicate on a base of water or silicate solution, - filtration allowing to recover a phase enriched in silica, possibly disintegration of the precipitated silica filtrate to prepare an easily manipulated aqueous suspension, possibly drying of the silica precipitated, optionally grinding and / or compacting the precipitated silica powder, - and optionally bagging the precipitated silica powder thus obtained.
- the preparation of precipitated silica used in the context of the invention is described in documents EP-A-0 520 862, WO-A-95/09127 and WO-A-95/09128.
- the precipitated silica used in the process according to the invention can be in the form of powder or in the form of an aqueous slurry taken at the filtration or disintegration stage.
- the term "powder” used to qualify precipitated silica denotes precipitated silica in the solid state, generally in powder form or in the form of granules or substantially spherical beads.
- one or more precipitation silica are chosen whose BET specific surface is between 50 and 400 m 2 / g and mixing conditions such as the dynamic viscosity at 25 ° C. the suspension (pasting) is less than or equal to 300 Pa.s, preferably less than or equal to 150 Pa.s.
- the BET specific surface is determined according to the method of BRUNAUER, EMMET, TELLER described in "The Journal of the American Chemical Society, vol. 80, page 309 (1938)" corresponding to standard NFT 45007 of November 1987.
- the silica filler preferably (precipitation) represents from 10 to 50% by weight of the suspension. In practice, this charge is of the order of 30 ⁇ 10% by weight.
- the stabilizer / initiator of hydrogen bonds is chosen from organic solvents, preferably from the group comprising alcohols (in particular isopropyl alcohol, ethanol and butanol), ketones (in particular MethyllsoButylKetone: MIBK), amides (in particular DiMethylACetamide: DMAC), alkanes (in particular tetrahydrofuran: THF) and their mixtures.
- organic solvents preferably from the group comprising alcohols (in particular isopropyl alcohol, ethanol and butanol), ketones (in particular MethyllsoButylKetone: MIBK), amides (in particular DiMethylACetamide: DMAC), alkanes (in particular tetrahydrofuran: THF) and their mixtures.
- the acidification of the aqueous suspension (aqueous phase) which optionally occurs in the process according to the invention, is rather carried out using an acid, preferably a mineral acid, and more preferably another acid is chosen from the group comprising: HC1, H 2 S0 4 , H 3 P0 4 and their mixtures.
- the silicone material MS comprises at least one oligoorganosiloxane, preferably a diorganosiloxane, and more preferably still hexamethyldisiloxane (M 2 ).
- the oligoorganosiloxane (s) of the MS can can (can) be associated (s) with one or more polyorganosiloxanes (POS) of all types, in particular A, B, C, D, E as referred to above and defined in more detail below.
- POS polyorganosiloxanes
- oligoorganosiloxane denotes a siloxane oligomer comprising from 2 to 10 siloxy units of type M, D, or T, as defined above, while a polyorganosiloxane denotes a polymer comprising from 11 to 10,000, preferably 100 to 5,000.
- the silicone material MS of oligoorganosiloxane nature preferably corresponds to the first fraction optionally used, during step Ilb) of the process according to the invention for the preparation of a suspension of silica in a silicone oil.
- the halosilane precursor of hydrophobic units is an alkylhalosilane, preferably an alkylchlorosilane, and more preferably still a methylchlorosilane.
- This alkylhalosilane is very advantageously a blocker of the monosilane type, for example (CH 3 ) SiCl. This blocker limits the growth of silica, or even of the siloxane resin obtained from the preferably sodium silicate, used in step Ha) or 11a).
- halosilane (s) (s) in the group comprising: dialkyldihalogenonosilanes for example (CH 3 ) SiCl 2 , dialkylhydrogenohalogenonosilanes for example (CH 3 ) 2 SiCl2, alkylhydrogenodihalogenonosilanes, for example CH 3 S-HCI2, alkylalkenyldihalogenomonosilanes, for exampleCl ( 3 ) dialkylalkenylhalogenonosilanes, for example (CH 3 ) 2 ViSiCl, alkyltrihalogenonosilanes, for example (CH 3 ) SiCl 3 , hydrogenotrihalogenomonosilanes, for example HSiCl 3 , lesion cenyltrihalomenonosilanes, for example NiSi
- the alkyl may be a C1-C 30 alkenyl alkenyl, C2-C30.
