EP1499660A2 - Ensemble catalytique pour hydrosilylation, son procede de preparation et compositions silicone l incorporant - Google Patents
Ensemble catalytique pour hydrosilylation, son procede de preparation et compositions silicone l incorporantInfo
- Publication number
- EP1499660A2 EP1499660A2 EP03747466A EP03747466A EP1499660A2 EP 1499660 A2 EP1499660 A2 EP 1499660A2 EP 03747466 A EP03747466 A EP 03747466A EP 03747466 A EP03747466 A EP 03747466A EP 1499660 A2 EP1499660 A2 EP 1499660A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- inhibitor
- formula
- radical
- linear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 129
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000003112 inhibitor Substances 0.000 claims abstract description 134
- 239000003054 catalyst Substances 0.000 claims abstract description 120
- 230000003197 catalytic effect Effects 0.000 claims abstract description 69
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 150000004756 silanes Chemical class 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 239000002779 cholinesterase reactivator Substances 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 129
- -1 cyclic alkyl radical Chemical class 0.000 claims description 84
- 229910052697 platinum Inorganic materials 0.000 claims description 61
- 239000000654 additive Substances 0.000 claims description 58
- 230000000996 additive effect Effects 0.000 claims description 40
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 150000003254 radicals Chemical class 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229920002545 silicone oil Polymers 0.000 claims description 10
- 150000005840 aryl radicals Chemical class 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 230000002401 inhibitory effect Effects 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000013626 chemical specie Substances 0.000 claims 3
- 238000001816 cooling Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000000712 assembly Effects 0.000 abstract description 5
- 238000000429 assembly Methods 0.000 abstract description 5
- 239000000470 constituent Substances 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 35
- 150000001875 compounds Chemical class 0.000 description 25
- 230000005764 inhibitory process Effects 0.000 description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010668 complexation reaction Methods 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 238000010348 incorporation Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 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 5
- 230000000694 effects Effects 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 4
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000003060 catalysis inhibitor Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000013538 functional additive Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007970 homogeneous dispersion Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000003057 platinum Chemical class 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 229920006137 organovinylpolysiloxane Polymers 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZBVOEVQTNYNNMY-UHFFFAOYSA-N O=P1=CCCC1 Chemical class O=P1=CCCC1 ZBVOEVQTNYNNMY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 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
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 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
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012763 reinforcing filler 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
Definitions
- the invention relates to new catalyst inhibitors for hydrosilylation reactions involving polyorganosiloxanes (POS) carrying Si-H units and POSs carrying ethylenic and / or acetylenic unsaturation (s), hereinafter referred to as POS carrying Si- [ethylenic or acetylenic unsaturation] units and to the catalytic units obtained from the mixture of these inhibitors and catalysts.
- POS polyorganosiloxanes
- POSs ethylenic and / or acetylenic unsaturation
- the invention also relates to monocomponent silicone compositions crosslinking by hydrosilylation reactions and comprising such an inhibitor or catalytic unit.
- the invention also relates to specific methods for using inhibitors of hydrosilylation catalysts, to methods for preparing mixtures of inhibitors and catalysts, to methods for preparing monocomponent silicone compositions and to compositions capable of 'be obtained by the implementation of these processes.
- the Karstedt complex can be prepared by bringing 1, 3-divinyltetramethyldisiloxane into contact with chloroplatinic acid (H 2 PtCI 6 ), in the presence of NaHCO 3 and an aqueous-alcoholic solvent (eg isopropanol).
- chloroplatinic acid H 2 PtCI 6
- NaHCO 3 aqueous-alcoholic solvent
- aqueous-alcoholic solvent eg isopropanol
- FR-A-2 801 887 discloses metal complexes useful as hydrosilylation catalysts, of formula:
- R 3 represents a hydrogen atom; an (C ⁇ -Cs) alkyl group; or a group
- T 1 and T 2 are identical and represent (C ⁇ -C ⁇ ) alkyl or (C 3 -C 8 ) cycloalkyl;
- R d and R e are identical and represent (d-CsJalkyle or (C 3 -C 8 ) cycloalkyle;
- US-A-3 188 300 describes the use of various phosphine or phosphite ligands of formula:
- R 1 , R 2 and R 3 are alkyl, aryl, aralkyl, alkaryl, alkoxy, aryloxy, aralkoxy, alkaryloxy radicals.
- US-A-5 380 812 proposes di- and trihydrocarbylphosphines, di- and trihydrocarbylphosphine oxides, di- and triorganophosphites of formula
- R 1 is a substituted or unsubstituted monovalent hydrocarbon radical, for example alkyl, aralkyl, alkaryl, and a is 2 or 3.
- the phosphines make it possible to instantaneously inhibit platinum but their affinity for platinum is such that the catalytic system finally obtained exhibits poor reactivity.
- the phosphites exhibit a more interesting inhibition / reactivity compromise.
- the properties of the catalytic systems can depend on the conditions of their implementation and on the dispersion of the inhibitor / catalyst couple in the silicone material.
- organophosphorus compounds are generally little or not soluble in silicone oils, which is likely to cause poor dispersion of these compounds.
- the complexation of platinum, and therefore its inhibition can be long to obtain with such a process, which therefore exposes to non-optimal homogeneity and to premature crosslinking of the final composition.
