WO1992011266A1 - Silanes tetraalcoxiliques, leur procede de production et leur utilisation - Google Patents
Silanes tetraalcoxiliques, leur procede de production et leur utilisation Download PDFInfo
- Publication number
- WO1992011266A1 WO1992011266A1 PCT/EP1991/002426 EP9102426W WO9211266A1 WO 1992011266 A1 WO1992011266 A1 WO 1992011266A1 EP 9102426 W EP9102426 W EP 9102426W WO 9211266 A1 WO9211266 A1 WO 9211266A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- transesterification
- general formula
- tetramethoxy
- double
- hydrotalcite
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000004756 silanes Chemical class 0.000 title abstract 4
- 238000004519 manufacturing process Methods 0.000 title description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001298 alcohols Chemical class 0.000 claims abstract description 25
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 hydroxide compound Chemical class 0.000 claims abstract description 14
- 239000012530 fluid Substances 0.000 claims abstract description 8
- 239000005068 cooling lubricant Substances 0.000 claims abstract description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 23
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 21
- 229960001545 hydrotalcite Drugs 0.000 claims description 21
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 21
- 150000004679 hydroxides Chemical class 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 150000001768 cations Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- XULHFMYCBKQGEE-UHFFFAOYSA-N 2-hexyl-1-Decanol Chemical compound CCCCCCCCC(CO)CCCCCC XULHFMYCBKQGEE-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000008406 cosmetic ingredient Substances 0.000 claims description 3
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- LOIMOHMWAXGSLR-UHFFFAOYSA-N 2-hexyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCC LOIMOHMWAXGSLR-UHFFFAOYSA-N 0.000 claims description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 claims description 2
- JYZLSYFPFQTNNO-UHFFFAOYSA-N 2-octyldecan-1-ol Chemical compound CCCCCCCCC(CO)CCCCCCCC JYZLSYFPFQTNNO-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- 150000003138 primary alcohols Chemical class 0.000 claims 1
- 150000003333 secondary alcohols Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 27
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 150000002763 monocarboxylic acids Chemical class 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052599 brucite Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- COTJEVAHCUGDRP-UHFFFAOYSA-N 2-hexyltridecan-1-ol Chemical compound CCCCCCCCCCCC(CO)CCCCCC COTJEVAHCUGDRP-UHFFFAOYSA-N 0.000 description 1
- FGZXHVORLPLICA-UHFFFAOYSA-N 2-methylundecan-1-ol Chemical compound CCCCCCCCCC(C)CO FGZXHVORLPLICA-UHFFFAOYSA-N 0.000 description 1
- PDBKSKNFOPOYTP-UHFFFAOYSA-N 2-nonyltridecan-1-ol Chemical compound CCCCCCCCCCCC(CO)CCCCCCCCC PDBKSKNFOPOYTP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000723347 Cinnamomum Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JIFPTBLGXRKRAO-UHFFFAOYSA-K aluminum;magnesium;hydroxide;sulfate Chemical compound [OH-].[Mg+2].[Al+3].[O-]S([O-])(=O)=O JIFPTBLGXRKRAO-UHFFFAOYSA-K 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000017803 cinnamon Nutrition 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
- WFRBMXFCEAHLGH-UHFFFAOYSA-N cyclodecanol Chemical compound OC1CCCCCCCCC1 WFRBMXFCEAHLGH-UHFFFAOYSA-N 0.000 description 1
- YOXHCYXIAVIFCZ-UHFFFAOYSA-N cyclopropanol Chemical compound OC1CC1 YOXHCYXIAVIFCZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229960004018 magaldrate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QICOYMKINDJWAH-UHFFFAOYSA-N octacosan-13-ol Chemical compound CCCCCCCCCCCCCCCC(O)CCCCCCCCCCCC QICOYMKINDJWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C07F7/04—Esters of silicic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Definitions
- the invention relates to tetraalkoxysilanes from Guerbet alcohols, a process for the preparation of light-colored tetraalkoxysilanes of the general formula Si (0R . 4 by transesterification of tetramethoxy or tetraethoxysilane with an alcohol in the presence of catalytic amounts of at least one double-layer hydroxide compound with continuous removal of methanol or ethanol, and the like Use of the light-colored tetraalkoxysilanes as cosmetic ingredients, cooling lubricants, hydraulic fluids, heat transfer fluids or defoamers.