- the alkyl, alkenyl or hydrogen substituents can be combined or replaced by an aryl.
- These alkyl, alkenyl or aryl groups may be optionally substituted (preferably halogen).
- the method according to route II may for example consist essentially in using a precipitated silica powder and in implementing the following operations:
- the aqueous suspension of silica optionally in several fractions, the stabilizer / initiator of hydrogen bonds-preferably consisting of isopropyl alcohol- , optionally an acid, preferably HCl;
- an alosilane precursor of hydrophobic units -Si- (R c ) j to 3 with R c as defined above and corresponding for example to a C 1 alkyl
- a part of the DM consisting of at least one oligoorganosiloxane - preferably hexamethyldisiloxane (M 2 ) -; • heating to a temperature close to the reflux temperature of the stabilizer / initiator of hydrogen bonds-preferably that of isopropyl alcohol between 70 and 80 ° C;
- this non-aqueous phase is washed with an aqueous liquid and then the aqueous washing phase is eliminated;
- - silica 100; - acid (e.g. HC1): 20 to 60, preferably 30 to 50;
- H bonds e.g. isopranol: 0 to 20, preferably from 1 to 10;
- - MS oil 40 to 2000, consisting exclusively or not of oligoorganosiloxane - preferably M 2 ; - water: 2 to 8000, preferably 200 to 1000.
- the silica used is in practice essentially in the form of a precipitated silica slurry (s). This avoids the step of preparing the porridge in the preparation enclosure. Furthermore, it is clear that the handling of a slurry is much easier than the handling of large volumes of powder, which moreover oblige to expel the corresponding air from the mixture being produced.
- the dryness of the silica slurry is generally between 1 and 50% by weight, preferably between 10 and 40% by weight.
- This new preparation process proves to be particularly economical and allows easy incorporation of the ingredients with tools that consume little energy. Indeed, the composition remains easily malleable throughout the process without it requiring a great deal of power for the kneading. This process also results, in the case of crosslinkable silicone elastomers, in the use properties of the elastomers that are entirely up to the expected specifications, compared to the conventional processes using combustion silica. The same applies with regard to pastings intended for preparing anti-foam compositions.
- the different stages of the process can be of variable duration and accomplished in separate apparatus.
- silicone oils used in the process according to the invention linear or cyclic, and preferably linear, polydiorganosiloxanes will preferably be chosen.
- the silicone material can be, first of all, a polyaddition MSi comprising:
- POS B reactive silicone oil whose crosslinking functions Fb are hydrogen functions, this POS B comprising at least two Si-H groups per molecule (preferably at least three when the POS A comprises only two Si- Vi per molecule), these Si-H being advantageously located in the chain,
- a catalytic system comprising a metal polyaddition catalyst (preferably of platinum nature) and optionally an inhibitor;” optionally one or more semi charge (s) - reinforcing (s), not reinforcing (s) or stuffing; "optionally water;” optionally one or more additive (s) chosen from pigments, plasticizers, other rheology modifiers, stabilizers and / or adhesion promoters.
- POS A can be - for example - a polydialkyle- (methyl) -siloxane ⁇ , o divinylated oil.
- the POS A used for the preparation of the suspension is a vinylated POS A carrying at least two Si-Vi units per molecule, preferably at least three per molecule, when the POS B comprises only two Si- Vi units H per molecule.
- POS B is for example ⁇ olyalkyl (methyl) hydrogenosiloxane or alternatively a branched hydrogenated POS comprising tri or tetrafunctional units and units carrying SiH.
- POS E can be a polydiorganosiloxane, such as a polyalkylesiloxane, preferably a polydimethylsiloxane with trimethylsilyl ends, optionally at the chain end and in the chain of functions such as, for example, hydroxyls.