- inhibitors which make it possible to reconcile a high inhibitory power and a good catalytic activity, and which make it possible to prepare monocomponent compositions having a satisfactory pot life (“pot-life”), eg from 1 day to several months. It would also be interesting to have efficient methods of implementing these inhibitors / catalysts.
- the present invention therefore aims to meet this need by proposing new inhibitors and more particularly a new catalytic assembly comprising a catalyst and an inhibitor, the catalytic activity being inhibited (not detectable) at room temperature.
- Another objective of the invention is to propose methods for implementing inhibitor / catalyst pairs which make it possible to ensure, under the best conditions, the catalyst / inhibitor coupling and / or the dispersion of the catalyst, of the inhibitor and of the catalytic assemblies. in a silicone composition.
- Yet another objective of the invention is to provide catalytic assemblies having improved ease of implementation, in particular for their mixing with silicone compositions.
- Yet another objective of the invention is to provide a silicone composition crosslinkable by hydrosilylation and comprising, as catalyst, such a catalytic assembly having activity inhibited at room temperature, so as to allow the production of monocomponent compositions comprising the catalyst and suitable compounds to react hot by hydrosilylation of unsaturated units (eg POS SiH / POS Si-alkenyl), while being stable at room temperature for long periods (eg 1 d to several months).
- unsaturated units eg POS SiH / POS Si-alkenyl
- composition or catalytic assembly comprising a metal catalyst capable of catalyzing a hydrosilylation reaction and an inhibitor corresponding to the following formula (I):
- R, R, R, R and R identical or different, represent a linear, branched or cyclic alkyl radical, or a substituted or unsubstituted aryl radical, in particular:
- - a linear or branched alkyl radical, in particular having from 2 to 30 carbon atoms (C), preferably from 2 to 12 C, - an alkyl radical comprising one or more rings, in particular 1 or 2, a ring which may in particular have 4 to 14 C, preferably 5 to 8 C, or
- an aryl or alkylaryl radical comprising one or more adjoining or non-adjoining aromatic rings, in particular 1 or 2 rings, a cycle possibly comprising from 4 to 14 C, preferably from 6 to 8 C, optionally substituted by 1 or several, in particular from 1 to 2, linear or branched alkyl (s), in particular having from 1 to 12 C, preferably from 4 to 12 C, composition or assembly in which the inhibitor inhibits the action catalytic converter.
- the catalytic action is inhibited at room temperature, but can be restored by heating (e.g. between 50 and 200 ° C, more particularly between 100 and 150 ° C).
- inhibitor and catalyst are complexed.
- inhibition covers a so-called complete inhibition, due to the incorporation of a sufficient amount of inhibitor (in particular with 1 atom or preferably more than 1 atom of phosphorus P for a metal atom of the catalyst).
- the term also covers a so-called incomplete inhibition, if the quantity of inhibitor incorporated is not sufficient. In the latter case in particular, it may be supplemented by the separate incorporation of the same type of inhibitor or by another inhibitor.
- the composition comprises, as solvent, an organosilicon compound, such as a silane, a siloxane, a silicone oil and / or a silicone gum.
- the composition can thus comprise one or more unsaturated silanes and / or one or more unsaturated siloxanes comprising one or more siloxane units (eg from 2 to 200, preferably from 2 to 30). They are preferably vinylsilanes and / or vinylsiloxanes. More than details as to their nature will be given later.
- the silanes and siloxanes described in US-A3 775452 and US-A-3,715,334, to which reference is made later, are possible methods.
- the composition can also comprise one or more oils or silicone gums such as those which are described below, and which cover alkenylated species, in particular vinylated, and species which are not (eg based on units corresponding to the formula ( V) defined below).
- the invention relates to a catalytic composition or assembly comprising, optionally in an organosilicon solvent as described above, the metal catalyst capable of catalyzing a hydrosilylation reaction and an inhibitor of formula (I), in which : R, R 1 , R 2 , R 3 and R 4 , identical or different, represent a linear, branched or cyclic alkyl radical, or a substituted or unsubstituted aryl radical, in particular:
- - a linear or branched alkyl radical having from 2 to 30 carbon atoms (C), preferably from 2 to 12 C, an alkyl radical comprising one or more rings, in particular 1 or 2, a ring which may in particular have from 4 to 14 C, preferably 5 to 8 C, or
- R is advantageously a cyclic alkyl radical, and even better an alryl radical, in particular bi-phenyl.
- R 1 , R 2 , R 3 and R 4 are advantageously cyclic alkyl radicals, and even better aryl radicals and more preferably alkylaryl radicals, in particular substituted phenyl, eg tert-butyl-phenyl.
- R 1 , R 2 , R 3 and R 4 are preferably identical.
- compounds with aryl or cyclic alkyl radicals are preferred for their inhibitory activity of longer duration than compounds with linear or branched alkyl radicals.
- radicals R which are identical or different, preferably identical, are linear or branched alkyls, having in particular from 1 to 12 C, preferably from 4 to 12 C.
- the preferred inhibitor corresponds to formula (III):
- the metal molar ratios of the catalyst to the inhibitor can be between 1 / 0.5 and 1/10, preferably between 1/1 and 1/5.