- Tetraalkoxysilanes of the general formula Si (0R) 4 which are also referred to as silica tetraesters, are derived from long-chain fatty alcohols and are known, for example, as textile treatment agents.
- silicic acid esters of unsaturated straight-chain fatty alcohols give textiles a soft feel.
- textile materials that have been treated with these silicic acid esters at higher temperatures show a yellowing that is unacceptable for light textiles.
- Oxo alcohols of this type are essentially saturated and also have 35 to 65% by weight, branched alcohols such as 2-methylundecanol, 2-n-octyldecanol and 2-n-hexyltridecanol. Despite the high proportion of branched alcohols, the hydrolysis stability of their aqueous ones Emulsions are not sufficient if the emulsion is still free
- a further disadvantage is that, owing to the production process, the tetraalkoxysilanes can already have their own color or that corrosive hydrochloric acid is produced in the production process.
- the tetraalkoxysilanes can be prepared either by direct alcoholysis of tetrachlorosilane or by transesterification of tetramethoxy or tetraethoxysilane with the corresponding alcohols.
- the transesterification reactions of alkoxysilanes with alcohols have been known in the art for some time (see, for example, in H. Steinmann, G. Tschernko and H. Hamann, Z. Che. Vol. 17, pp. 89-92, 1977).
- Transesterification catalysts have hitherto generally been used both acids, such as hydrogen chloride, hydrogen fluoride, sulfuric acid, trifluoroacetic acid or p-toluenesulfonic acid, and bases, such as alkali metal hydroxides, methanolates or ethanolates.
- acids such as hydrogen chloride, hydrogen fluoride, sulfuric acid, trifluoroacetic acid or p-toluenesulfonic acid
- bases such as alkali metal hydroxides, methanolates or ethanolates.
- bases such as alkali metal hydroxides, methanolates or ethanolates.
- tetraalkoxysilanes can no longer be purified from higher alcohols with a chain length of more than 12 carbon atoms by distillation.
- the basic catalyst must first be neutralized and then the salt formed must be separated off, which means an additional process step.
- the object of the present invention was to provide a new process for the preparation of tetraalkoxysilanes by transesterification of the easily accessible tetramethoxysilane or tetraethoxysilanes with higher alcohols, which, using a suitable catalyst, had the shortest possible reaction times with a high degree of esterification leads to high-purity, light-colored tetraalkoxysilanes.
- Another object of the present invention was to provide tetraalkoxysilanes which show improved hydrolysis stabilities.
- the present invention accordingly relates to a process for the preparation of light-colored tetraalkoxysilanes of the general formula Si (0R) 4, in which R represents a straight-chain and / or branched-chain, saturated and / or unsaturated, aliphatic hydrocarbon radical, by transesterification of Tetramethoxy or tetraethoxysilane with at least one alcohol in the presence of a catalyst, characterized in that the transesterification at temperatures of 80 to 250 ° C in the presence of at least one double-layer hydroxide compound of the general formula
- B represents an equivalent of an inorganic anion, from the group formed by carbonate, hydrogen carbonate, sulfate, nitrate, nitrite, phosphate, hydroxide and halides, and in which the conditions 0.1 _ x _ 0.5, 0 ⁇ a ⁇ 0.5, 0 _ b _ 0.5, 0 ⁇ a + b _ 0.5 and 0 _ z _ 10 are considered to be heterogeneous catalysts and the methanol or ethanol is continuously removed from the reaction mixture.
- the divalent metal cation of the formula (I) is preferably selected from magnesium, calcium, manganese, zinc and copper.
- the trivalent metal cation of formula (I) is preferably selected from iron and aluminum. If the above - in connection with the explanation of the general formula (I) - is spoken of at least one divalent and trivalent metal cation, this means that in such double-layer hydroxide compounds there may be several divalent or trivalent metal cations next to each other can be present.
