DE10223073C1 - Organosilicon compounds with one or two long-chain alkoxy groups attached to silicon, used as coupling agents for fillers in rubber mixtures, e.g. for tires or tubing are new - Google Patents
Organosilicon compounds with one or two long-chain alkoxy groups attached to silicon, used as coupling agents for fillers in rubber mixtures, e.g. for tires or tubing are newInfo
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- DE10223073C1 DE10223073C1 DE10223073A DE10223073A DE10223073C1 DE 10223073 C1 DE10223073 C1 DE 10223073C1 DE 10223073 A DE10223073 A DE 10223073A DE 10223073 A DE10223073 A DE 10223073A DE 10223073 C1 DE10223073 C1 DE 10223073C1
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- 239000000203 mixture Substances 0.000 title claims abstract description 10
- 150000003961 organosilicon compounds Chemical class 0.000 title claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 title abstract description 4
- 239000010703 silicon Substances 0.000 title abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 title abstract 2
- 239000000945 filler Substances 0.000 title abstract 2
- 239000007822 coupling agent Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 229920000570 polyether Polymers 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 150000004756 silanes Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 3
- 238000003379 elimination reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000005011 alkyl ether group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 150000002602 lanthanoids Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 125000005369 trialkoxysilyl group Chemical group 0.000 abstract 2
- 150000005215 alkyl ethers Chemical class 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- -1 chloro, amino- Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000001408 amides Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 150000003949 imides Chemical class 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 150000007944 thiolates Chemical class 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 101100243399 Caenorhabditis elegans pept-2 gene Proteins 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000013028 medium composition Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 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
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000011022 operating instruction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910000057 polysulfane Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009419 refurbishment Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium 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
- C07F7/08—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Organosiliciumverbindungen.The invention relates to a method for manufacturing of organosilicon compounds.
Aus Appl. Organomet. Chem. (2001), 15(8), 649-657 ist die Umesterung von organofunktionellen Silanen mit sterisch gehinderten Alkoholen (2-Methoxyethanol; i- Propanol) bekannt. Die mit Titanaten beziehungsweise Sn(OR)2 katalysierten Reaktionen an Chloro, Amino-, Methacrylato- und Isocyanato- substituierten Methoxysilanen verlaufen nicht quantitativ und ergeben breite Gemische an unterschiedlich substituierten Alkoxysilanen.From appl. Organomet. Chem. (2001), 15 (8), 649-657 the transesterification of organofunctional silanes with sterically hindered alcohols (2-methoxyethanol; i-propanol) is known. The reactions on chloro, amino-, methacrylato- and isocyanato-substituted methoxysilanes catalyzed with titanates or Sn (OR) 2 do not proceed quantitatively and result in broad mixtures of differently substituted alkoxysilanes.
Aus Chem. Mater., 1998, 10, 1604-1612 ist eine vergleichende Untersuchung von metallhaltigen Lewissäuren (Ti(OiPr)4, OV(OiPr)3) mit Bröndstedt-Säuren (Trifluormethansulfonsäure) als Katalysatoren für Umesterungen an Alkoxysilanen bekannt. Dabei wird festgestellt, daß die metallhaltigen Katalysatoren erheblich schlechter als die verwendete Bröndtstedt- Säure für Umesterungen an Alkoxysilanen geeignet sind.From Chem. Mater., 1998, 10, 1604-1612 is a comparative investigation of metal-containing Lewis acids (Ti (O i Pr) 4 , OV (O i Pr) 3 ) with Bröndstedt acids (trifluoromethanesulfonic acid) as catalysts for transesterification on alkoxysilanes known. It is found that the metal-containing catalysts are considerably less suitable than transesterification on alkoxysilanes than the Bröndtstedt acid used.
Ferner ist aus US 4,500,725 die Umesterung von organisch modifizierten Alkoxysilanen mit Doppelbindungen enthaltenen Alkoholen bekannt. Der Substituentenaustausch erfolgt in 12 h bei 150-200°C unter Schutzgas. Es entsteht ein Gemisch an substituierten Alkylalkoxysilanen.From US 4,500,725 the transesterification of organically modified alkoxysilanes with Alcohols containing double bonds are known. The Substitution exchange takes place in 12 h at 150-200 ° C under protective gas. A mixture is formed substituted alkylalkoxysilanes.