- the catalysts targeted by the invention include all the catalysts useful for the hydrosilylation of POS carrying Si-H units and of POS carrying Si- [ethylenic or acetylenic unsaturation] units. They can therefore be platinum, rhodium, iridium, nickel, ruthenium and / or palladium compounds. They are more particularly compounds of iridium or better still of platinum.
- the platinum compound can be any complex of platinum and an organic product, eg those described in patents US-A-3,159,601, US-A-3,159,602, US-A-3,220,972 and European patents EP-A-0 057 459, EP-A-0 188 978 and EP-A-0 190 530, or any complex of platinum and vinylated organosiloxanes, eg those described in patents US-A-3,419,593, US -A-3,715,334, US-A-3,377,432 and US-A-3,814,730.
- chloroplatinic acid Mention may be made of chloroplatinic acid, a chloroplatinic acid modified by an alcohol, or alternatively a complex of chloroplatinic acid with an olefin, an aldehyde or a vinylsiloxane among others.
- the patent US-A-2 823 218 discloses a hydrosilylation catalyst of the chloroplatinic acid type and the patent US-A-3419 593 relates to catalysts formed by chloroplatinic acid and organosilicone complexes of the vinylsiloxane type.
- Platinum and hydrocarbon complexes useful as hydrosilylation catalyst are disclosed by US-A-3,159,601 and 3,159,602.
- US-A-3,723,497 describes a platinum acetylacetonate and US patent A-3,220,972 relates to catalysts based on platinum alcoholate.
- the invention relates more particularly to the platinum / unsaturated siloxane complexes, in particular the platinum / vinylsiloxane complexes, in particular those obtained by reaction between a platinum halide and an unsaturated organosilicon material such as an unsaturated silane or an unsaturated siloxane, eg according to the invention.
- the invention preferably applies to solutions or complexes from Karstedt.
- the catalytic assembly according to the invention comprises a mixture of the catalyst and the inhibitor leading to a new complex species between these two compounds.
- the new species (I ') has a structure of the type:
- the subject of the present invention is also: - these new species,
- a metal catalyst in particular of platinum, in particular hydrosilylation catalyst, in particular in a monocomponent silicone composition crosslinking by hydrosilylation reaction
- the catalyst is inhibited by the inhibitor at room temperature. Its activation can be induced by temperature rise.
- the inhibitors according to the invention are soluble in unsaturated silanes, in particular vinylated ones such as vinyltrimethoxysilane (VTMO) and in unsaturated siloxanes, eg vinylsiloxanes and in solutions platinum / unsaturated silane and platinum / unsaturated siloxane, eg platinum / vinyisiloxane.
- unsaturated silanes in particular vinylated ones such as vinyltrimethoxysilane (VTMO) and in unsaturated siloxanes, eg vinylsiloxanes and in solutions platinum / unsaturated silane and platinum / unsaturated siloxane, eg platinum / vinyisiloxane.
- VTMO vinyltrimethoxysilane
- platinum / unsaturated silane and platinum / unsaturated siloxane eg platinum / vinyisiloxane.
- the catalyst solution and the inhibitor can be mixed until the inhibitor is completely dissolved.
- the inhibitor is added to the catalyst solution.
- An additive or catalytic assembly in which catalyst and inhibitor are present in the form of a complex, is first prepared.
- the catalyst is thus inhibited at room temperature.
- This additive is intended to be added to the single-component silicone composition under conditions ensuring a fine and homogeneous dispersion.
- the present invention therefore also relates to a process for the preparation of an additive or catalytic assembly (or catalytic composition) comprising an inhibitor / catalyst pair.
- R is an alkylaryl radical having in particular from 7 to 31 carbon atoms, preferably substituted phenyl radicals, eg substituted by linear or branched alkyls, preferably identical, having in particular from 1 to 12 C, preferably from 4 to 12 C, for example t-Bu.
- R 2 , R 4 and R 5 represent H and R 1 and R 3 represent preferably identical aliphatic radicals, eg t-Bu.
- this ratio can be between 1/1 and 1/10, preferably between 1/2 and 1/5.
- At least one inhibitor of formula (I) and at least one inhibitor of formula (VIII) are used (e.g. an inhibitor of formula
- the amounts of inhibitors can be determined in order to substantially maintain the P ratio of the inhibitor / Pt of the catalyst resulting from the application of the ratios set out above. above.
- the respective amounts of inhibitors are chosen to ensure a metal to catalyst ratio of phosphorus of between 1/1 and 1/10.
- a solution comprising the catalyst and the inhibitor is prepared, by mixing the organophosphorus inhibitor in the catalyst.
- an unsaturated silane eg vinylsilane, or unsaturated siloxane, preferably unsaturated siloxane such as vinylsiloxane, eg in the platinum / unsaturated siloxane solution, especially in the platinum / vinyisiloxane solution, preferably in the Karstedt solution.
- the inhibitors of formula (I), in particular the inhibitors of formula (II) and (III), are soluble in silanes and unsaturated siloxanes, which allows easy and rapid dissolution of these inhibitors in a catalytic solution, in particular of the siloxane type, eg in the Karstedt solution, and rapid and effective inhibition of the catalyst.
- the catalyst-inhibitor solution can comprise from 0.1 to 15%, preferably from 5 to 10%, by weight of platinum metal.