- Double-layer hydroxide compounds Two-dimensional inorganic polycations with intra-crystalline charge balancing by means of movable interlayer anions are also known under the name “double-layer hydroxide compounds” and have been described several times in the literature. Is referred to, for. B. on R. Allmann, "Double-layer structures with brucite-like layered ions", Chimia 24, 99 to 108 (1970). Chemical pose these compounds are mixed hydroxy salts of 2- and 3-valent metal ions and can be characterized by the general formula II:
- hydrotalcite which occurs as a mineral in nature.
- hydrotalcites which are described, for example, in DE-C-1 592 126, DE-A-3 346 943, DE-A-3 306 822 and EP-A-207 811.
- Hydrotalcite is a natural mineral with the ideal formula [Mg6Al 2 (0H) i5] C03.4H 2 0, whose structure is derived from that of brucite (Mg (0H) 2 ).
- Brucite crystallizes in a layer structure with the metal ions in octahedral gaps between two layers of densely packed hydroxyl ions, only every second layer of the octahedral gaps being occupied.
- some magnesium ions are replaced by aluminum ions, which means that the shift package receives a positive charge. This is compensated for by the anions which are located in the intermediate layers together with zeolitic crystal water.
- calcined double-layer hydroxide compounds of the general formula (I) can also be used in the process according to the invention.
- the calcined compounds of the general formula (I) are obtained by heating or calcining by continuously releasing water. In general, the crystal water is completely released at temperatures around 200 ° C. A further increase in temperature leads both to the elimination of water from the hydroxide structure and of carbon dioxide from the carbonate which is usually present as a counter anion.
- a prototype of such compounds is the calcined hydrotalcite, of which, for example from DE-A-30 19 632, the anion reuptake is known, with reformation of the layer structure.
- the double-layer hydroxide compounds of the general formula (I) used can be the hydrophobic double-layer hydroxide compounds described in the not yet published German patent applications P 40 10 606.3 and P 40 34 305.7 of the applicant.
- the hydrophobic double-layer hydroxide compounds are reacted in a low-boiling organic solvent, preferably alcohols with 1 to 6 carbon atoms, open-chain and cyclic ethers and / or ketones, by reacting monocarboxylic acids and / or dicarboxylic acids with double-layer hydroxide.
- a low-boiling organic solvent preferably alcohols with 1 to 6 carbon atoms, open-chain and cyclic ethers and / or ketones
- the hydrophobization is particularly preferably carried out in isopropanol, diethyl ether, tetrahydrofuran and / or acetone.
- hydrophobicized double-layer hydroxide compounds of the general formula I can also be obtained by direct reaction of double-layer hydroxide compounds of the general formula II with mono- and / or dicarboxylic acids without the addition of a solvent using any stirring tool, preferably a kneader.
- the compounds of the general formula I can also be analogous to the process known from the teaching of DE-A-3731 919 by reacting double-layer hydroxide compounds with an aqueous suspension of an alkali metal and / or alkaline earth metal salt, preferably sodium salts Produce mono- and / or dicarboxylic acid.
- hydrophobicized double layer hydroxide compounds can also be obtained from calcined double layer hydroxide compounds by reacting them with the mono- or dicarboxylic acids be preserved; carbonate-free or carbonate-containing products can be obtained with the exclusion of air or COg or in the presence of carbon dioxide.
- the stoichiometric water content of the hydrophobic double-layer hydroxide compounds can - depending on the type of production and the drying conditions - be in the range from 0 to 10 molecules; a range from 0 to 4 molecules is preferred, which is generally obtained if the hydrophobic double-layer hydroxide compounds are dried to constant weight at temperatures in the range from 100 to 250 ° C., preferably from 150 to 220 ° C., so that a particularly high catalytic activity can be guaranteed.
- compounds derived from hydrotalcite are used as double-layer hydroxide compounds of the general formula I.
- the reaction mixture containing tetramethoxy or tetraethoxysilane, at least one alcohol and at least one catalyst of the general formula (I) is raised to 80 at a temperature of from 2 to 5 ° C. per minute to 140 ° C, preferably 110 to 130 ° C, heated and then with continuous removal of the methanol or ethanol formed at a reduced temperature heating rate of 0.1 to 2 ° C, preferably 0.3 to 1 ° C, per minute to 150 to 250 ° C, preferably 180 to 200 ° C, heated.