Aus DE 101 37 809.2 ist ein Verfahren zur Herstellung von
Organosiliciumverbindungen der allgemeinen Formel
DE 101 37 809.2 describes a process for the preparation of organosilicon compounds of the general formula
wobei man Silane der allgemeinen Formel III
wherein silanes of the general formula III
mit Alkoholen der allgemeinen Formel R'-OH, unter Abspaltung von R-OH, umsetzt und R-OH durch Destillation kontinuierlich vom Reaktionsgemisch abtrennt.with alcohols of the general formula R'-OH, under Elimination of R-OH, implemented and R-OH by Distillation continuously from the reaction mixture separates.
Die bekannten Verfahren haben die Nachteile, daß die Reaktionen zu langsam, nicht energieeffizient (hohe Temperaturen), mit einem erhöhten Handhabungsaufwand behaftet und die Umsätze gering sind.The known methods have the disadvantages that the Reactions too slow, not energy efficient (high Temperatures), with an increased handling effort afflicted and sales are low.
Aufgabe der Erfindung ist es, ein Verfahren zur Verfügung zu stellen, mit dessen Hilfe man eine schnelle und energieeffiziente Reaktion bei hohem Umsatz und geringem Handhabungsaufwand erzielt.The object of the invention is to provide a method for To provide, with the help of which one fast and energy-efficient response at high Sales and low handling effort achieved.
Gegenstand der Erfindung ist ein Verfahren zur
Herstellung von Organosiliciumverbindungen der
allgemeinen Formel I und/oder II
The invention relates to a process for the preparation of organosilicon compounds of the general formula I and / or II
wobei R eine Methyl- oder Ethyl-Gruppe ist,
R' gleich oder verschieden und eine C9-C30 verzweigte
oder unverzweigte einbindige Alkyl- oder Alkenyl-
Gruppe, Arylgruppe, Aralkylgruppe, verzweigte oder
unverzweigte C2-C30 Alkylethergruppe, verzweigte oder
unverzweigte C2-C30 Alkylpolyethergruppe oder R'''3Si,
mit R''' gleich C1-C30 verzweigte oder unverzweigte
Alkyl- oder Alkenyl-Gruppe, Aralkylgruppe oder
Arylgruppe, ist,
R'' eine verzweigte oder unverzweigte, gesättigte oder
ungesättigte, aliphatische, aromatische oder gemischt
aliphatische/aromatische zweibindige C1-C30
Kohlenwasserstoffgruppe ist,
X ist NH(3-n) mit n = 1, 2, 3 und m = 1, O (C=O)-R''' mit n = 1
und m = 1, SH mit n = 1 und m = 1, S mit n = 2 und m = 1-10 und
Gemische davon, S(C=O)-R''' mit n = 1 und m = 1 oder H mit
n = 1 und m = 1,
indem man Silane der allgemeinen Formel III
where R is a methyl or ethyl group,
R 'the same or different and a C 9 -C 30 branched or unbranched monovalent alkyl or alkenyl group, aryl group, aralkyl group, branched or unbranched C 2 -C 30 alkyl ether group, branched or unbranched C 2 -C 30 alkyl polyether group or R''' 3 Si, with R''' being C 1 -C 30 branched or unbranched alkyl or alkenyl group, aralkyl group or aryl group,
R "is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C 1 -C 30 hydrocarbon group,
X is NH (3-n) with n = 1, 2, 3 and m = 1, O (C = O) -R '''with n = 1 and m = 1, SH with n = 1 and m = 1 , S with n = 2 and m = 1-10 and mixtures thereof, S (C = O) -R '''with n = 1 and m = 1 or H with n = 1 and m = 1,
by using silanes of the general formula III
in der R, R'', X, m und n die oben angegebene Bedeutung aufweisen, mit Alkoholen der allgemeinen Formel R'-OH, in der R' die oben angegebene Bedeutung aufweist, unter Abspaltung von R-OH, umsetzt und R-OH durch Destillation kontinuierlich vom Reaktionsgemisch abtrennt, welches dadurch gekennzeichnet ist, daß man Metallverbindungen als Katalysator einsetzt. in the R, R '', X, m and n the meaning given above have, with alcohols of the general formula R'-OH, in which R 'has the meaning given above, under Elimination of R-OH, implemented and R-OH by Distillation continuously from the reaction mixture separates, which is characterized in that one Metal compounds used as a catalyst.