- the preferred silicone oils (A, B, E) essentially comprise units R ' 2 SiO, the symbols R 1 , identical or different, representing (cyclo) alkyl groups C, -C 10 optionally halogen, alkenyl groups C 1 -C 12 , aryl groups, these radicals R being optionally substituted or halogens.
- alkyl mention may in particular be made of methyl, ethyl propyl and butyl groups,
- the silicone material can be an MS 2 polycondensation comprising:
- R represents identical or different monovalent hydrocarbon radicals
- Y represents hydrolysable or condensable groups OR 1 1 with R 11 corresponding to the same definition as that given above for R c ,
- a catalytic system comprising a metallic condensation catalyst; "possibly one or more semi-reinforcing, non-reinforcing or tamping filler (s);” possibly water;
- additive chosen from pigments, plasticizers, other rheology modifiers, stabilizers and / or adhesion promoters.
- radicals R are methyl radicals
- the other radicals can generally be phenyl radicals.
- hydrolyzable groups Y there may be mentioned amino, acylamino, aminoxy, ketiminoxy, iminoxy, enoxy, alkoxy, alkoxy-alkylene-oxy, acyloxy and phosphato groups and, for example, among these:
- Y groups n-butylamino, sec-butylamino and cyclohexylamino groups
- - for substituted N acylamino groups the benzoyl-amino group
- iminoxy and ketiminoxy groups those derived from acetophenone oxime, acetone oxime, benzophenone oxime, methyl ethyl ketoxime, diisopropyl ketoxime and chlorocyclohexanone oxime,
- alkoxy groups Y groups having from 1 to 8 carbon atoms such as methoxy, propoxy, isopropoxy, butoxy, hexyloxy and octyloxy groups,
- acyloxy Y groups groups having from 1 to 8 carbon atoms such as formyloxy, acetoxy, propionyloxy and 2-ethyl hexanoyloxy groups,
- phosphato Y groups those deriving from dimethyl phosphate, diethyl phosphate and dibutyl phosphate groups.
- condensable groups Y mention may be made of hydrogen atoms and halogen atoms, preferably chlorine.
- POS C hydroxyls of formula (1) a mixture consisting of several polymers hydroxyls which differ from each other by the value of the viscosity and / or the nature of the substituents linked to the silicon atoms.
- the hydroxyl polymers of formula (1) may optionally include, alongside the units D of formula R_, SiO. T units of formula RSiO, -, and / or Q units of formula SiO- in the proportion of at most 1% (these% expressing the number of T and / or Q units per 100 silicon atoms).
- This MS 2 polycondensation can also comprise a non-reactive silicone oil comprising non-reactive POS E corresponding to the following formula (2):
- radicals R mention may be made of alkyl radicals having from 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl and octyl, phenyl radicals.
- substituted R radicals mention may be made of trifluoro-radicals.
- the hydroxylated polymers of formula (2) may optionally comprise, alongside the units D of formula R-SiO, units T of formula RSi0 3 / -, and / or units Si0 2 in the proportion at most 1% (these percentages expressing the number of T and / or Q units per 100 silicon atoms).
- the latter is preferably chosen from:
- crosslinking agent D being compulsory when the reactive POS (s) are ⁇ , ⁇ - dihydroxylated POS, and optional (but desirable) when the reactive POS C (s) carry at each end of the chains condensable (other than OH) or hydrolysable groups.
- crosslinking agents D selected from monomeric silanes
- polyacyloxysilanes there may be mentioned more particularly polyacyloxysilanes, polyalkoxysilanes, polyketiminoxysilanes and polyiminoxysilanes, and in particular the following silanes: CH 3 Si (OCOCH 3 ) 3 ; C 2 H-Si (OCOCH.) 3 ;
- CH 2 CHSi (OCH 3 ) 3 ;
- Partial hydrolysis products for example, polyalkoxysilanes, usually called alkyl polysilicates, are well known products. The most commonly used product is ethyl polysilicate 40® resulting from the partial hydrolysis of Si (OC 2 H 5 ) 4 .