- the transesterification is carried out in such a way that, based on the amount of methanol or ethanol distilled off, a degree of transesterification of 50 to 99%, preferably 85 to 95%, is achieved.
- the degree of transesterification is understood to mean a percentage which results from the quotient of the amount of alcohol actually distilled off and the amount of alcohol which can theoretically be achieved with quantitative conversion.
- the transesterification of tetramethoxy or tetraethoxysilane with the corresponding alcohol is carried out in a molar ratio of 1: 4 to 1:10, preferably 1: 4.5 to 1: 6.
- a slight excess of alcohol is therefore preferred, which is either removed together with the methanol or ethanol in the course of the distillative separation or is separated off in a separate distillation step.
- straight and / or branched-chain, saturated and / or unsaturated, aliphatic alcohols having 3 to 32 carbon atoms can be used for the transesterification according to the invention.
- propanol, butanol, fatty alcohols having 6 to 32 carbon atoms and mixtures of these compounds are to be mentioned here.
- Guerbet alcohols with 6 to 20 carbon atoms, such as 2-methylpentanol, 2-ethylhexanol, 2-hexyldecanol, 2-0ctyldecanol, 2-Hexyldodecanol and / or 2-octyldodecanol, preferably used.
- aromatic alcohols such as benzyl alcohol, cinnamon alcohol, phenol, dihydroxy- or trihydroxy-benzene derivatives, and cycloaliphatic alcohols having 3 to 20 carbon atoms, such as cyclopropanol, cyclobutanol or cyclodecanol, can also be used according to the invention for the transesterification.
- the double-layer hydroxide compounds of the general formula I are used in an amount of 1 to 20% by weight, preferably 5 to 15% by weight, based on the respective amount of tetramethoxy or tetraethoxysilane.
- smaller amounts of double-layer hydroxide compounds can also be added, although longer reaction times must be expected.
- the double-layer hydroxide compounds can be used several times for further transesterification even without special work-up.
- the present invention furthermore relates to tetraalkoxysilanes of the general formula Si (0R) 4, in which R represents the rest of Guerbet alcohols having 12 to 38 C atoms, preferably R each represents the same radical of a Guerbet alcohol.
- Suitable examples of Guerbet alcohols are 2-butyloctanol, 2-hexyldecanol, 2-nonyltridecanol, 2-0ctyldodecanol and n-dodecylhexadecanol.
- Technical Guerbet alcohols are preferred, the technical Guerbet alcohols due to it Manufacturing process can contain up to 20 wt .-% tri- and tetramer Guerbet alcohols.
- tetraalkoxysilanes according to the invention can either be prepared by the process according to the invention or by one of the processes known from the prior art.
- the decisive factor here is whether particularly light-colored tetraalkoxy lanes are desired for the application or not. If the color is not important, the preparation is carried out by the processes known from the prior art, preferably by transesterification of tetramethoxy or tetraethoxysilane in the presence of bases, preferably sodium methoxide, as a catalyst, for example in accordance with the American patents US Pat. No. 2,643,263 or 26 73870.
- tetramethoxy or tetraethoxysilane to be used and the respective Guerbet alcohols correspond to the details of the process according to the invention.
- the tetraalkoxysilanes are expediently the
- Guerbet alcohols with 12 to 38 carbon atoms are then neutralized in a conventional manner, for example with an acid such as the dilute phosphoric acid.
- the resulting sodium phosphate is then separated off via the aqueous phase. If light-colored tetraalkoxysilanes according to the invention of Guerbet alcohols are desired, they must be prepared by the process according to the invention.
- the invention furthermore relates to the use of the light-colored tetraalkoxysilanes prepared by the process according to the invention as cosmetic ingredients, cooling lubricants, hydraulic fluids, heat transfer fluids or defoamers.
- reaction mixture was then heated to 80-90 ° C. in the course of 15-20 minutes and, after the reaction had started, the methanol formed as the reaction temperature rose (heating rate approx. 0.5 ° C. per minute, up to 200 ° C. ) separated by distillation. At a degree of transesterification of approximately 85 to 95% (determined by indirectly determining the amount of methanol), the reaction was stopped. After cooling, the crude product was mixed with water in a volume ratio of 1: 1 and dilute phosphoric acid was added until neutralization. The organic phase was separated off and then fractionally distilled (bp at 1 torr: 194 ° C., tetra-2-ethylhexylsilane).