R'' kann CH2, CH2CH2, CH2CH2CH2, CH2CH2CH2CH2, CH(CH3),
CH2CH(CH3), C(CH3)2, CH(C2H5), CH2CH2CH(CH3), CH2CH(CH3)CH2
oder
R '' can be CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH (CH 3 ), CH 2 CH (CH 3 ), C (CH 3 ) 2 , CH (C 2 H 5 ), CH 2 CH 2 CH (CH 3 ), CH 2 CH (CH 3 ) CH 2 or
bedeuten.mean.
Bei dem erfindungsgemäßen Verfahren kann ein Gemisch entstehen, bei dem keine, eine, zwei oder drei der RO- Gruppen durch R'O-Gruppen ersetzt sind. Das Verhältnis der RO- zu R'O-Gruppen kann durch das molare Verhältnis des Silans der allgemeinen Formel III zu dem Alkohol der allgemeinen Formel R'-OH bestimmt werden.In the method according to the invention, a mixture arise in which none, one, two or three of the RO Groups are replaced by R'O groups. The relationship the RO to R'O groups can by the molar ratio of the silane of the general formula III to the alcohol of the general formula R'-OH can be determined.
Beispielsweise kann bei n = 1 durch Umsetzung von zwei Moläquivalenten des Alkohols der allgemeinen Formel R'- OH mit einem Moläquivalent des Silans der allgemeinen Formel III, eine Organosiliciumverbindung mit einer mittleren Zusammensetzung gemäß der Formel I hergestellt werden. Beispielsweise kann bei n = 2 durch Umsetzung von vier Moläquivalenten des Alkohols der allgemeinen Formel R'-OH mit einem Moläquivalent des Silans der allgemeinen Formel III, eine Organosiliciumverbindung mit einer mittleren Zusammensetzung gemäß der Formel I hergestellt werden.For example, at n = 1 by implementing two Molar equivalents of alcohol of the general formula R'- OH with a molar equivalent of the silane of the general Formula III, an organosilicon compound with a medium composition according to formula I. getting produced. For example, with n = 2 Implementation of four molar equivalents of the alcohol general formula R'-OH with one molar equivalent of Silanes of the general formula III, a Organosilicon compound with a medium Composition according to formula I can be prepared.
Das Gemisch kann als solches, aufgetrennt in einzelne Verbindungen oder isolierte Fraktionen verwendet werden.The mixture as such can be separated into individual ones Compounds or isolated fractions used become.
Für R' = R'''3Si kann das Silan der allgemeinen Formel III mit R'''3Si-OH oder mit R'''3Si-O-SiR'''3 umgesetzt werden. Die Verbindung R'''3Si-O-SiR'''3 kann zu R'''3Si-OH hydrolisieren und mit dem Silan der allgemeinen Formel III reagieren.For R '= R''' 3 Si, the silane of the general formula III can be reacted with R ''' 3 Si-OH or with R''' 3 Si-O-SiR ''' 3 . The compound R ''' 3 Si-O-SiR''' 3 can hydrolyze to R ''' 3 Si-OH and react with the silane of the general formula III.
Metallverbindungen können auch Übergangsmetallverbindungen sein.Metal connections can too Transition metal compounds.
Als Metallverbindungen für die Katalysatoren können Metallchloride, Metalloxide, Metalloxychloride, Metallalkoholate, Metalloxyalkoholate, Metallamide, Metallimide oder Übergangsmetallverbindungen mit multiplen gebundenen Liganden eingesetzt werden.Can be used as metal compounds for the catalysts Metal chlorides, metal oxides, metal oxychlorides, Metal alcoholates, metal oxy alcoholates, metal amides, Metal imides or transition metal compounds with multiple bound ligands can be used.