- the crosslinking agents D preferably used in the case of the preferred use of ⁇ , ⁇ -dihydroxylated POS of formula (1), are the alkyltrialkoxysilanes and the tetraalkoxysilanes of formula (3) where R represents an alkyl radical having from 1 to 4 carbon atoms, and the partial hydrolysis products of these preferred silanes.
- the MS silicone material can be of the MS 3 type crosslinkable by poçlydehydrogenocondensation.
- the POS B 'and C of MS 3 correspond to the same definitions as those given above for the POS B and C respectively.
- the invention also relates to a process for the preparation of a silicone composition which can be crosslinked by polydehydrogenation, characterized in that in that an MS 3 polydehydrogen condensation is used comprising: "at least one type C POS carrying functions of hydroxyl crosslinking
- the reinforcing filler / silicone oil suspension prepared in accordance with the invention is to be used in obtaining liquid or pasty silicone compositions which can be crosslinked by polyaddition or polycondensation, preferably in silicone elastomer in the ambient atmosphere at temperature. normal or at a higher temperature, or non-reactive liquid or pasty silicone compositions (anti-foam).
- the present invention relates to a process for obtaining a crosslinkable silicone composition by polyaddition, consisting in incorporating in particular into the suspension as prepared according to the process as defined above, the following products:
- POS E POS E
- a catalytic system comprising a catalyst, preferably of a platinum nature, and possibly an inhibitor.
- composition is produced in the form of two-component systems Pi and P 2 intended to be brought into contact with one another to produce an elastomer crosslinked by polyaddition between POS A and B, and it is ensured that the only one of the parts Pi or P 2 contains catalyst ⁇ , the other containing the POS B.
- compositions which can be crosslinked by polyaddition of elastomers may also comprise one or more functional additives ⁇ , such as for example a non-reinforcing filler formed by chalk, quartz powder, diatomaceous earth, mica, kaolin, aluminas or iron oxides.
- functional additives ⁇ can also consist of pigments, non-stick agents, plasticizers or rheology modifiers, stabilizers or adhesion promoters.
- the invention also relates to a process for obtaining a crosslinkable silicone composition by polycondensation, characterized in that it consists in incorporating, in particular, into the suspension as prepared according to the process as defined above, the following products:
- crosslinking agent (s) D - ⁇ '- optionally one or more POS E, as defined above and useful (s) as diluent (s);
- additive chosen from pigments, plasticizers, other rheology modifiers, stabilizers and / or adhesion promoters.
- the charges v ′ generally have a particle diameter greater than 0.1 ⁇ m and are preferably chosen from ground quartz, zirconates, calcined clays, diatomaceous earths, calcium carbonate, aluminas .
- a single-component composition (that is to say a single package) is produced intended to crosslink in the presence of moisture, in particular humidity provided by the ambient air or by the water present and / or added within the composition, at ambient temperature and / or under the effect of the temperature which can range, for example from 25 ° C. to a value of less than 100 ° C.
- the crosslinking catalyst ⁇ 'used is a metal catalyst which is chosen in particular from tin monocarboxylates, diorgano tin dicarboxylates, a valence IV tin chelate, a chelate of hexacoordinated valence IV tin, amino silanes, an organic derivative of titanium, an organic derivative of zirconium.
- each composition is produced in the form of a two-component system (or two packages) PI and P2, intended to be brought into contact with each other to result in a polycondensation elastomer,
- the polycondensation catalyst ⁇ 'used is preferably an organic derivative of tin as defined above, an amine or a mixture of these species or an organic derivative of titanium.
- the mixtures involved in these processes can be produced using known and appropriate devices. These can be, for example, conventional mixers usually used for these preparations:
- the mixing operation is carried out at normal temperature and pressure and preferably under an inert atmosphere (N 2 ). It should moreover that, under these conditions, the silicone oil, the water but also the accounting agent are in liquid form to facilitate mixing.
- the aqueous phase containing approximately 380-400 g of clear water (without silica) is removed from the mixer and the silicone phase, which has remained in the tank, is returned to stirring.
