WO1998000463A1 - Use of platinum complexes particularly as homogeneous and heat activable catalysts for hydrosilylation - Google Patents
Use of platinum complexes particularly as homogeneous and heat activable catalysts for hydrosilylation Download PDFInfo
- Publication number
- WO1998000463A1 WO1998000463A1 PCT/FR1997/001157 FR9701157W WO9800463A1 WO 1998000463 A1 WO1998000463 A1 WO 1998000463A1 FR 9701157 W FR9701157 W FR 9701157W WO 9800463 A1 WO9800463 A1 WO 9800463A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- platinum
- reactive
- formula
- alkyl
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 150000003057 platinum Chemical class 0.000 title claims abstract description 16
- 238000006459 hydrosilylation reaction Methods 0.000 title claims description 48
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 119
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 150000001993 dienes Chemical class 0.000 claims description 47
- 239000003446 ligand Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- -1 siloxanes Chemical class 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000012429 reaction media Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000004756 silanes Chemical class 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 230000002411 adverse Effects 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000002815 homogeneous catalyst Substances 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 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 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 125000005023 xylyl group Chemical group 0.000 claims description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 229920001187 thermosetting polymer Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 238000004132 cross linking Methods 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 16
- 229910000077 silane Inorganic materials 0.000 description 16
- 239000000758 substrate Substances 0.000 description 12
- 238000007792 addition Methods 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 9
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000036632 reaction speed Effects 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 5
- KIAJWKWOKTWTIZ-UHFFFAOYSA-N 1,4-dioxonaphthalene-2,3-dicarbonitrile Chemical compound C1=CC=C2C(=O)C(C#N)=C(C#N)C(=O)C2=C1 KIAJWKWOKTWTIZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- SVPKNMBRVBMTLB-UHFFFAOYSA-N 2,3-dichloronaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(Cl)=C(Cl)C(=O)C2=C1 SVPKNMBRVBMTLB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003060 catalysis inhibitor Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYCXGQSQHAXLPK-VAWYXSNFSA-N (e)-1,4-diphenylbut-2-ene-1,4-dione Chemical group C=1C=CC=CC=1C(=O)\C=C\C(=O)C1=CC=CC=C1 WYCXGQSQHAXLPK-VAWYXSNFSA-N 0.000 description 1
- CCTJHVLTAJTPBV-UHFFFAOYSA-N 2-chloro-1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C(Cl)=CC(=O)C2=C1 CCTJHVLTAJTPBV-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- 229910000497 Amalgam Inorganic materials 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
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000008763 Mercury poisoning Diseases 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- WHGYFGNRTSDCBM-UHFFFAOYSA-N O=C(C(C12)C3c4ccccc4C1c1c3cccc1)C=CC2=O Chemical compound O=C(C(C12)C3c4ccccc4C1c1c3cccc1)C=CC2=O WHGYFGNRTSDCBM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002978 dental impression material Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IQSBKDJPSOMMRZ-UHFFFAOYSA-N ethenyl(methyl)silane Chemical compound C[SiH2]C=C IQSBKDJPSOMMRZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000011017 operating method Methods 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
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 210000004722 stifle Anatomy 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
-
- 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
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
-
- 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
-
- 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
-
- 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
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
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- 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
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- 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
-
- 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
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- 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
-
- 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
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- 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
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- 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
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- 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
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- 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
Definitions
- the present invention relates to the field of catalysis of crosslinking or functionalization reactions of polymer chains, e.g. silicones. It is more particularly question, in the present description, of substrates to be crosslinked of polyorganosiloxane type A having, per molecule, at least one reactive radical Si-H, while being free of silicon atoms bonded to more than two atoms of hydrogen. These substrates A are intended to react with substrates of type B having, per molecule, at least one reactive unsaturated aliphatic group and / or at least one reactive function, eg epoxide, in the presence of a catalyst comprising at least one platinum complex, such a reaction being initiated or activated thermally.