- the mixing can be carried out by any conventional stirring means, e.g. with a paddle stirrer.
- the method comprises the dispersion of the organophosphorus inhibitor in an oil and / or a silicone gum,
- the oil or the silicone gum is heated to the appropriate temperature before, during and / or after the addition of the organophosphorus derivative.
- the organophosphorus compound is first dispersed in the oil or gum maintained at a temperature below the melting point, then the composition is heated to a temperature above the melting or softening temperature of the organo compound. -phosphorus.
- the organophosphorus compound disperses quickly, efficiently and homogeneously in silicone oil or gum. It can generally be considered that a duration of dispersion greater than a few minutes, in particular of the order of 5 min to 1 h, preferably from 15 min to 30 min, is sufficient.
- the silicone material is preferably brought to a temperature higher than 1 to 50 ° C, in particular 5 to 20 ° C, preferably 10 to 20 ° C, above the melting or softening temperature of the organo-compound. phosphorus used.
- stirring of the mixture of silicone material and inhibitor is maintained, for a sufficient time to ensure good fusion of the dispersed organophosphorus compound. It can generally be considered that a heating and stirring period greater than a few minutes, in particular of the order of 5 min to 1 h, preferably from 15 min to 30 min, is sufficient.
- the catalyst can then be added to the composition previously obtained. To avoid denaturing the catalyst, when necessary, the above composition is cooled to a temperature below the denaturation point of the catalyst.
- the previous composition it is preferable to bring the previous composition to room temperature, eg of the order of 25 ° C.
- the Karstedt solution or complex is added and the whole is mixed.
- the mixing is continued until homogeneous dispersion of the catalyst in the silicone material and the formation of an inhibitor / catalyst complex generated in situ is obtained, remarkably dispersed in a fine and homogeneous manner in the silicone gum or oil.
- the silicone gum or oil, or a mixture, used to form this solution is chosen to be compatible with the final silicone composition.
- an oil, gum or mixture with a viscosity close to or identical to that of the final silicone composition or of the portion of the latter in which the inhibitor-catalyst solution will first be mixed is used.
- PDMS polydimethylsiloxane gum
- the viscosity of these non-vinylated (non-alkenylated) oils or gums can range from a few mPa / s to a few million mPa / s, the choice possibly depending in particular on the type of final silicone composition, eg RTV, LSR or EVC, of which it is question below.
- the mixing of the ingredients at the different stages is carried out using a mixing device adapted to the viscosity of the oil or gum used. For rather high viscosities, as in the case of oils or gums used in EVCs, it is possible to use a roller mixer or an arm mixer.
- both modes 1 and 2 it may be useful to add to the composition each time obtained, one or more ingredients intended to facilitate mixing with the final silicone composition. It may in particular be a question of adapting the viscosity, in order to bring it closer to that of the constituent or of the mixture of constituents of the final silicone material in which the additive is provided. It can in particular be an oil or silicone gum having a viscosity compatible with POS A. Depending on the silicone composition, the person skilled in the art is perfectly capable of choosing a suitable oil or gum, especially suitable in terms of viscosity, for diluting the inhibitor composition. catalyst previously obtained. According to a particular method, an oil or gum is used in particular chosen from the oils or gums C defined above, in particular PDMS, or also from the POS A described with regard to the silicone composition.
- the additive obtained according to mode 1 or mode 2 after possible dilution in an oil or gum, comprises from 0.001 to 10%, better still from 0.01 to 1% by weight of platinum metal.
- the additive thus obtained is a simple pasting intended to be then added to the silicone composition proper.
- this additive constitutes a fraction of the final single-component silicone composition.
- the pasting is based on one of the constituents of this composition and in particular based on POS A, or based on PDMS.
- compositions, or additives or catalytic assemblies obtained by implementing the methods of preparation which have just been described also constitute objects of the present invention. They preferably comprise at least one inhibitor of formula (I), (II), (III), (VIII) or (IX) and a catalyst according to the invention.
- the catalytic composition comprises the catalyst, the inhibitor, and an unsaturated silane, or an unsaturated siloxane, comprising one or more siloxane units (eg from 2 to 200, preferably from 2 to 30), particular according to the teaching of the patents US-A-3,775,452 and US-A-3,715,334 mentioned above. They are preferably vinylsilanes and / or vinylsiloxanes.
- the composition is obtained from a solution of unsaturated platinum / silane or unsaturated platinum / siloxane, in particular a solution of platinum / vinyisiloxane, in particular obtained by reaction between a platinum halide and an unsaturated organosilicon material such as an unsaturated silane or an unsaturated siloxane, eg the Karstedt solution or complex.
- the catalytic composition comprises the catalyst, the inhibitor, a silicone gum or oil, and optionally a silane or a siloxane as just described.
- the oil or gum is preferably identical to or close to one or more of the compounds of the final silicone composition.
- an oil or an eraser with an alkenyl group, preferably vinylated, such as POS A according to the invention, and even more preferably POS A used in the targeted monocomponent silicone composition is used.
- a polyorganosiloxane C oil or gum eg a PDMS.
- the catalytic composition comprises at least one inhibitor of formula (I), (II) or (III), optionally combined with an inhibitor of formula (VIII) or (IX), and an oil or gum with an alkenyl group , preferably vinylated, preferably POS A, and / or a polyorganosiloxane C oil or gum, preferably PDMS.