- 175 g of ⁇ , ⁇ -dihydroxylated polydimethylsiloxane oil (“hydroxylated” oil) with a viscosity of approximately 50,000 mPa.s are then added to the tank, then an amount x of ⁇ , ⁇ -dihydroxylated polydimethylsiloxane oil (“hydroxylated” oil) of very low viscosity (4-5 Si per chain) and the whole is heated under nitrogen sweeping for 1.5 hours at approximately 100 ° C. Heating is further continued at 150 ° C for 2 h under vacuum (about 20-50 mmHg).
- aqueous phase containing 402 g of clear water (without silica) is removed from the mixer and the silicone phase, which has remained in the tank, is returned to stirring.
- 122.5 g of ⁇ , ⁇ -dihydroxylated polydimethylsiloxane oil (“hydroxylated” oil) with a viscosity of approximately 50,000 mPa.s are then added to the tank, then 5 g of very, ⁇ -dihydroxylated polydimethylsiloxane oil (“hydroxylated” oil). low viscosity (4-5 Si per chain) and the whole is heated under nitrogen sweeping for 1.5 hours at approximately 100 ° C.
- a sample is then taken to analyze the rheology.
- the viscosity of the products is monitored as a function of x.
- the measurement is carried out with the needle
- the mashings are stable over time, as shown by the lack of change in viscosity over several weeks.
- aqueous phase containing approximately 400 g of clear water (without silica) is removed from the mixer and the silicone phase, which has remained in the tank, is returned to stirring. Then added to the tank 122 g of ⁇ , ⁇ -dihydroxylated polydimethylsiloxane oil ("hydroxylated” oil) with a viscosity of approximately 14,000 mPa.s then 105 g of ⁇ , de-dihydroxylated polydimethylsiloxane oil ("hydroxylated” oil) of very low viscosity (4-5 Si per chain) and the whole is heated under nitrogen sweeping for 1.5 hours at approximately 100 ° C.
- Heating is further continued at 150 ° C for 2 h under vacuum (about 20-50 mmHg). It is then cooled and when the temperature has dropped to about 60 ° C., 143 g of ⁇ , ⁇ -trimethylsilylpolydimethylsiloxane oil ("methylated” oil) with a viscosity of about 50 mPa.s, 53.0 g of oil are added with stirring. hydroxylated "with a viscosity of 14000 mPa.s and 10.0 g of fluid hydroxylated oil. After 30 min of mixing (always at 400 rpm), the tank is emptied.
- the composition was crosslinked using a catalyst comprising a mixture of silanes and a polycondensation catalyst with tin in the proportions 100 / 1.5.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003299365A AU2003299365A1 (en) | 2002-12-30 | 2003-12-19 | Method for preparing a silica suspension in a potentially crosslinkable silicone material |
EP03799648A EP1578860A1 (fr) | 2002-12-30 | 2003-12-19 | Proc d de pr paration d'une suspension de silice dans une matiere silicone eventuellement r ticulable |
US10/541,139 US20060241222A1 (en) | 2002-12-30 | 2003-12-19 | Method for preparing a silica suspension in an potentially crosslinkable silicone material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0216868A FR2849441B1 (fr) | 2002-12-30 | 2002-12-30 | Procede de preparation d'une suspension de silice dans une matiere silicone eventuellement reticulable |
FR0216868 | 2002-12-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004063266A1 true WO2004063266A1 (fr) | 2004-07-29 |
Family
ID=32480294
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2003/003817 WO2004063266A1 (fr) | 2002-12-30 | 2003-12-19 | Procédé de préparation d'une suspension de silice dans une matiere silicone eventuellement réticulable |
Country Status (8)
Country | Link |
---|---|