- reaction mixture was then heated to 90-100 ° C. in the course of 15-20 minutes and, after the reaction had started, the resulting ethanol or methanol at an increasing reaction temperature (heating rate approx. 0.5 ° C. per minute, up to 200 ° C) separatively separated.
- heating rate approx. 0.5 ° C. per minute, up to 200 ° C
- the reaction was stopped, after cooling the crude product was mixed with 1: 1 by volume with H2O and dilute phosphoric acid was added until neutralization.
- the organic phase was separated and fractionally distilled.
- Table 3 Reaction of tetraethoxysilane with 2-ethylhexanol
- Example 2 Analogously to Example 1, 114 g (0.75 mol) of tetramethoxysilane were reacted with 1399 g (3.4 mol) of 2-0ctyldodecanol in the presence of 11.4 g of a hydrophobicized hydrotalcite (1 kg lauric acid to 2 kg hydrotalcite). After the hydrotalcite had been separated off, the excess 2-0ctyldodecanol was distilled off in vacuo. A colorless tetraalkoxysilane was obtained.
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Abstract
L'invention concerne des silanes tétraalcoxyliques d'alcools de Guerbet, un procédé de production de silanes tétraalcoxyliques de couleur claire répondant à la formule générale Si(OR)4 par transestérification de silane tétraméthoxylique ou tétraéthoxylique avec un alcool en présence de quantités catalytiques d'au moins un composé hydroxyde à couche double répondant à la formule générale (I), alors que le méthanol ou l'éthanol sont éliminés en continu, ainsi que l'utilisation des silanes tétraalcoxyliques de couleur claire comme ingrédients de produits cosmétiques, comme réfrigérants lubrifiants, comme fluides hydrauliques, comme fluides caloporteurs ou comme agents antimousse.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE4040679A DE4040679A1 (de) | 1990-12-19 | 1990-12-19 | Verfahren zur herstellung von hellfarbigen tetraalkoxysilanen und deren verwendung |
DEP4040679.2 | 1990-12-19 |
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WO1992011266A1 true WO1992011266A1 (fr) | 1992-07-09 |
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PCT/EP1991/002426 WO1992011266A1 (fr) | 1990-12-19 | 1991-12-17 | Silanes tetraalcoxiliques, leur procede de production et leur utilisation |
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DE (1) | DE4040679A1 (fr) |
WO (1) | WO1992011266A1 (fr) |
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US8591605B2 (en) | 2007-07-26 | 2013-11-26 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno | Methods, systems, and apparatus for obtaining biofuel from coffee and fuels produced therefrom |
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DE19629760A1 (de) * | 1996-07-23 | 1998-01-29 | Wacker Chemie Gmbh | Verfahren zur Herstellung von Alkoxysilanen |
KR100574249B1 (ko) * | 2004-08-26 | 2006-04-26 | 주식회사 두본 | 인(p)이 염착된 하이드로탈사이트의 제조방법 |
US8481776B2 (en) | 2008-03-14 | 2013-07-09 | Kao Corporation | Functional substance-releasing agent |
Citations (1)
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DD251353A1 (de) * | 1986-07-23 | 1987-11-11 | Akad Wissenschaften Ddr | Verfahren zur umesterung von kieselsaeureestern |
-
1990
- 1990-12-19 DE DE4040679A patent/DE4040679A1/de not_active Withdrawn
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- 1991-12-17 WO PCT/EP1991/002426 patent/WO1992011266A1/fr active Application Filing
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DD251353A1 (de) * | 1986-07-23 | 1987-11-11 | Akad Wissenschaften Ddr | Verfahren zur umesterung von kieselsaeureestern |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, (Online STN), American Chemical Society 1992, Accession-No. CA104(2):7778j; & SU,A,1 155 602. * |
CHEMICAL ABSTRACTS, (Online STN), American Chemical Society 1992, Accession-No. CA113(19):171486u; & JP,A,02 160 792. * |
Cited By (1)
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US8591605B2 (en) | 2007-07-26 | 2013-11-26 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno | Methods, systems, and apparatus for obtaining biofuel from coffee and fuels produced therefrom |
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