- a catalyst comprising at least one platinum complex
- the present invention relates, first of all, to the use of thermoactive organoplatinic complexes in crosslinking by hydrosilylation of polyorganosiloxanes A of Si-H type and of compounds B with aliphatic unsaturation and / or with reactive function.
- the present invention also relates to a hydrosilylation process in which the above complexes are used, as well as compositions crosslinkable by thermoactivation and containing, inter alia, the substrates A and B as well as the above complexes.
- the invention also encompasses the functionalization of silicone oils containing SiH units by terminal unsaturated derivatives. These can include other functions other than unsaturation, for example: epoxide, alcohol, ester, amino, etc.
- this KARSTEDT catalyst suffers from its too weak activity.
- the loss of activity is due to the formation of inactive species in catalysis and insoluble in the reaction medium.
- This catalyst can also be improved, as regards the reaction rate and its effective lifetime in the reaction medium.
- KARSTEDT catalyst has relatively poor storage stability (gel time at 25 ° C less than or equal to 1 min)
- Another objective of the invention is to provide a hydrosilylation process by thermoactivation of reactive products , and in particular of silicones, in which the abovementioned catalytic systems are used, said process having to be implemented a easy, fast, and inexpensive
- Another objective of the invention is to provide compositions of silicone oils crosslinkable by thermoactivation - which comprise the above homogeneous catalytic systems,
- compositions stable in storage, can be used, for example, for paper anti-adhesion, dental impressions, sealing or jointing materials, adhesives, or for any other application in which it is advantageous to use performs cross-linking in situ (solvent-free) of silicone elastomers.
- platinum complexes with a formal oxidation state 0 as a heat-activated, homogeneous catalyst, based on platinum and useful in particular in hydrosilylation.
- silanes and / or siloxanes A having, per molecule, at least one reactive radical SiH and free of silicon atom bonded to more than two hydrogen atoms and, on the other hand, compounds B having at least one reactive group and / or at least one reactive function, of at least one platinum complex of formula:
- n 1 or 2
- ⁇ L ⁇ and L ⁇ . are identical or different and are selected from among the binding olefins, preferably from the following olefinic residues, substituted or not: • + norbornene
- L ⁇ and L ⁇ . can also together form a single diolefin ligand, preferably formed by:
- R 1 , R 2 , R 3 , R 4 are different or similar to each other and represent an alkyl and or acyl group, preferably an alkyl having from 1 to 18 carbon atoms, the methyl, ethyl, propyl, pentyl groups , hexyl, allyl, acetyl, propionyie being particularly preferred and especially methyl,
- L is chosen from ligands ⁇ , L 2 defined below
- Y 1 , Y 2 , Y 3 , Y 4 independently represents a hydrogen, a halogen, an alkyl, an aryl, an alkoxyl, a hydroxyl, or else Y 1 and Y 4 or Y 2 and Y 3 can also form together at least a cyclic group, aromatic or not, and comprising one or more rings, condensed or not, the said cycles being optionally substituted by monovalent radicals corresponding to the definition given above for Y 1 to Y 4 , ⁇ E 1 , E 2 are identical or different and represent.
- NR 5 with R 5 C r C 6 alkyl or alkenyl
- the present invention therefore consists of an advantageous and inventive selection of platinum complexes (I) which are particularly suitable for reaction catalysis, in particular of the hydrosilylation type, and which can be activated thermally.
- heat-activated catalysts envisaged in the context of the use according to the invention are particularly advantageous in the context of crosslinking or functionalization, for example of silicones of the SiH and SIVI type, by hydrosilylation.
- the ligands L platinum complexes (I) are selected from the following L 1 and L 2 subgroups ⁇ L,
- L ⁇ and L ⁇ . together form (II).
- the catalyst is advantageously used in a reaction medium consisting of a stable solution of said catalyst and of the reactants , in at least one organic solvent.