US (1) | US20060241222A1 (fr) |
EP (1) | EP1578860A1 (fr) |
KR (1) | KR100689682B1 (fr) |
CN (1) | CN1745132A (fr) |
AU (1) | AU2003299365A1 (fr) |
FR (1) | FR2849441B1 (fr) |
TW (2) | TWI306465B (fr) |
WO (1) | WO2004063266A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006067225A1 (fr) * | 2004-12-22 | 2006-06-29 | Ge Bayer Silicones Gmbh & Co. Kg | Composes amino-polyorganosiloxane reticules et compositions les contenant |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101481549B (zh) * | 2009-01-20 | 2012-11-28 | 蓝星有机硅(上海)有限公司 | 沉淀法二氧化硅的表面处理方法及其应用 |
KR20150063561A (ko) * | 2012-10-05 | 2015-06-09 | 스페셜티 미네랄스 (미시간) 인코포레이티드 | 충전제 현탁액 및 종이 제조에 있어서의 이의 용도 |
CN104190280A (zh) * | 2014-09-05 | 2014-12-10 | 无锡贺邦金属制品有限公司 | 硅悬浮液及其制备方法 |
US10150842B2 (en) * | 2014-12-19 | 2018-12-11 | Dow Silicones Corporation | Method of preparing condensation cross-linked particles |
WO2017064730A1 (fr) * | 2015-10-16 | 2017-04-20 | Wacker Metroark Chemicals Pvt. Ltd. | Composition de mélange maître contenant une charge prétraitée, processus par étapes pour sa fabrication, et utilisations associées |
CN118185361B (zh) * | 2024-05-16 | 2024-09-10 | 沭阳凤凰美术颜料有限公司 | 一种环保型美术颜料的制备工艺 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0778307A2 (fr) * | 1995-11-29 | 1997-06-11 | Dow Corning Corporation | Méthode de préparation d'un mélange de polydiorganosiloxane-silice, le mélange ainsi obtenu et joint silicone réticulable à température ambiante |
US5750610A (en) * | 1997-02-24 | 1998-05-12 | Dow Corning Corporation | Hydrophobic organosilicate-modified silica gels |
EP0475132B1 (fr) * | 1990-08-27 | 1998-06-10 | Idemitsu Kosan Company Limited | Sol de dioxide de silicium hydrofuge et procédé pour sa préparation |
WO1998058997A1 (fr) * | 1997-06-24 | 1998-12-30 | Rhodia Chimie | Procede de preparation d'une suspension de silice dans une matrice silicone vulcanisable pour former des elastomeres |
WO2000037549A1 (fr) * | 1998-12-22 | 2000-06-29 | Rhodia Chimie | Procede de preparation d'une suspension de silice dans une matrice silicone reticulable par polycondensation pour former des elastomeres |
EP0900829B1 (fr) * | 1997-09-03 | 2001-11-14 | Dow Corning Corporation | Procédé de préparation de silice précipitée hydrophobe |
FR2817262A1 (fr) * | 2000-11-30 | 2002-05-31 | Rhodia Chimie Sa | Procede de preparation d'une suspension de silice dans une matrice silicone eventuellement reticulable |
EP1217042A1 (fr) * | 2000-12-20 | 2002-06-26 | General Electric Company | Préparation de caoutchouc de silicone liquide en continu |
EP0982268B1 (fr) * | 1998-08-24 | 2003-04-16 | Dow Corning Corporation | Procédé de préparation de silice colloidale non aggrégée hydrophobe |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2676182A (en) * | 1950-09-13 | 1954-04-20 | Dow Corning | Copolymeric siloxanes and methods of preparing them |
US2814601A (en) * | 1954-04-29 | 1957-11-26 | Dow Corning | Organopolysiloxane adhesive and pressure-sensitive adhesive tape containing same |
US3122520A (en) * | 1959-10-05 | 1964-02-25 | Dow Corning | Method of making silicone rubber fillers |
US3159662A (en) * | 1962-07-02 | 1964-12-01 | Gen Electric | Addition reaction |
US3220972A (en) * | 1962-07-02 | 1965-11-30 | Gen Electric | Organosilicon process using a chloroplatinic acid reaction product as the catalyst |
US3159601A (en) * | 1962-07-02 | 1964-12-01 | Gen Electric | Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes |
NL129346C (fr) * | 1966-06-23 | |||
US3814730A (en) * | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