Beispielsweise können als Metallverbindungen eingesetzt
werden:
Halogenide, Amide oder Alkoholate der 3. Hauptgruppe
(M3+ = B, Al, Ga, In, Tl: M3+(OMe)3, M3+(OEt)3, M3+(OC3H7)3,
M3+(OC4H9)3),
Halogenide, Oxide, Imide, Alkoholate, Amide, Thiolate
und Kombinationen der genannten Substituentenklassen
mit multiple gebundenen Liganden an Verbindungen der
Lanthaniden-Gruppe (Seltenen Erden, Ordnungszahl 58 bis
71 im Periodensystem der Elemente),
Halogenide, Oxide, Imide, Alkoholate, Amide, Thiolate
und Kombinationen der genannten Substituentenklassen
mit multiple gebundenen Liganden an Verbindungen der 3.
Nebengruppe (M3+ = Sc, Y, La: M3+(OMe)3, M3+(OEt)3,
M3+(CO3H7)3, M3+(OC4H9)3, cpM3+(Cl)2, cp cpM3+(OMe)2,
cpM3+(OEt)2, cpM3+(NMe2)2 mit cp = Cyclopentadienyl),
Halogenide, Amide, Thiolate oder Alkoholate der 4.
Hauptgruppe (M4+ = Si, Ge, Sn, Pb: M4+(OMe)4, M4+(OEt)4,
M4+(OC3H7)4, M4+(OC4H9)4; M2+ = Sn, Pb: M2+(OMe)2, M2+(OEt)2,
M2+(OC3H7)2, M2+(OC4H9)2, Zinndilaurat, Zinndiacetat,
Sn(OBu)2),
Halogenide, Oxide, Imide, Alkoholate, Amide, Thiolate
und Kombinationen der genannten Substituentenklassen
mit multiple gebundenen Liganden an Verbindungen der 4.
Nebengruppe (M4+ = Ti, Zr, Hf: M4+(F)4, M4+(Cl)4, M4+(Br)4,
M4+(I)4; M4+(OMe)4, M4+(OEt)4, M4+(OC3H7)4, M4+(OC4H9)4,
cp2Ti(Cl)2, cp2Zr(Cl)2, cp2Hf(Cl)3, cp2Ti(OMe)2,
cp2Zr(OMe)2, cp2Hf(OMe)2, cpTi(Cl)3, cpZr(Cl)3, cpHf(Cl)3,
cpTi(OMe)3, cpZr(OMe)3, cpHf(OMe)3, M4+(NMe2)4, M4+(NET2)4,
M4+(NHC4H9)4),
Halogenide, Oxide, Imide, Alkoholate, Amide, Thiolate
und Kombinationen der genannten Substituentenklassen
mit multiple gebundenen Liganden an Verbindungen der 5.
Nebengruppe (M5+, M4+ oder M3+ = V, Nb, Ta: M5+(OMe)5,
M5+(OEt)5, M5+(OC3H7)5, M5+(OC4H9)5, M3+O(OMe)3, M3+O(OEt)3,
M3+O(OC3H7)3, M3+O(OC4H9)3, cpV(OMe)4, cPNb(OMe)3,
cpTa(OMe)3; cpV(OMe)2, cpNb(OMe)3, cpTa(OMe)3,
Halogenide, Oxide, Imide, Alkoholate, Amide, Thiolate
und Kombinationen der genannten Substituentenklassen
mit multiple gebundenen Liganden an Verbindungen der 6.
Nebengruppe (M6+, M5+ oder M4+ = Cr, Mo, W: M6+(OMe) 6,
M6+(OEt)6, M6+(OC3H7)6, M6+(OC4H9)6, M6+O(OMe)4, M6+O(OEt)4,
M6+O(OC3H7)4, M6+O(O4H9)4, M6+O2(OMe)2, M5+O2(OEt)2,
M6+O2(OC3H7)2, M6+O2(OC4H9)2, M6+O2(OSiMe3)2) oder
Halogenide, Oxide, Imide, Alkoholate, Amide, Thiolate
und Kombinationen der genannten Substituentenklassen
mit multiple gebundenen Liganden an Verbindungen der 7.