- this organic solvent can for example be an alkane such as hexane, cyclohexane, methylcyclohexane or their mixtures.
- the solvent can also be chosen from the following products: toluene, xylene, chlorobenzene, and mixtures thereof, eg
- the catalyst contains, in the free state, at least one stabilizing agent formed by at least one ligand Ls of formula L, or L 2 as defined above.
- the ligand Ls forming the stabilizing agent can be identical or different to the ligands (L ,, L 2 ) of the complexes (I).
- Ls radical ligands mention may be made of naphthoquinone, methylnaphthoquinone, chloronaphthoquinone or tetracyanoethylene. According to the invention, it is advantageous to use the compound Ls in the catalytic system in an excess of 1 to 30, preferably 10 to 20 molar equivalents relative to the platinum present.
- This Ls compound can in fact be considered as a catalyst inhibitor. It is moreover possible to use in combination or as a replacement for Ls other conventional inhibitors of hydrosilylation catalysts. These inhibitors also known under the name of thermal blockers make it possible to increase the "pot life" of the compositions considered (stabilities greater than 3-5 days) without harming the kinetics of hydrosililation.
- R is a linear or branched alkyl radical, or a phenyl radical; . R 'is H or a linear or branched alkyl radical, or a phenyl radical; the radicals R, R 1 and the carbon atom located at ⁇ of the triple bond which can optionally form a ring; the total number of carbon atoms contained in R and R 1 being at least 5, preferably from 9 to 20.
- Said alcohols are preferably chosen from those having a boiling point above 250 ° C. Mention may be made, by way of examples:. ethynyl-1-cyclohexanol 1;
- the synthesis of the platinum complexes (I) according to the invention consists in reacting a ligand L with products of average formula [Pt 2 ] [V ⁇ e 2 Si - O - Si Me 2 V ⁇ ] 3 These products are preferably formed by a KARSTEDT catalyst solution. This reaction can be carried out in bulk or in a solvent, such as toluene, ethanol or isopropanol.
- the invention also relates to new platinum complexes of formula (I) as defined above, in which L ⁇ and L ⁇ are identical or different and are selected from binding olefins, preferably from the following olefin residues, substituted or not + norbornene
- the present invention also relates to a heat-activatable catalyst based on platinum and useful in particular in hydrosilylation between, on the one hand, silanes and / or siloxanes A having, per molecule, at least a reactive radical SiH and free of silicon atom bonded to more than two hydrogen atoms and, on the other hand, compounds B having at least one reactive group and / or at least one reactive function, characterized
- This catalyst can be one of those suitable for use in accordance with the invention and set out above.
- One of the forms of presentation of the above heat-activated catalyst can be, in accordance with the invention, a stable and homogeneous solution of said catalyst in at least one organic solvent, preferably chosen from alkanes, for example hexane, cyclohexane or methylcyclohexane and their mixtures or even among the following products: toluene, xylene, chlorobenzene, eg and their mixtures.
- the platinum complexes (I) are homogeneous and have a high efficiency in hydrosilylation. olefins. They generate a high reaction speed and are endowed with a long effective life which results in their capacity for catalysis for a large number of cycles.
- the catalyst can comprise a precursor of the complexes (I).
- a precursor is advantageously constituted by a composition of the starting materials for the synthesis of the complexes (I), namely: catalyst of KARSTEDT and ligand L in excess for (I) and for example (nbn) 3 Pt for ( II).
- the formation of the platinum complexes takes place in situ, before and / or during the use of the crosslinkable composition containing the precursor composition. This greatly simplifies the preparation.
- the present invention relates to a hydrosilylation process between, on the one hand, silanes and / or siloxanes such as polyorganosiloxanes A having, per molecule, at least one reactive radical Si-H and free silicon atoms linked to more than two hydrogen atoms, and on the other hand, compounds B preferably chosen from polyorganosiloxanes and having, per molecule, at least one reactive unsaturated aliphatic group and / or at least one function reactive, process in which at least one platinum complex is used as catalyst.