DE2535334B2 (de) * | 1975-08-07 | 1978-09-28 | Bayer Ag, 5090 Leverkusen | Verfahren zur homogenen Verteilung hochdisperser aktiver Füllstoffe in Poly organosiloxanen |
DE2654893A1 (de) * | 1976-12-03 | 1978-06-15 | Wacker Chemie Gmbh | Verfahren zum herstellen von klebrige stoffe abweisenden ueberzuegen |
US4785047A (en) * | 1987-07-30 | 1988-11-15 | Dow Corning Corporation | Method for preparing clear polyorganosiloxane elastomers |
FR2663340B1 (fr) * | 1990-06-13 | 1994-04-08 | Rhone Poulenc Chimie | Procede de preparation d'empatage en extrudeuse double-vis pour compositions rtv sih/sivi. |
FR2678259B1 (fr) * | 1991-06-26 | 1993-11-05 | Rhone Poulenc Chimie | Nouvelles silices precipitees sous forme de granules ou de poudres, procedes de synthese et utilisation au renforcement des elastomeres. |
FR2710630B1 (fr) * | 1993-09-29 | 1995-12-29 | Rhone Poulenc Chimie | Nouvelles silices précipitées, leur procédé de préparation et leur utilisation au renforcement des élastomères. |
US6169135B1 (en) * | 1993-09-29 | 2001-01-02 | Rhone Poulenc Chimie | Precipitated silica |
US5942590A (en) * | 1997-02-24 | 1999-08-24 | Dow Corning Corporation | Process for making hydrophobic silica with reduced surface area under neutral conditions |
US5919298A (en) * | 1998-01-12 | 1999-07-06 | Dow Corning Corporation | Method for preparing hydrophobic fumed silica |
US6184408B1 (en) * | 1999-04-28 | 2001-02-06 | Dow Corning Corporation | Method for preparation of hydrophobic precipitated silica |
-
2002
- 2002-12-30 FR FR0216868A patent/FR2849441B1/fr not_active Expired - Fee Related
-
2003
- 2003-12-19 EP EP03799648A patent/EP1578860A1/fr not_active Withdrawn
- 2003-12-19 KR KR1020057012467A patent/KR100689682B1/ko not_active Expired - Fee Related
- 2003-12-19 US US10/541,139 patent/US20060241222A1/en not_active Abandoned
- 2003-12-19 WO PCT/FR2003/003817 patent/WO2004063266A1/fr not_active Application Discontinuation
- 2003-12-19 CN CNA2003801094650A patent/CN1745132A/zh active Pending
- 2003-12-19 AU AU2003299365A patent/AU2003299365A1/en not_active Abandoned
- 2003-12-29 TW TW092137354A patent/TWI306465B/zh not_active IP Right Cessation
-
2004
- 2004-01-06 TW TW093100350A patent/TW200523212A/zh unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0475132B1 (fr) * | 1990-08-27 | 1998-06-10 | Idemitsu Kosan Company Limited | Sol de dioxide de silicium hydrofuge et procédé pour sa préparation |
EP0778307A2 (fr) * | 1995-11-29 | 1997-06-11 | Dow Corning Corporation | Méthode de préparation d'un mélange de polydiorganosiloxane-silice, le mélange ainsi obtenu et joint silicone réticulable à température ambiante |
US5750610A (en) * | 1997-02-24 | 1998-05-12 | Dow Corning Corporation | Hydrophobic organosilicate-modified silica gels |
WO1998058997A1 (fr) * | 1997-06-24 | 1998-12-30 | Rhodia Chimie | Procede de preparation d'une suspension de silice dans une matrice silicone vulcanisable pour former des elastomeres |
EP0900829B1 (fr) * | 1997-09-03 | 2001-11-14 | Dow Corning Corporation | Procédé de préparation de silice précipitée hydrophobe |
EP0982268B1 (fr) * | 1998-08-24 | 2003-04-16 | Dow Corning Corporation | Procédé de préparation de silice colloidale non aggrégée hydrophobe |
WO2000037549A1 (fr) * | 1998-12-22 | 2000-06-29 | Rhodia Chimie | Procede de preparation d'une suspension de silice dans une matrice silicone reticulable par polycondensation pour former des elastomeres |
FR2817262A1 (fr) * | 2000-11-30 | 2002-05-31 | Rhodia Chimie Sa | Procede de preparation d'une suspension de silice dans une matrice silicone eventuellement reticulable |