- the catalytic composition comprises, or essentially consists of, at least one inhibitor of formula (VIII) or (IX), and a polyorganosiloxane C oil or gum, preferably PDMS.
- the inhibitor inhibits the catalytic action of the catalyst at room temperature.
- the inhibitor and the catalyst are complexed.
- the invention particularly relates to such an additive, in which the catalyst + inhibitor assembly represents from 0.001 to 40% by weight, preferably from 0.01 to 30%, better still from 0.1 to 20%.
- the subject of the present invention is also a silicone composition crosslinkable by hydrosilylation, comprising at least one PolyOrganoSiloxane (POS) having ethylenic and / or acetylenic unsaturation (s), at least one hydrogenated polyorganosiloxane B (ci -after POS B), as well as (a) a hydrosilylation catalyst and an inhibitor of formula (I), (II) or (III), or (b) a catalytic assembly obtained as just described.
- POS PolyOrganoSiloxane
- s ethylenic and / or acetylenic unsaturation
- ci -after POS B hydrogenated polyorganosiloxane B
- a silicone composition or an additive or catalytic assembly comprises such or such inhibitor of formula (I), (II), (III), (VIII) or (IX), it is meant free inhibitor, inhibitor complexed with the catalyst, or a mixture of these two species.
- the composition comprises an additive or catalytic unit according to the invention, preferably provided in the form of a mash prepared according to one of the modes of preparation 1 and 2 defined above.
- the catalyst and the inhibitor are added separately to the silicone composition. It is therefore preferable to add them in the
- POS A or in a composition containing POS A and one or more other ingredients, with the exception of POS B.
- POS B is incorporated after a thorough mixing of POS A, the catalyst and the inhibitor and advantageously after a certain latency.
- the inhibitor can advantageously be in solution in a vinylsiloxane.
- the invention is aimed both at polyaddition silicone compositions which can be vulcanized at RTV ambient temperature (and whose crosslinking can be accelerated when hot) as well as those known as EVC hot vulcanizable elastomers.
- the POS A can in particular be formed from siloxyl units of formula: ⁇ a Z b SiQ (4, a, b) (IV)
- Y is a C 2 -C 6 alkenyl, preferably vinyl
- Z is a monovalent hydrocarbon group having no adverse action on the activity of the catalyst
- Z is generally chosen from alkyl groups having 1 with 8 carbon atoms included such as methyl, ethyl, propyl and 3,3,3-trifluoropropyl and aryl groups such as xylyl, tolyl and phenyl
- a is 1 or 2
- b is 0, 1 or 2
- a + b is between 1 and 3, possibly all the other units being units of average formula:
- POS B can in particular be formed from siloxyl units of formula:
- W is a monovalent hydrocarbon group having no unfavorable action on the activity of the catalyst and corresponding to the same definition as Z, d is 1 or 2, e is 0, 1 or 2, d + a value between 1 and 3, possibly all the other units being units of average formula:
- g has a value between 0 and 3.
- POS A & B are for example respectively a polyorganovinylsiloxane and a polyorganohydrogensiloxane.
- the organic substituents other than the vinyl and hydrogen reactive groups are, for example, methyls or cyclohexyls.
- T [- (R) SiO-].
- These hydrogenated or vinyl M, D units each have one or more H or Vinyl, preferably only one.
- the number of SiH or SiVi units per molecule is preferably greater than or equal to 2. This can in particular represent from 0.01% to 10% (preferably
- Suitable POS B are polymethylhydrogensiloxanes with -Si (CH 3 ) 3 ends and polydimethylsiloxanes with -Si (CH 3 ) 2H ends, methylhydrogenodimethylsiloxane copolymers with -Si (CH 3 ) 2H ends, methylhydrogenomethyloctylsiloxane copolymers, and methylhydroxyiloxanes
- POS A & B have an average molecular weight of between 1.1O 2 and 1.1O 7 (g / mol).
- POS A this includes in particular, in terms of dynamic viscosity at 25 ° C: o in the case of silicone compositions which can be vulcanized hot (EVC) by polyaddition, POS A having in particular a viscosity at least equal to 5.10 5 mPa.
- POS A having in particular a viscosity preferably comprised 1.10 4 and 5.10 5 mPa.s, and o in the case of silicone compositions vulcanizable at room temperature (vulcanization being accelerated while hot) by polyaddition or RTV, POS A having in particular a viscosity of between 100 and 10 4 mPa.s , preferably between 1000 and 5000 mPa.s.
- the POS B generally have a viscosity between 10 and 10,000 mPa.s, preferably between 50 and 1000 mPa.s.
- the silicone compositions concerned are POSs which can be vulcanized hot (EVC) by polyaddition and in which the POS A can in practice have a viscosity at 25 ° C. of eg 1.10 6 to 5.10 6 mPa.s and POS B from 10 to 5000 mPa.s, in particular from 50 to 1000 mPa.s (eg 300 mPa.s).
- EMC vulcanized hot
- POS B from 10 to 5000 mPa.s, in particular from 50 to 1000 mPa.s (eg 300 mPa.s).