Nebengruppe (M7+, M6+, M5+ oder M4+ = Mn, Re: M7+O(OMe)5,
M7+O(OEt)5,) M7+O(OC3H7)5, M7+O(OC4H9)5, M7+O2(OMe)3,
M7+O2(OEt)3, M7+O2(OC3H7)3, M7+O2(OC4H9)3, M7+O2(OSiMe3)3,
M7+O3(OSiMe3), M7+O3(CH3)).For example, the following can be used as metal compounds:
Halides, amides or alcoholates of the 3rd main group (M 3+ = B, Al, Ga, In, Tl: M 3+ (OMe) 3 , M 3+ (OEt) 3 , M 3+ (OC 3 H 7 ) 3 , M 3+ (OC 4 H 9 ) 3 ),
Halides, oxides, imides, alcoholates, amides, thiolates and combinations of the substituent classes mentioned with multiple bound ligands on compounds of the lanthanide group (rare earths, atomic number 58 to 71 in the periodic table of the elements),
Halides, oxides, imides, alcoholates, amides, thiolates and combinations of the substituent classes mentioned with multiple bound ligands on compounds of sub-group 3 (M 3+ = Sc, Y, La: M 3+ (OMe) 3 , M 3+ (OEt ) 3 , M 3+ (CO 3 H 7 ) 3 , M 3+ (OC 4 H 9 ) 3 , cpM 3+ (Cl) 2 , cp cpM 3+ (OMe) 2 , cpM 3+ (OEt) 2 , cpM 3+ (NMe 2 ) 2 with cp = cyclopentadienyl), halides, amides, thiolates or alcoholates of the 4th main group (M 4+ = Si, Ge, Sn, Pb: M 4+ (OMe) 4 , M 4+ ( OEt) 4 , M 4+ (OC 3 H 7 ) 4 , M 4+ (OC 4 H 9 ) 4 ; M 2+ = Sn, Pb: M 2+ (OMe) 2 , M 2+ (OEt) 2 , M 2+ (OC 3 H 7 ) 2 , M 2+ (OC 4 H 9 ) 2 , tin dilaurate, tin diacetate, Sn (OBu) 2 ),
Halides, oxides, imides, alcoholates, amides, thiolates and combinations of the substituent classes mentioned with multiple bound ligands on compounds of subgroup 4 (M 4+ = Ti, Zr, Hf: M 4+ (F) 4 , M 4+ (Cl ) 4 , M 4+ (Br) 4 , M 4+ (I) 4 ; M 4+ (OMe) 4 , M 4+ (OEt) 4 , M 4+ (OC 3 H 7 ) 4 , M 4+ ( OC 4 H 9 ) 4 , cp 2 Ti (Cl) 2 , cp 2 Zr (Cl) 2 , cp 2 Hf (Cl) 3 , cp 2 Ti (OMe) 2 , cp 2 Zr (OMe) 2 , cp 2 Hf (OMe) 2 , cpTi (Cl) 3 , cpZr (Cl) 3 , cpHf (Cl) 3 , cpTi (OMe) 3 , cpZr (OMe) 3 , cpHf (OMe) 3 , M 4+ (NMe 2 ) 4 , M 4+ (NET 2 ) 4 , M 4+ (NHC 4 H 9 ) 4 ),
Halides, oxides, imides, alcoholates, amides, thiolates and combinations of the substituent classes mentioned with multiple bound ligands on compounds of subgroup 5 (M 5+ , M 4+ or M 3+ = V, Nb, Ta: M 5+ (OMe ) 5 , M 5+ (OEt) 5 , M 5+ (OC 3 H 7 ) 5 , M 5+ (OC 4 H 9 ) 5 , M 3+ O (OMe) 3 , M 3+ O (OEt) 3 , M 3+ O (OC 3 H 7 ) 3 , M 3+ O (OC 4 H 9 ) 3 , cpV (OMe) 4 , cPNb (OMe) 3 , cpTa (OMe) 3 ; cpV (OMe) 2 , cpNb (OMe) 3 , cpTa (OMe) 3 ,