- silanes and / or siloxanes such as polyorganosiloxanes A having, per molecule, at least one reactive radical Si-H and free silicon atoms linked to more than two hydrogen atoms
- compounds B preferably chosen from polyorganosiloxanes and having, per molecule, at least one reactive unsaturated aliphatic group and / or at least one function reactive, process in which at least one platinum complex is used as catalyst.
- This process differs from its similar in that it consists essentially in reacting compounds A and B in the presence of a catalytic system of the type of that according to the invention described above, and / or by using simultaneously a synthesis of either complexes (I) in which a precursor is formed, as described above, formed by a composition of the starting materials (excess ligand + KARSTEDT catalyst or (nbn) 3 Pt, the initiation of the reaction being carried out by thermoactivation.
- the compounds A are chosen from polyorganohydrogensiloxanes comprising: * units of the following formula:
- W are similar or different and representing a monovalent hydrocarbon group, free from any adverse action on the activity of the catalyst and preferably chosen from (cyclo) alkyl groups having from 1 to 18 carbon atoms inclusive and, advantageously, from methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl groups and also from C 6 -C 12 aryl or aralkyl groups and, advantageously, among the xylyl and totyl and phenyl radicals, all of these groups being optionally halogenated (eg fluorine) and / or hydroxylated and / or alkoxylated.
- a is 1 or 2
- b is 0, 1 or 2
- the sum (a + b) has a value between 1 and 3, * and possibly other units of average formula: W c SiQ 4 .
- Organopolysiloxane A can only be formed of units of formula (1) or additionally comprise units of formula (2)
- Organopolysiloxane A can have a linear, branched or unbranched, cyclic or network structure.
- the degree of polymerization is greater than or equal to 2. More generally, it is less than 5,000.
- Examples of units of formula (1) are: H (CH 3 ) Si0 1/2 , HCH 3 Si0 2/2 , H (C 6 H 5 ) Si0 2/2 ,
- linear polymers When linear polymers are involved, these essentially consist of "D" W 2 Si0 2/2 , WHSi0 2/2 , and “M” W 3 Si0 1/2 or W 2 HSi0 1/2 units. , WH 2 Si0 1/2 ; the blocking terminal "M” units can be trialkylsiloxy, dialkylarylsiloxy groups.
- terminal "M” units mention may be made of trimethylsiloxy, dimethylphenylsiloxy, dimethylethoxysiloxy, dimethylethyltriethoxy-silylsiloxy groups, etc.
- Said linear polyorganosiloxanes A can be oils of dynamic viscosity at 25 ° C of the order of 1 to 100,000 mPa.s at 25 ° C, generally of the order of 10 to 5,000 mPa.s at 25 ° C, or gums having a molecular mass of the order of 1,000,000.
- cyclic polyorganosiloxanes these consist of units
- Said cyclic polyorganosiloxanes have a viscosity of the order of 1 to 5000 mPa.s
- the dynamic viscosity at 25 ° C all the silicone polymers considered in this presentation can be measured using a BROOKFIELD viscometer, according to AFNOR standard NFT 76 102 of February 1972
- the viscosity in question in this presentation is the dynamic viscosity at 25 ° C called “Newtonian”, that is to say the dynamic viscosity which is measured, in a manner known per se, at a shear rate gradient low enough for the viscosity measured to be independent of the speed gradient
- organopolysiloxanes A are examples of organopolysiloxanes A.
- compounds B they are selected from polyorganosiloxanes comprising similar or different units of formula W ′ d X e YfSi ⁇ 4. (d + e + f) (3)
- the symbols X are similar or different and represent a hydrogen atom or a reactive function, preferably epoxyfunctional, linked to silicon by a divalent radical eg C 1 -C 20 optionally comprising at least one heteroatom, the radicals X more particularly preferred being 3-glyc ⁇ doxypropyl, 4-éthaned ⁇ yle
- Y residues they are advantageously chosen from the following list vinyl, propenyl, 3-butenyl, 5-hexenyl, 9 decenyl, 10-undecenyl, 5.9 - decadienyl, 6-11-dodecad ⁇ enyl
- Organopolysiloxanes B can have a linear (branched or not) cyclic or network structure. Their degree of polymerization is preferably between 2 and 5000
- linear polymers When linear polymers are concerned, these essentially consist of units "D" W 2 S ⁇ 0 2/2 , XSiO 2/2 , YSiO 2/2 , and "M" W 3 Si0 1/2 , W 2 YSiO 1/2 , W 2 XS ⁇ O 1/2 , the terminal blocking "M” units can be t ⁇ alkylsiloxy, dialkylarylsiloxy, dialkylvinylsiloxy, dialkylalkenylsiloxy groups
- terminal "M" units mention may be made of tnmethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy, dimethylhexenylsiloxy, dimethylethoxysiloxy, dimethylethyltnethoxysilylsiloxy groups
- units "D” mention may be made of dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylesiloxy, methyldecadienylsiloxy, methyl-3-hydroxypropyls ⁇ loxy, methyl-3-glycidoxypropyl , 4'-epoxycyclohexyl) ethylsiloxy, methyl-butoxysiloxy, methyl- ⁇ -tnmethoxysilylethylsiloxy, methyl- ⁇ -t ⁇ ethoxysilylethylsiloxy
- Said linear polyorganosiloxanes B can be oils of dynamic viscosity at 25 ° C of the order of 1 to 100,000 mPa s at 25 ° C, generally of the order of 10 to 5,000 mPa s at 25 ° C, or gums with a molecular mass of the order of 1,000,000
- cyclic polyorganosiloxanes B consist of "D" units W 2 S ⁇ 0 2/2 , WS ⁇ 0 2/2 , WYS ⁇ 0 2/2 , which may be of the dialkylsiloxy, alkylarylsiloxy, alkylvinylsiloxy, alkylYsiloxy, alkylXsiloxy type, examples of such units have already been mentioned above
- Said cyclic polyorganosiloxanes B have a viscosity ⁇ e of the order of 1 to 5000 mPa s
- aliphatic unsaturated compounds B useful in the context of the process according to the invention are, for example, those with olefinic or acetylenic unsaturation well known in the technical field under consideration In this regard, reference may be made to American patents Nos .
- the reaction mixture comprises compounds A and compounds B in an amount such that the molar ratio Si-H / unsaturated groups and / or reactive function eg epoxy, ie between 0.4 and 10 preferably between 1 and 4 and, more preferably still, of the order of 1.7
- the catalyst being present in an amount of 1 to 400, preferably from 10 to 300 and, more preferably, from 20 to 200 ppm of platinum metal, exp ⁇ més by weight relative to the compounds A and B present
- crosslinking reactions of silicone oils in particular hydrosilylation (e g SI-H / SI-VI), catalyzed by heat-sensitive platinum complexes, in accordance with the invention, obey a process of homogeneous catalysis
- thermoreticutable composition characterized in that it comprises the compounds A and B and a catalyst and / or a precursor thereof, as defined above
- the weight quantities of compounds A and B and of the catalyst are also given above
- compositions according to the invention are prepared either before (or even long before) or even immediately before the implementation of the hydrosilylation process
- compositions are particularly stable on storage and that, in accordance with the process of the invention, they offer rapid crosslinking kinetics. In addition, they offer great ease of handling, application or placement. on different supports or other shaping molds
- compositions and / or the process according to the invention can incorporate different additives, chosen according to the intended final application.
- II can be, for example, mineral fillers or not and / or pigments such as fibers. crushed or natural (polymers) calcium carbonate, talc, titanium dioxide clay or fumed silica This can improve eg the mechanical characteristics of the final materials
- Soluble dyes, oxidation inhibitors and or any other material which does not interfere with the catalytic activity of the platinum complex can also be added to the composition or used in the context of the process according to the invention Once prepared by mixing all the compounds referred to above, the composition can be applied, for vanity purposes, on the surface of any solid substrate.
- These solid supports can be paper, cardboard, wood, plastic (eg polyester, nylon, polycarbonate), fibrous supports woven or not made of cotton, polyester, nylon etc, or a metal, glass or ceramic
- compositions according to the invention are, in particular, those of crosslinkable silicone oils, useful for the preparation of non-stick coatings on fibrous supports of any kind and in particular on paper
- the above compositions make it possible to achieve very high coating speeds, due to their very rapid crosslinking kinetics
- the operating method used consists in reacting a ligand of type ⁇ on the KARSTEDT complex of ideal formula Pt 2 (V ⁇ Me 2 S ⁇ -0-S ⁇ Me 2 V ⁇ ) 3 This reaction can be carried out in bulk or in a solvent such as toluene, ethanol or isopropanol,
- Additional purification can be carried out by chromatography on silica using a diethyl ether / hexane mixture as eluent.
- the crystals of the various products are obtained by slow evaporation of a hexane solution.
- TETCE Tetra-ethyl tetra-carboxylato ethylene
- MeNQ Methyl-naphthoquinone YId: 64.8%
- ADB 9.10 dihydro-9, 10-ortho-benzenoanthracene-1, 4-dione (dihydro 9, 10 triptycenequinone)
- nbn norbomylene or bicyclo [2.2.1] hept-2-ene
- EXAMPLE II EVALUATION OF CATALYSTS (I) AND (II) IN HYDROSILYLATION.
- the temperature is regulated by reflux of a solvent. This removes the calories generated during the reaction and allows greater reproducibility of the catalysis.
- the solvent chosen is hexane. Its boiling point is 72 ° C. Following various tests carried out in the laboratory and in industry, the optimum alkene / silane ratio has a value of 2.
- the quantity of catalyst will be fixed at 6, 6. 10 " 6 mole of platinum for 3. 10 _ 3 mo
- the temperature is regulated at 30 ° C.
- the substrates are introduced at the same time.
- the substrates used are models for hydrosilylation, namely trimethylvinylsilane and triethylhydrogenosilane.
- the catalysts tested will be: (MeNQ) Pt (diene), (TCNE) Pt (diene), (FN) Pt (diene), (TETCE) Pt (diene), (NQ) Pt (diene), (DCNQ) Pt ( diene) and (P1) Pt (diene).
- the manipulations are carried out protected from light. Solvents and reagents are degassed before use. A comparison to the Karstedt catalyst is made. For the nomenclature, see example 1.
- the most effective catalyst is the platinum complex carrying Naphtoquinone.
- the ligand reactivity orders, thereafter, are TETCE> TCNE> FN.
- Several derivatives of this type have been synthesized and complexed.
- diene tetramethyldivinylsiloxane
- Fig. 2 appended shows a curve of the% of SiH consumed as a function of time.
- the various catalysts used have proven to be very effective in catalyzing the hydrosilylation of trimethylvinylsilane by triethylsilane. The most reactive is the complex (MeNQ) Pt (diene).
- the new synthesized catalysts are more effective than the Karstedt catalyst.
- the most reactive seem to be the quinone complexes. Their average half-reaction time is of the order of 35 minutes.
- the tetraethyl-tetracarboxylato-ethylene complex is also of comparable reactivity.
- the platinum complex (MeNQ) Pt (diene) was compared under the same operating conditions to the existing Karstedt catalyst in dimé ⁇ que type Pt2 (TMDVS) 3 Two tests were carried out at identical platinum concentration on the substrates previously used. The results are shown in the attached FIG. 3, which shows the curve of the% of silane SiH consumed as a function of time.
- the catalyst according to the invention has a longer lifespan than that of its known counterparts. In other words, this catalyst is recyclable
- Fig. 5 appended gives the curve of% of SiH consumed as a function of time, with ( ⁇ ) and without Hg (+) for the MeNQ Pt diene catalyst.
- Fig. 7 appended gives the% of SiH consumed as a function of time.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP10503882A JP2000514849A (en) | 1996-06-28 | 1997-06-27 | Use of platinum complexes as thermally activatable homogeneous hydrosilylation catalysts. |
EP97930610A EP0907685A1 (en) | 1996-06-28 | 1997-06-27 | Use of platinum complexes particularly as homogeneous and heat activable catalysts for hydrosilylation |
AU34495/97A AU3449597A (en) | 1996-06-28 | 1997-06-27 | Use of platinum complexes particularly as homogeneous and heat activable catalysts for hydrosilylation |
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FR9608302A FR2750349B1 (en) | 1996-06-28 | 1996-06-28 | USE OF PLATINUM COMPLEXES IN PARTICULAR AS HOMOGENEOUS AND THERMOACTIVABLE HYDROSILYLATION CATALYSTS |
FR96/08302 | 1996-06-28 |
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EP (1) | EP0907685A1 (en) |
JP (1) | JP2000514849A (en) |
AU (1) | AU3449597A (en) |
CA (1) | CA2259255A1 (en) |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7157541B2 (en) | 2003-10-04 | 2007-01-02 | Goldschmidt Gmbh | Process for an addition reaction of organic silicon compounds having SiH groups with compounds having olefinic double bonds |
EP1754740A2 (en) | 2005-08-20 | 2007-02-21 | Goldschmidt GmbH | Process for production of addition products produced from SiH containing compounds and compounds which contain double bonds in aqueous media |
CN100390219C (en) * | 2000-08-17 | 2008-05-28 | 罗狄亚化学公司 | Method for preparing silicone oils by hydrosilylation of synthons contaiing at least a hydrocarbon cycle where in is included an oxygen atom in presence of catalytic metal complex |
DE102007013608A1 (en) | 2007-03-21 | 2008-09-25 | Wacker Chemie Ag | Si-substituted quinones as co-catalysts in transition-metal-catalyzed hydrosilylation |
WO2016005157A1 (en) | 2014-07-11 | 2016-01-14 | Evonik Degussa Gmbh | Composition containing platinum |
EP3020749A1 (en) | 2014-11-12 | 2016-05-18 | Evonik Degussa GmbH | Method for the production of compositions containing platinum |
CN105854945A (en) * | 2016-03-03 | 2016-08-17 | 中科院广州化学有限公司南雄材料生产基地 | Platinum-based hydrosilylation catalyst capable of being stably stored and preparation method of platinum-based hydrosilylation catalyst |
EP3415548A1 (en) | 2017-06-13 | 2018-12-19 | Evonik Degussa GmbH | Method for producing sic-linked polyether siloxanes |
EP3415547A1 (en) | 2017-06-13 | 2018-12-19 | Evonik Degussa GmbH | Method for producing sic-linked polyether siloxanes |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19837855A1 (en) | 1998-08-20 | 2000-02-24 | Wacker Chemie Gmbh | Curable organopolysiloxane compositions |
FR2825709B1 (en) * | 2001-06-07 | 2005-07-01 | Rhodia Chimie Sa | HYDROSILYLATION ELASTOMER-CROSS-LINKABLE SILICONE COMPOSITION IN THE PRESENCE OF CARBENE-BASED METAL CATALYSTS AND CATALYSTS OF THIS TYPE |
FR2831544B1 (en) | 2001-10-30 | 2005-07-01 | Rhodia Chimie Sa | PROCESS FOR THE PREPARATION OF SILICON OILS CONTAINING AT LEAST ONE HYDROCARBON CYCLE INCLUDING AN OXYGEN ATOM |