- the viscosity is measured using a BROOKFIELD viscometer according to the indications in AFNOR NFT 76 106 of May 1982.
- an inhibitor of formula (I), (II) or (III) can be added, in particular by solution in a vinylsiloxane, and / or another crosslinking inhibitor, for example of formula (VIII) or (IX), an acetylenic alcohol (FR-A-2 372 874, FR-A-1 528 464), a compound of maleate type (US-A-4,256,870 and US-A-4,530,989) or an acetylene dicarboxylate compound (US-A-4,504,645 and US-A-4,347,346).
- the silicone compositions of the invention can also comprise usual functional additives.
- usual functional additives mention may be made of: fillers, hydroxylated POS oils useful as compatibilizers, adhesion promoters, "adhesion modulators, thermal resistance additives additives to increase the consistency of pigments, additives for thermal resistance, resistance to oils, to fire (for example metal oxides).
- the charges possibly provided are preferably mineral. They can in particular be siliceous.
- siliceous materials they can play the role of reinforcing or semi-reinforcing filler.
- the reinforcing siliceous fillers are chosen from colloidal silicas, combustion and precipitation silica powders or their mixtures. These powders have an average particle size generally less than 0.1 ⁇ m and a BET specific surface greater than 50 m / g, preferably between 150 and 350 m 2 / g.
- Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used.
- non-siliceous mineral materials they can act as a semi-reinforcing or tamping mineral filler.
- non-siliceous fillers which can be used alone or as a mixture are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, unexpanded vermiculite, calcium carbonate, l zinc oxide, mica, talc, iron oxide, barium sulfate and slaked lime. These fillers have a particle size generally between 0.001 and 300 ⁇ m and a BET surface area of less than 100 m 2 / g.
- the fillers used can be a mixture of quartz and silica.
- the charges can be treated with any suitable product.
- an amount of filler of between 10 and 50% by weight, preferably between 20 and 40% by weight relative to all of the constituents of the composition. More generally, quantitatively, the compositions according to the invention refer to standard proportions in the technical field under consideration, knowing that the intended application must also be taken into account.
- a subject of the invention is also a process for the preparation of a single-component silicone composition crosslinkable by hydrosilylation, comprising at least one PolyOrganoSiloxane (POS) With ethylenic and / or acetylenic unsaturation (s) carrier, at least a hydrogenated polyorganosiloxane B (hereinafter POS B), at least one hydrosilylation catalyst and at least one inhibitor of formula (I), (II), (III), (VIII) and / or (IX), process in which brings the inhibitor and the catalyst in the form of an additive or catalytic assembly previously prepared according to the invention, preferably a mash formed of the premix of the inhibitor and the catalyst.
- POS B PolyOrganoSiloxane
- s ethylenic and / or acetylenic unsaturation
- the catalyst is introduced in its inhibited form, combined with the inhibitor.
- the inhibition may relate to all or part of the catalyst molecules, depending on the amount of inhibitor present in the additive.
- the inhibition is preferably complete.
- This additive can be added to the rest of the silicone composition or to any fraction thereof, in particular in a fraction containing or consisting of POS A, POS B or a mixture of POS A and B. It is possible to also define the process as incorporating the production of the additive as described above, then the provision of this additive in the silicone composition.
- an additive prepared according to mode 1 described above (with or without dilution) is added.
- the additive is therefore derived from the dispersion of the inhibitor in a solution of the catalyst in an unsaturated silane or siloxane, preferably vinylsiloxane.
- an additive prepared according to mode 2 described above (with or without dilution) is added.
- the additive is then obtained from the mixture of the inhibitor in a silicone oil or gum at a temperature higher than the melting or softening temperature of the inhibitor, then addition of the catalyst.
- the additive can be added before, during or after addition of the other ingredients such as mineral filler, crosslinking inhibitor, hydroxylated POS oil, or other usual functional additives such as those described above.
- the additives or catalytic units according to the invention can be easily mixed in this silicone composition.
- the various mixing means usually used in the silicone industry can be used, and in particular arm mixers and cylinder mixers when the viscosity requires it, in particular in the case of EVCs.
- the mixing operation is continued to obtain an optimal dispersion of the additive or catalytic unit. Those skilled in the art are capable of determining the optimal conditions.
- a further subject of the invention is the single-component silicone compositions which can be obtained by implementing the preparation process which has just been described, compositions which are characterized in particular by a remarkably fine and homogeneous dispersion of the catalyst / inhibitor couple.
- Another object of the invention consists of a process for hydrosilylation of one or more POS A using one or more POS B, characterized in that it consists in using a silicone composition such as defined above and to heat it to the crosslinking temperature, generally between 50 and 200 ° C., more particularly between 100 and 150 ° C.
- a silicone composition such as defined above and to heat it to the crosslinking temperature, generally between 50 and 200 ° C., more particularly between 100 and 150 ° C.
- the crosslinking temperature generally between 50 and 200 ° C., more particularly between 100 and 150 ° C.
- humans those skilled in the art have no difficulty in determining the optimum temperature for triggering hydrosilylation.
- the relative amount of unsaturated compound and compound having an Si-H unit can be controlled so as to ensure the reaction of all unsaturations with Si-H bonds.
- the molar ratio of unsaturations to Si-H bonds varies between 1: 10 and 10: 1.