Halides, oxides, imides, alcoholates, amides, thiolates and combinations of the substituent classes mentioned with multiple bound ligands on compounds of subgroup 6 (M 6+ , M 5+ or M 4+ = Cr, Mo, W: M 6+ (OMe ) 6, M 6+ (OEt) 6 , M 6+ (OC 3 H 7 ) 6 , M 6+ (OC 4 H 9 ) 6 , M 6+ O (OMe) 4 , M 6+ O (OEt) 4 , M 6+ O (OC 3 H 7 ) 4 , M 6+ O (O 4 H 9 ) 4 , M 6+ O 2 (OMe) 2 , M 5+ O 2 (OEt) 2, M 6+ O 2 (OC 3 H 7 ) 2 , M 6+ O 2 (OC 4 H 9 ) 2 , M 6+ O 2 (OSiMe 3 ) 2 ) or
Halides, oxides, imides, alcoholates, amides, thiolates and combinations of the substituent classes mentioned with multiple bound ligands on compounds of sub-group 7 (M 7+ , M 6+ , M 5+ or M 4+ = Mn, Re: M 7+ O (OMe) 5 , M 7+ O (OEt) 5 ,) M 7+ O (OC 3 H 7 ) 5 , M 7+ O (OC 4 H 9 ) 5 , M 7+ O 2 (OMe) 3 , M 7+ O 2 (OEt) 3 , M 7+ O 2 (OC 3 H 7 ) 3 , M 7+ O 2 (OC 4 H 9 ) 3 , M 7+ O 2 (OSiMe 3 ) 3 , M 7+ O 3 (OSiMe 3 ), M 7+ O 3 (CH 3 )).
Die Metallverbindungen können eine freie Koordinationsstelle am Metall besitzen.The metal compounds can be a free one Have a coordination point on the metal.
Als Katalysatoren können auch Metallverbindungen eingesetzt werden, die durch Wasserzugabe zu hydrolisierbaren Metallverbindungen gebildet werden.Metal compounds can also be used as catalysts be used by adding water hydrolyzable metal compounds are formed.
In einer besonderen Ausführungsform kann man Titanate, wie beispielsweise Tetra-n-butyl-orthotitanat oder Tetra-iso-propyl-orthotitanat, als Katalysatoren einsetzen.In a special embodiment, titanates, such as tetra-n-butyl orthotitanate or Tetra-iso-propyl-orthotitanate, as catalysts deploy.
Die Metallverbindungen können wasserfrei sein.The metal compounds can be anhydrous.
Die Reaktion kann man bei Temperaturen zwischen 20 und 200°C, vorzugsweise zwischen 50 und 150°C, besonders bevorzugt zwischen 70 und 120°C, durchführen. Zur Vermeidung von Kondensationsreaktionen kann es vorteilhaft sein, die Reaktion in einer wasserfreien Umgebung, idealerweise in einer Inertgasatmosphäre, durchzuführen.The reaction can be carried out at temperatures between 20 and 200 ° C, preferably between 50 and 150 ° C, particularly preferably between 70 and 120 ° C. to It can avoid condensation reactions be advantageous to the reaction in an anhydrous Environment, ideally in an inert gas atmosphere, perform.
Die Reaktion kann man bei Normaldruck oder reduziertem Druck durchführen. Die Reaktion kann man kontinuierlich oder diskontinuierlich durchführen.The reaction can be carried out at normal pressure or reduced Carry out printing. The reaction can be done continuously or perform discontinuously.