FR2879612B1 (en) * | 2004-12-21 | 2007-05-04 | Rhodia Chimie Sa | SILICONE ELASTOMER COMPOSITION, ADHESIVE, MONOCOMPONENT AND CROSS-LINKABLE BY POLYADDITION |
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1997
- 1997-06-27 CA CA002259255A patent/CA2259255A1/en not_active Abandoned
- 1997-06-27 WO PCT/FR1997/001157 patent/WO1998000463A1/en not_active Application Discontinuation
- 1997-06-27 JP JP10503882A patent/JP2000514849A/en active Pending
- 1997-06-27 EP EP97930610A patent/EP0907685A1/en not_active Withdrawn
- 1997-06-27 AU AU34495/97A patent/AU3449597A/en not_active Abandoned
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DE1495917A1 (en) * | 1962-07-02 | 1969-04-10 | Gen Electric | Process for increasing the molecular weight of organopolysiloxanes |
US3775452A (en) * | 1971-04-28 | 1973-11-27 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
EP0416471A2 (en) * | 1989-08-31 | 1991-03-13 | Dow Corning Toray Silicone Company, Limited | Platinum catalyst composition, method for its preparation and curable organopolysiloxane compositions containing same |
WO1995025734A1 (en) * | 1994-03-18 | 1995-09-28 | Rhone Poulenc Chimie | Platinum complexes and light-activatable hydrosilylation catalysts containing same |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100390219C (en) * | 2000-08-17 | 2008-05-28 | 罗狄亚化学公司 | Method for preparing silicone oils by hydrosilylation of synthons contaiing at least a hydrocarbon cycle where in is included an oxygen atom in presence of catalytic metal complex |
US7157541B2 (en) | 2003-10-04 | 2007-01-02 | Goldschmidt Gmbh | Process for an addition reaction of organic silicon compounds having SiH groups with compounds having olefinic double bonds |
EP1754740A2 (en) | 2005-08-20 | 2007-02-21 | Goldschmidt GmbH | Process for production of addition products produced from SiH containing compounds and compounds which contain double bonds in aqueous media |
US7619035B2 (en) | 2005-08-20 | 2009-11-17 | Goldschmidt Gmbh | Method of producing addition products of compounds containing SiH groups onto reactants having one double bond on aqueous media |
DE102007013608A1 (en) | 2007-03-21 | 2008-09-25 | Wacker Chemie Ag | Si-substituted quinones as co-catalysts in transition-metal-catalyzed hydrosilylation |
WO2016005157A1 (en) | 2014-07-11 | 2016-01-14 | Evonik Degussa Gmbh | Composition containing platinum |
DE102014213507A1 (en) | 2014-07-11 | 2016-01-14 | Evonik Degussa Gmbh | Platinum-containing composition |
US10836867B2 (en) | 2014-07-11 | 2020-11-17 | Evonik Operations Gmbh | Composition containing platinum |
EP3020749A1 (en) | 2014-11-12 | 2016-05-18 | Evonik Degussa GmbH | Method for the production of compositions containing platinum |
CN105854945A (en) * | 2016-03-03 | 2016-08-17 | 中科院广州化学有限公司南雄材料生产基地 | Platinum-based hydrosilylation catalyst capable of being stably stored and preparation method of platinum-based hydrosilylation catalyst |
EP3415548A1 (en) | 2017-06-13 | 2018-12-19 | Evonik Degussa GmbH | Method for producing sic-linked polyether siloxanes |
EP3415547A1 (en) | 2017-06-13 | 2018-12-19 | Evonik Degussa GmbH | Method for producing sic-linked polyether siloxanes |
Also Published As
Publication number | Publication date |
---|---|
CA2259255A1 (en) | 1998-01-08 |
EP0907685A1 (en) | 1999-04-14 |
FR2750349B1 (en) | 1998-10-16 |
FR2750349A1 (en) | 1998-01-02 |
AU3449597A (en) | 1998-01-21 |
JP2000514849A (en) | 2000-11-07 |
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