- the hydrosilylation reaction is carried out in the presence of a catalytic amount of the catalyst according to the invention.
- catalytic amount means less than a molar equivalent of platinum relative to the amount of unsaturations present in the reaction medium.
- the compounds of formula (I,) (II) or (III) can be obtained in the usual manner by reaction between (i) a di-halogenated compound XRX (X for a halogen atom), R having the meaning given above with regard to formulas (I), (II) and (III), and (ii) an excess of PCI 3 , then by reaction of the compound obtained in the preceding step with the 4 alcohol molecules R'OH, making it possible to form the groups R 1 to R 4 of formulas (I), (II) and (III).
- the product obtained can then be purified using conventional techniques known to those skilled in the art. They can also be prepared according to the teaching of US-A-5 109 043.
- reaction mixture is kept stirring for a few minutes.
- a catalytic solution is obtained containing 8.4% of Platinum by weight. This clear, homogeneous and easily handled solution is used in the following examples.
- the reaction mixture is heterogeneous. It remains heterogeneous even after several minutes of agitation. After 3 hours of agitation, the reaction mixture becomes heterogeneous in white color. Stopping the agitation causes the white solid to settle at the bottom of the bottle.
- Example 3 Composition according to the invention (all parts are given by weight).
- an EVC 1 base is prepared by mixing for 2 hours at room temperature (23 ° C):
- a sample of catalyzed elastomer is compressed in a sealed chamber under a given pressure and at a given temperature.
- test chamber is formed by two half-chambers, one of which is subjected to low linear or rotary (disc) oscillations.
- This action produces in the test piece an alternating sinusoidal deformation, linear or in torsion, and a sinusoidal shear force or torque which depend on the rigidity (shear modulus) of the elastomer.
- the rigidity of the test piece increases as the vulcanization or polyaddition reaction takes place.
- the measurement as a function of the time of the torque necessary for the oscillation of the disc makes it possible to obtain, at the end of the measurement, the vulcanization characteristics of the elastomer.
- Vmax maximum vulcanization speed reached.
- Example 4 In-situ preparation. by a hot process, an additive based on a silicone matrix, Karstedt platinum and the inhibitor (III).
- Karstedt catalyst platinum with zero oxidation degree in solution in a vinyl silicone oil (10% by mass of platinum) (10% by mass of platinum) is then added, either on a cylinder mixer or in an arm mixer.
- an EVC 2 base consisting of: - 50 parts of vinyl polydimethylorganosiloxane containing in the chain 720 ppm of vinyl groups and having a viscosity of 5 million mPa.s at 25 ° C,
- Comparative Example 5 Preparation on a cylinder mixer, by a cold process, of an additive based on a silicone matrix.
- Karstedt platinum and inhibitor (lin. 1.305 g of inhibitor (III) powdered in 500 g of EVC 2 base of hardness 35 are added to a cylinder mixer. 1.755 g of Karstedt catalyst are added dropwise.
- Comparative Example 6 Preparation in an arm mixer, by a cold process, of an additive based on a silicone matrix, Karstedt platinum and inhibitor (HP.
- Example 5 The same type of additive, described in Example 5, was produced using an arm mixer. 6a / 1, 048 g of powdered inhibitor are added to 400 g of the base
- composition of this EVC formulation is as follows: for each 100 g of an EVC 1 base according to Example 3, 0.94 parts of oil at -SiH are added, using a cylinder mixer. 440 meq - SiH / 100 g of oil, viscosity 250 mPa.s). After incorporation, then the completion of 15 passages between the two cylinders (improvement of the dispersion of the additives), 0.037 parts of an additive composed of the base EVC 2 of hardness 35 and of inhibitor (III) are added according to Examples 4a and 6a.
- Example 9 Stability of the additives prepared according to Example 4
- Example 11 Evaluation of the quality of inhibition provided by C1 and C2
- a reaction system is prepared by mixing 20 grams of an organovinylpolysiloxane of viscosity 230 mPa.s and containing 0.61% of vinyls by weight, the catalyst mixture C1 or C2 so as to obtain 80 ppm by weight of platinum in the final mixture; then 5.4 grams of an organohydrogensiloxane with a viscosity of 300 mPa.s and containing 0.17% by weight of hydrogen are added. This final reaction mixture is homogenized by stirring for 5 minutes. To assess the quality of the inhibition, the gel time t ge ⁇ corresponding to the setting time of the reaction mixture is measured at room temperature. The comparative reactivity of the two systems is evaluated by DSC (Differential Scanning Calorimetry).
- a reaction system is prepared by mixing 20 grams of an organovinylpolysiloxane with a viscosity of 230 mPa.s and containing 0.61% of vinyl by weight, the amount of organophosphorus inhibitor (III) or (X) required to obtain a ratio P / Pt of 1.2, then the Karstedt catalyst (14.3% platinum solution in the DVTMS) so as to obtain 80 ppm by weight of platinum in the final mixture.
- This mixture is stirred for 10 minutes at ambient temperature, then 5.4 grams of an organohydrogensiloxane of viscosity 300 mPa.s and containing 0.17% by weight of hydrogen are added. This final reaction mixture is homogenized by stirring for a few minutes. To assess the quality of the inhibition, the gel time corresponding to the setting time of the reaction mixture is measured at room temperature.
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Abstract
Description
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Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0205380A FR2838985B1 (fr) | 2002-04-29 | 2002-04-29 | Ensemble catalytique pour hydrosilylation et compositions silicone l'incorporant |
FR0205380 | 2002-04-29 | ||
FR0215161A FR2847900B1 (fr) | 2002-12-02 | 2002-12-02 | Ensemble catalytique pour hydrosilylation, son procede de preparation et composition silicone l'incorporant |
FR0215161 | 2002-12-02 | ||
PCT/FR2003/001305 WO2003092890A2 (fr) | 2002-04-29 | 2003-04-24 | Ensemble catalytique pour hydrosilylation, son procede de preparation et compositions silicone l'incorporant |
Publications (1)
Publication Number | Publication Date |
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EP1499660A2 true EP1499660A2 (fr) | 2005-01-26 |
Family
ID=29404172
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03747466A Withdrawn EP1499660A2 (fr) | 2002-04-29 | 2003-04-24 | Ensemble catalytique pour hydrosilylation, son procede de preparation et compositions silicone l incorporant |
Country Status (5)
Country | Link |
---|---|
US (2) | US20060089455A1 (fr) |
EP (1) | EP1499660A2 (fr) |
KR (1) | KR100648880B1 (fr) |
AU (1) | AU2003246862A1 (fr) |
WO (1) | WO2003092890A2 (fr) |
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FR2848215B1 (fr) | 2002-12-04 | 2006-08-04 | Rhodia Chimie Sa | Composition elastomere silicone, adhesive, monocomposante et reticulable par polyaddition |
JP2007308581A (ja) * | 2006-05-18 | 2007-11-29 | Shin Etsu Chem Co Ltd | 付加硬化型シリコーンゴム組成物の硬化方法及び付加硬化型シリコーンゴム組成物 |
US20080033136A1 (en) * | 2006-07-13 | 2008-02-07 | Rinard Chauncey J | Selective hydrosilylation conditions |
US7259220B1 (en) * | 2006-07-13 | 2007-08-21 | General Electric Company | Selective hydrosilylation method |
US20080227938A1 (en) * | 2007-03-12 | 2008-09-18 | Shin-Etsu Chemical Co., Ltd. | Hydrosilylation inhibitor, hydrosilylation catalyst composition, and curable composition |
JP2009091403A (ja) * | 2007-10-04 | 2009-04-30 | Shin Etsu Chem Co Ltd | 付加硬化型シリコーンゴム組成物及びその硬化方法 |
JP2009220384A (ja) * | 2008-03-17 | 2009-10-01 | Shin Etsu Chem Co Ltd | シリコーンゴム薄膜被覆層の形成方法、及びシリコーンゴム薄膜被覆物品 |
US8052836B2 (en) | 2008-11-26 | 2011-11-08 | Corning Cable Systems Llc | Laser-based methods of stripping fiber optic cables |
US9791624B2 (en) | 2014-11-07 | 2017-10-17 | Corning Optical Communications LLC | Methods for stripping an optical fiber coating using blue or blue-violet radiation |
US9891384B2 (en) | 2014-11-07 | 2018-02-13 | Corning Optical Communications LLC | Systems and methods for multiple-pass stripping of an optical fiber coating |
JP6260519B2 (ja) * | 2014-11-25 | 2018-01-17 | 信越化学工業株式会社 | 一液付加硬化型シリコーン組成物の保存方法及び硬化方法 |
CN106582846A (zh) * | 2016-11-18 | 2017-04-26 | 南昌大学 | 一种高效抗中毒Karstedt催化剂及合成和在硅氢加成反应中的应用 |
TWI762649B (zh) | 2017-06-26 | 2022-05-01 | 日商杜邦東麗特殊材料股份有限公司 | 黏晶用固化性矽組合物 |
CN112961192A (zh) * | 2021-02-26 | 2021-06-15 | 畅的新材料科技(上海)有限公司 | 一种高稳定性硅氢加成用铂金催化剂的制备方法和应用 |
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-
2003
- 2003-04-24 WO PCT/FR2003/001305 patent/WO2003092890A2/fr not_active Application Discontinuation
- 2003-04-24 KR KR1020047017516A patent/KR100648880B1/ko not_active IP Right Cessation
- 2003-04-24 EP EP03747466A patent/EP1499660A2/fr not_active Withdrawn
- 2003-04-24 AU AU2003246862A patent/AU2003246862A1/en not_active Abandoned
- 2003-04-25 US US10/512,977 patent/US20060089455A1/en not_active Abandoned
-
2008
- 2008-06-26 US US12/146,974 patent/US7750171B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO03092890A2 * |
Also Published As
Publication number | Publication date |
---|---|
AU2003246862A8 (en) | 2003-11-17 |
KR20050007356A (ko) | 2005-01-17 |
AU2003246862A1 (en) | 2003-11-17 |
US20080262170A1 (en) | 2008-10-23 |
KR100648880B1 (ko) | 2006-11-24 |
WO2003092890A2 (fr) | 2003-11-13 |
WO2003092890A3 (fr) | 2004-04-22 |
US7750171B2 (en) | 2010-07-06 |
US20060089455A1 (en) | 2006-04-27 |
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