EP1217042A1 (fr) * | 2000-12-20 | 2002-06-26 | General Electric Company | Préparation de caoutchouc de silicone liquide en continu |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006067225A1 (fr) * | 2004-12-22 | 2006-06-29 | Ge Bayer Silicones Gmbh & Co. Kg | Composes amino-polyorganosiloxane reticules et compositions les contenant |
Also Published As
Publication number | Publication date |
---|---|
FR2849441B1 (fr) | 2006-07-28 |
US20060241222A1 (en) | 2006-10-26 |
TW200420625A (en) | 2004-10-16 |
KR100689682B1 (ko) | 2007-03-12 |
KR20050093814A (ko) | 2005-09-23 |
FR2849441A1 (fr) | 2004-07-02 |
TW200523212A (en) | 2005-07-16 |
EP1578860A1 (fr) | 2005-09-28 |
CN1745132A (zh) | 2006-03-08 |
AU2003299365A1 (en) | 2004-08-10 |
TWI306465B (en) | 2009-02-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0991712B1 (fr) | Procede de preparation d'une suspension de silice dans une matrice silicone vulcanisable pour former des elastomeres | |
AU615122B2 (en) | Process for rendering hydrophobic a particulate solid containing si-oh groups and the use of the resulting hydrophobic particulate solid in a process for preparing compositions, based on diorganopolysiloxanes, which can be cured to form elastomers | |
WO2004063265A1 (fr) | Procédé de préparation d'une suspension de silice dans une matiere silicone eventuellement réticulable | |
EP0055957B2 (fr) | Procédé de moulage par injection de compositions organopolysiloxaniques pâteuses | |
EP1877470B1 (fr) | Compositions organopolysiloxanes durcissant en elastomeres des la temperature ambiante en presence d' humidite | |
FR2471947A1 (fr) | Silice de precipitation, notamment utilisable comme charge renforcante | |
JP2986746B2 (ja) | 低分子有機珪素化合物及び架橋性材料 | |
US7790829B2 (en) | Curable and cured silicone rubber compositions and methods therefor | |
CN105705599B (zh) | 树脂-线性有机硅氧烷嵌段共聚物的组合物 | |
FR2734833A1 (fr) | Resines de silicone de faible masse moleculaire pour moulage par injection de liquide presentant une teneur elevee en groupes vinyle | |
WO2018066572A1 (fr) | Nouveau copolymère séquencé résine – organopolysiloxane linéaire, et application ainsi que procédé de fabrication de celui-ci | |
JP2006307226A (ja) | 流動性の架橋可能なポリオルガノシロキサン材料及びその製造方法 | |
EP1578860A1 (fr) | Proc d de pr paration d'une suspension de silice dans une matiere silicone eventuellement r ticulable | |
EP1141108B1 (fr) | Procede de preparation d'une suspension de silice dans une matrice silicone reticulable par polycondensation pour former des elastomeres | |
FR2474517A1 (fr) | Compositions organosiliciques contenant de nouvelles silices de precipitation a proprietes renforcantes ameliorees | |
EP1337581A1 (fr) | Procede de preparation d'une suspension de silice dans une matrice silicone eventuellement reticulable | |
FR2639950A1 (fr) | ||
EP3625299B1 (fr) | Composition silicone reticulant par polyaddition utile pour le surmoulage de pieces |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2003799648 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020057012467 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20038A94650 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 1020057012467 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2003799648 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006241222 Country of ref document: US Ref document number: 10541139 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 10541139 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |