WO2011028141A1 - Synthesis of fluorocarbofunctional alkoxysilanes and chlorosilanes - Google Patents
Synthesis of fluorocarbofunctional alkoxysilanes and chlorosilanes Download PDFInfo
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- WO2011028141A1 WO2011028141A1 PCT/PL2010/000072 PL2010000072W WO2011028141A1 WO 2011028141 A1 WO2011028141 A1 WO 2011028141A1 PL 2010000072 W PL2010000072 W PL 2010000072W WO 2011028141 A1 WO2011028141 A1 WO 2011028141A1
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- Prior art keywords
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- fluorocarbofunctional
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 28
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000010948 rhodium Substances 0.000 claims abstract description 29
- 229910000077 silane Inorganic materials 0.000 claims abstract description 20
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 19
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 17
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 150000004756 silanes Chemical class 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000005374 siloxide group Chemical group 0.000 claims abstract description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 16
- 150000001336 alkenes Chemical class 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- -1 Fluoroalkyl silanes Chemical class 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000006136 alcoholysis reaction Methods 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NWKBSEBOBPHMKL-UHFFFAOYSA-N dichloro(methyl)silane Chemical compound C[SiH](Cl)Cl NWKBSEBOBPHMKL-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910004721 HSiCl3 Inorganic materials 0.000 description 2
- 229910019032 PtCl2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- DTDFWYZVBJYVPL-UHFFFAOYSA-N 3-(1,1,2,2-tetrafluoroethoxy)prop-1-ene Chemical compound FC(F)C(F)(F)OCC=C DTDFWYZVBJYVPL-UHFFFAOYSA-N 0.000 description 1
- PIJBSAHLEOMSSJ-UHFFFAOYSA-N 3-(1,2,2,2-tetrafluoroethoxy)prop-1-ene Chemical compound FC(F)(F)C(F)OCC=C PIJBSAHLEOMSSJ-UHFFFAOYSA-N 0.000 description 1
- BGAVFOWTHSTHQQ-UHFFFAOYSA-N FC(C[SiH](Cl)C)(C(OCC)(F)F)F Chemical class FC(C[SiH](Cl)C)(C(OCC)(F)F)F BGAVFOWTHSTHQQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 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 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KTAQYFZUMFKWBE-UHFFFAOYSA-N chloro-[3-(1,1,2,3,3,3-hexafluoropropoxy)propyl]-methylsilane Chemical class C[SiH](Cl)CCCOC(F)(F)C(F)C(F)(F)F KTAQYFZUMFKWBE-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- VIRVTHOOZABTPR-UHFFFAOYSA-N dichloro(phenyl)silane Chemical compound Cl[SiH](Cl)C1=CC=CC=C1 VIRVTHOOZABTPR-UHFFFAOYSA-N 0.000 description 1
- JGRBHWNAFYZGSF-UHFFFAOYSA-N dichloro-[3-(1,1,2,2,3,3,4,4,5,7,7,7-dodecafluoroheptoxy)propyl]-phenylsilane Chemical compound FC(F)(F)CC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)OCCC[Si](Cl)(Cl)C1=CC=CC=C1 JGRBHWNAFYZGSF-UHFFFAOYSA-N 0.000 description 1
- SMQQUMOBNWNYJU-UHFFFAOYSA-N dichloro-methyl-[3-(1,1,2,2,3,5,5,5-octafluoropentoxy)propyl]silane Chemical compound C[Si](Cl)(Cl)CCCOC(F)(F)C(F)(F)C(F)CC(F)(F)F SMQQUMOBNWNYJU-UHFFFAOYSA-N 0.000 description 1
- SUUYDMDGZWFQNU-UHFFFAOYSA-N diethoxy(phenyl)silane Chemical compound CCO[SiH](OCC)C1=CC=CC=C1 SUUYDMDGZWFQNU-UHFFFAOYSA-N 0.000 description 1
- FZFUHRFBVKSMGR-UHFFFAOYSA-N diethoxy-[3-(1,1,2,2,3,5,5,5-octafluoropentoxy)propyl]-phenylsilane Chemical compound FC(F)(F)CC(F)C(F)(F)C(F)(F)OCCC[Si](OCC)(OCC)C1=CC=CC=C1 FZFUHRFBVKSMGR-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006342 heptafluoro i-propyl group Chemical group FC(F)(F)C(F)(*)C(F)(F)F 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000012451 post-reaction mixture Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- QWNRMPOVGMXEKG-UHFFFAOYSA-N trichloro-[3-(1,3,3,3-tetrafluoropropoxy)propyl]silane Chemical compound FC(F)(F)CC(F)OCCC[Si](Cl)(Cl)Cl QWNRMPOVGMXEKG-UHFFFAOYSA-N 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical class Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- RPMSRHWHLXNMAF-UHFFFAOYSA-N triethoxy-[3-(1,1,2,2,3,5,5,5-octafluoropentoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOC(F)(F)C(F)(F)C(F)CC(F)(F)F RPMSRHWHLXNMAF-UHFFFAOYSA-N 0.000 description 1
- ORXWFNORGLUZKA-UHFFFAOYSA-N triethoxy-[3-(1,3,3,3-tetrafluoropropoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOC(F)CC(F)(F)F ORXWFNORGLUZKA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
Definitions
- the subject of invention is the synthesis of fluorocarbofunctional silanes of the general formula 1 ,
- - n takes values from 1 to 12
- m takes values from 1 to 4,
- R 1 stands for an alkoxy group or halogen
- R 2 and R 3 can be the same as R 1 or different from it and stand for:
- R 1 stands for a halogen
- Fluoroalkyl silanes are used as surfactants, for surface modification of lenses and optical fibres, for production of oil-, dirt- and water- repellent surfaces, as lubricants, as components of many cosmetic preparations and as modifiers of fluorine and silicon rubber.
- fluoroalkyl silanes are not commonly applied mainly because of problems in their synthesis, high price and poor accessibility of raw products.
- Fluorocarbofunctional alkyl-, alkoxy- or arylsilanes containing at least one alkoxy group are obtained by alcoholysis of appropriate fluorocarbofunctional chlorosilanes.
- fluorinated olefins are obtained from fluoroalkyl iodide as a precursor, which means that the olefin obtained can contain certain amounts of iodide ions that have adverse effect on hydrosilylation as they poison the catalyst.
- the catalyst is dissolved in the olefin and silane is introduced to this mixture, so if the iodide ions present in the olefin lead to the catalyst poisoning, the reaction will not take place and the mixture of expensive raw products is unsuitable for further use.
- Hydrosilylation is the main reaction used in synthesis of fluorinated silanes (1).
- the catalysts of hydrosilylation of fluorolefines are platinum species; WO 2006/127664 patent describes the use of hexachloroplatinic acid H 2 PtCl 6 with platinum at the fourth state of oxidation as a catalyst, while EP 0075865 patent describes the use of compound with platinum at the second state of oxidation [PtCl 2 (cod)] and US 6255516 patent describes the use of Karstedt's catalyst with platinum at the zero state of oxidation. Platinum compounds show catalytic activity in hydrosilylation of a wide group of different functional olefins, but they are susceptible to poisoning by different impurities, in particular iodide ions (2).
- JP 06239872 patent describes the high pressure process performed for 48h, at 150°C with the yield of 88%
- WO94/20442 patent presents the process run at 100°C for 50h with the yield of 89%.
- Long time of the reaction and high temperature needed have negative effect on the selectivity of the process as such conditions favour isomerization of olefins and shifting of the double bond from the terminal to inner position. Addition of silane to the double bond does not take place at the position other than terminal, which means that a lot of side products are formed and that the yield decreases.
- Hydrosilylation is an exothermic process, which means that after initiation of the reaction and in particular in the presence of highly active platinum catalysts, the temperature of the process rapidly increases that can lead to isomerization of fluorinated olefins, so to decrease in the yield and selectivity.
- different solvents are used: e.g. toluene, isooctane, hexane, trifluoromethylbenzene , l,3-bis(trifluoromethyl)benzene, in the amount of 10-90%.
- solvents prevents from rapid and hard to control temperature increase, but on the other hand, it implies the need of additional stage of the solvent removal, most often by energy and time consuming distillation.
- HSiMe n Cl 3-n silane is introduced dropwise to a mixture of the fluorinated olefin and catalyst that has been heated to a certain desired temperature.
- the patents US 5869728 and US 6255516 propose dropwise introduction of fluorinated olefin into a mixture of silane and catalyst, which reduces the risk of the catalyst poisoning with iodide ions present in the fluorinated olefin and permits interruption of the process in the beginning stage thus limiting the loss of expensive olefins.
- mixing silane with catalyst can also lead to many undesired side processes, like e.g. redistribution of silanes, which drastically decreases the yield of the main process.
- the substrates are fluoroalkyl-allyl ethers and perfluorinated allyl polyethers.
- the European patent EP0075864 describes the synthesis of (tetrafluoro- ethyloxypropyl)methylchlorosilanes by hydrosilylation of allyl-tetrafluoro-ethyl ether with trichlorosilane and methyldichlorosilane.
- the process is conducted in a pipe reactor under a pressure of 5 bars at 100°C in the presence of [ ⁇ PtCl 2 (octene) ⁇ 2 ] as a catalyst.
- the main product obtained with the yield of 78-90% is accompanied by many products of redistribution of the initial silane and fluoroalkyl-allyl ether.
- the patent also describes an analogous reaction performed under atmospheric pressure over the same catalyst. In these conditions the main product was obtained with the yield of 46%. To obtain satisfactory yield the reaction needs to be carried out under high pressures, moreover, the product contains many impurities.
- the patent EP0075865 describes the method of synthesis of (hexafluoropropyloxypropyl)methylchlorosilanes by hydrosilylation of allyl- hexafluoropropyl ether with trichloro- and methyldichlorosilanes (analogous as in EP0075864). By alcoholysis of the main products (hexafluoropropyloxy-propyl)trialkoxy- and (hexafluoropropyloxypropyl)-methyldialkoxy-silanes were obtained.
- R 1 can be CF 3 , C 2 F 5 , CF(CF 3 ) 2 or other similar groups.
- the derivatives of this type at the first stage are subjected to the reaction with sodium hydride and transformed into the corresponding sodium alcoholates, which subsequently in the reaction with allyl bromide are transformed into polyethers containing an allyl group. These derivatives are subsequently subjected to hydrosilylation with trichlorosilane.
- This process is conducted in a high pressure reactor at a temperature from the range 165-175°C range for 8 hours. After the reaction, the crude product is purified by distillation and the yield of the process is 95%. At the next stage, the trichlorosilyl derivative is subjected to alcoholysis by methanol leading to the appropriate trialkoxysilyl derivative of perfluorinated polyethers.
- Chlorosilyl and methyldichlorosilyl fluorocarbofunctional silanes are susceptible to hydrolysis in the presence of trace amounts of moisture, so the process of alcoholysis must be conducted in absolutely anhydrous environment, which poses additional difficulty and implies the need to use fully dried substrates, protect the reaction system against moisture and use the apparatuses made of materials resistant to corrosion.
- the subject of invention is a cheap and effective method of synthesis of fluorocarbofunctional alkoxysilanes and chlorosilanes.
- - n takes values from 1 to 12
- m takes values from 1 to 4,
- R 1 stands for an alkoxy group or halogen
- R 2 and R 3 can be the same or different and
- R 1 stands for an alkoxy group
- R 2 and R 3 stand for an alkoxy group containing
- R 1 stands for a halogen
- n and m take the same values as specified above,
- R 1 stands for a halogen
- R 1 stands for an alkoxy group
- allyl-fluoroalkyl ether in excess with respect to the appropriate silane or chlorosilane to ensure complete consumption of silane as its remains weaken the stability of the product.
- the most beneficial is the excess in the amount of close to 1.1 or from the range of 1.1 - 1.4.
- the catalyst is used in the amount of 10 "4 to 10 "6 mol Rh per 1 mol of silane or chlorosilane; the best results are obtained with the catalyst in the amount of 5x10 "5 mol per 1 mol of silane or chlorosilane.
- an appropriate allyl-fluoroalkyl ether and the catalyst [ ⁇ Rh(OSiMe3)(cod) ⁇ 2 ] are introduced into the reactor in the amounts corresponding to the concentrations corresponding to 10 "4 do 10 "6 mol of Rh per 1 mol of Si-H groups.
- the substrates are stirred to get a homogenous system to which an appropriate silane is introduced in doses.
- the content of the reactor is stirred on heating to a temperature from the range 25-60°C at which the reactor is kept till the reaction completion, which usually takes from 1 to 4 hours.
- the product can be directly used in many applications, but when it must be of high purity the post-reaction mixture is subjected to fractional distillation to remove the remains of unreacted substrates and the catalyst.
- the method of synthesis which is the subject of this invention permits obtaining fluorocarbofunctional alkoxysilanes or chlorosilanes in a single stage process.
- siloxide rhodium complex as a catalyst in the hydrosilylation of ethers in the method proposed permitted a decrease in the temperature of the process and significant shortening of the process, which prevents from the occurrence of many side reactions (e.g. isomerization of fluoroalkyl-allyl ether) improving the yield and selectivity of the process.
- the rhodium catalysts show greater resistance to poisoning and are less sensitive to the impurities contained in the substrates.
- the rhodium catalysts permit a single-stage synthesis of a variety of fluoroalkyl alkoxysilane or chlorosilane derivatives with ho need of modification of the method for particular groups of derivatives.
- Fluoroalkyl-allyl ether used in the synthesis proposed is obtained by the known Williamson method from fluorinated alcohols being much easier accessible and cheaper than fluoroalkyl iodides used in other known methods.
- Rh/1 mol Si-H) of siloxide rhodium complex [ ⁇ Rh(OSiMe 3 )(cod) ⁇ 2 ] were placed in a flask equipped with a magnetic stirrer, reflux and dropping funnel protected against moisture. Upon stirring of the flask content, 11.5 g (70 mmol) of HSi(OEt) 3 were added dropwise. After introduction of the whole load of silane, the content was stirred for 2h at 25°C. Then the mixture was subjected to distillation under reduced pressure, collecting the fraction boiling at 84-87°C/2mmHg. The final product of (tetrafluoropropyloxypropyl)triethoxysilane was obtained in the amount of 21.2 g, which makes 92% of the theoretical yield. The identity of the product was confirmed by NMR analysis.
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP10757641A EP2473514A1 (en) | 2009-09-01 | 2010-08-16 | Synthesis of fluorocarbofunctional alkoxysilanes and chlorosilanes |
CN2010800387955A CN102482300A (en) | 2009-09-01 | 2010-08-16 | Synthesis of fluorocarbofunctional alkoxysilanes and chlorosilanes |
US13/393,371 US20120165565A1 (en) | 2009-09-01 | 2010-08-16 | Synthesis of fluorocarbofunctional alkoxysilanes and chlorosilanes |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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PLP.388930 | 2009-09-01 | ||
PL388929A PL217830B1 (en) | 2009-09-01 | 2009-09-01 | Process for the preparation of fluorocarbfunctional alkoxysilanes |
PLP.388929 | 2009-09-01 | ||
PL388930A PL217829B1 (en) | 2009-09-01 | 2009-09-01 | Process for the preparation of fluorocarbfunctional chlorosilanes |
Publications (1)
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WO2011028141A1 true WO2011028141A1 (en) | 2011-03-10 |
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Family Applications (1)
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PCT/PL2010/000072 WO2011028141A1 (en) | 2009-09-01 | 2010-08-16 | Synthesis of fluorocarbofunctional alkoxysilanes and chlorosilanes |
Country Status (5)
Country | Link |
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US (1) | US20120165565A1 (en) |
EP (1) | EP2473514A1 (en) |
KR (1) | KR20120093185A (en) |
CN (1) | CN102482300A (en) |
WO (1) | WO2011028141A1 (en) |
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CN108822726A (en) * | 2018-06-13 | 2018-11-16 | 朱冠华 | A kind of preparation method of waterproof coating |
CN108842176A (en) * | 2018-06-13 | 2018-11-20 | 朱冠华 | A kind of waterproof aluminum profile and preparation method thereof |
Citations (10)
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EP0075865A2 (en) | 1981-09-25 | 1983-04-06 | Wacker-Chemie GmbH | Hexafluoropropyl-oxy-alkyl silanes |
EP0075864A2 (en) | 1981-09-25 | 1983-04-06 | Wacker-Chemie GmbH | Process for the preparation of tetrafluoroethyloxy-alkyl silanes |
JPH02178292A (en) | 1988-12-28 | 1990-07-11 | Neos Co Ltd | Fluorine-containing silicone compound |
EP0538061A2 (en) | 1991-10-17 | 1993-04-21 | Shin-Etsu Chemical Co., Ltd. | Fluorine-containing organosilicon compound and process of producing the same |
JPH06239872A (en) | 1993-02-17 | 1994-08-30 | Shin Etsu Chem Co Ltd | Production of fluorine-containing silane compound |
WO1994020442A1 (en) | 1993-03-12 | 1994-09-15 | Daikin Industries, Ltd. | Fluorinated aromatic compound |
US5869728A (en) | 1996-10-26 | 1999-02-09 | Huels Aktiengesellschaft | Process for preparing fluoroalkyl-containing organosilicon compounds, and their use |
WO2005058919A1 (en) | 2003-12-19 | 2005-06-30 | Degussa Ag | Specific process for preparing silicon compounds bearing fluoroalkyl groups by hydrosilylation |
WO2006127664A1 (en) | 2005-05-23 | 2006-11-30 | Innovation Chemical Technologies, Ltd. | Fluorinated organic silicon coating material |
GB2443626A (en) | 2006-11-07 | 2008-05-14 | Dow Corning | Fluorosilicones |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3774917B2 (en) * | 1995-10-30 | 2006-05-17 | 昭和電工株式会社 | Fluorine-containing organosilicon compound |
-
2010
- 2010-08-16 EP EP10757641A patent/EP2473514A1/en not_active Withdrawn
- 2010-08-16 US US13/393,371 patent/US20120165565A1/en not_active Abandoned
- 2010-08-16 WO PCT/PL2010/000072 patent/WO2011028141A1/en active Application Filing
- 2010-08-16 CN CN2010800387955A patent/CN102482300A/en active Pending
- 2010-08-16 KR KR1020127008298A patent/KR20120093185A/en not_active Application Discontinuation
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0075865A2 (en) | 1981-09-25 | 1983-04-06 | Wacker-Chemie GmbH | Hexafluoropropyl-oxy-alkyl silanes |
EP0075864A2 (en) | 1981-09-25 | 1983-04-06 | Wacker-Chemie GmbH | Process for the preparation of tetrafluoroethyloxy-alkyl silanes |
JPH02178292A (en) | 1988-12-28 | 1990-07-11 | Neos Co Ltd | Fluorine-containing silicone compound |
EP0538061A2 (en) | 1991-10-17 | 1993-04-21 | Shin-Etsu Chemical Co., Ltd. | Fluorine-containing organosilicon compound and process of producing the same |
JPH06239872A (en) | 1993-02-17 | 1994-08-30 | Shin Etsu Chem Co Ltd | Production of fluorine-containing silane compound |
WO1994020442A1 (en) | 1993-03-12 | 1994-09-15 | Daikin Industries, Ltd. | Fluorinated aromatic compound |
US5869728A (en) | 1996-10-26 | 1999-02-09 | Huels Aktiengesellschaft | Process for preparing fluoroalkyl-containing organosilicon compounds, and their use |
US6255516B1 (en) | 1996-10-26 | 2001-07-03 | Huels Aktiengesellschaft | Process for preparing fluoroalkyl-containing organosilicon compounds, and their use |
WO2005058919A1 (en) | 2003-12-19 | 2005-06-30 | Degussa Ag | Specific process for preparing silicon compounds bearing fluoroalkyl groups by hydrosilylation |
WO2006127664A1 (en) | 2005-05-23 | 2006-11-30 | Innovation Chemical Technologies, Ltd. | Fluorinated organic silicon coating material |
GB2443626A (en) | 2006-11-07 | 2008-05-14 | Dow Corning | Fluorosilicones |
Non-Patent Citations (4)
Title |
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AUNER, N. ET AL.: "Organosilicon Chemistry VI: from molecules to materials", 2005, WILEY-VCH VERLAG GMBH & CO, Weinheim, Germany, ISBN: 978-3-527-31214-6 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 2005, MACIESJEWSKI, H. ET AL.: "Synthesis of glycidoxypropyl-silanes and siloxanes via rhodium siloxide-catalyzed hydrosilylation", XP002614136, retrieved from STN Database accession no. 151:289615 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 2007, MARCINIEC, B. ET AL.: "3-Butoxy (or phenoxy) propyltriethoxysilanes and processes for their preparation and also for 3-glycidoxypropylsilanes by rhodium-catalyzed addition of triethoxysilane to the corresponding allyl ethers", XP002614135, Database accession no. 148:192072 * |
MARCINIEC, B. ET AL.: "Catalytic activity of siloxy-rhodium(I) complexes in hydrosilation of alkenes", JOURNAL OF MOLECULAR CATALYIS A: CHEMICAL, vol. 144, 1999, pages 263 - 271, XP002614134 * |
Also Published As
Publication number | Publication date |
---|---|
US20120165565A1 (en) | 2012-06-28 |
CN102482300A (en) | 2012-05-30 |
KR20120093185A (en) | 2012-08-22 |
EP2473514A1 (en) | 2012-07-11 |
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