Das erfindungsgemäße Verfahren hat den Vorteil, daß der Umsatz der Umesterung, bei vergleichbaren Katalysatorkonzentrationen, bei niedrigeren Temperaturen verbessert ist und durch die Katalysatoren kein zusätzliches Wasser eingebracht werden. Durch den insgesamt geringeren Wassereintrag in die Reaktionsmischung und die geringere Reaktionstemperatur entstehen weniger oligomere Silanverbindungen. Zudem ist die Reaktionsführung vereinfacht, da nur eine Reaktionsapparatur, im Gegensatz zu zwei Reaktionsapparaturen, wie in DE 101 37 809.2, benötigt wird. Es entsteht zudem das reine Produkt in einem Schritt, ohne daß weitere Aufarbeitungs- oder Reinigungsschritte notwendig sind.The inventive method has the advantage that the Transesterification sales, at comparable Catalyst concentrations, at lower Temperatures are improved and by the catalysts no additional water can be introduced. By the overall lower water input into the Reaction mixture and the lower reaction temperature fewer oligomeric silane compounds are formed. moreover the reaction is simplified because only one Reaction apparatus, in contrast to two Reaction apparatus, as in DE 101 37 809.2, is required becomes. The pure product is also created in one Step without further refurbishment or Cleaning steps are necessary.
Am Rotationsverdampfer werden im 1-Liter-Kolben ein Gemisch bestehend aus 150 g Si 69 (Verbindung III mit R = -CH2CH3, R2 = -CH2CH2CH2-, X = S, n = 2, m = 1 bis 10 und einem mittlerem m von 3,8), und eine vierfach molare Menge an Tetradecanol mit den angegebenen Katalysatormengen bei den angegebenen Temperaturen erhitzt und entstehendes Ethanol im Vakuum bei 40 mbar innerhalb von 120 min abdestilliert (Tabelle 1). Man erhält nach Abkühlen eine gelbe bis gelb-orange, höherviskose Flüssigkeit der Formel I mit R = -CH2CH3, R2 = -CH2CH2CH2-, X = S mit n = 2 und m = 1 bis 10. A mixture consisting of 150 g Si 69 (compound III with R = -CH 2 CH 3 , R 2 = -CH 2 CH 2 CH 2 -, X = S, n = 2, m = 1 to 10 and an average m of 3.8), and a four-fold molar amount of tetradecanol is heated with the stated amounts of catalyst at the stated temperatures and ethanol is distilled off in vacuo at 40 mbar within 120 min (Table 1). After cooling, a yellow to yellow-orange, highly viscous liquid of the formula I with R = -CH 2 CH 3 , R 2 = -CH 2 CH 2 CH 2 -, X = S with n = 2 and m = 1 to 10 is obtained ,
Si 69 ist Bis-(3-triethoxysilylpropyl)polysulfan mit einer mittleren Sulfankettenlänge von 3,8 der Firma Degussa AG.Si 69 is bis (3-triethoxysilylpropyl) polysulfane with an average sulfane chain length of 3.8 from the company Degussa AG.
Ti(OC2H5)4, Ti(OC3H7)4 und Ti(OC4H9)4 werden von der Firma Aldrich hergestellt. P-Toluolsulfonsäure und p- Toluolsulfonsäure-Natriumsalz werden von der Firma Merck-Schuchardt hergestellt.Ti (OC 2 H 5 ) 4 , Ti (OC 3 H 7 ) 4 and Ti (OC 4 H 9 ) 4 are manufactured by Aldrich. P-toluenesulfonic acid and p-toluenesulfonic acid sodium salt are manufactured by Merck-Schuchardt.
In einem 500 ml 3-Halskolben wird ein Gemisch bestehend aus 100 g Si 69 (Verbindung II mit R = -CH2CH3, R2 = -CH2CH2CH2-, X = S, n = 2, m = 1 bis 10 und einem mittlerem m von 3,8), und eine vierfach molare Menge des entsprechenden Alkohols mit den angegebenen Katalysatormengen bei 130°C erhitzt und entstehendes Ethanol innerhalb von 120 min abdestilliert (Tabelle 2). Man erhält nach Abkühlen eine gelbe bis gelb- orange, höherviskose Flüssigkeit der Formel I mit R = -CH2CH3, R2 = -CH2CH2CH2-, X = S mit n = 2 und m = 1 bis 10).In a 500 ml 3-neck flask, a mixture consisting of 100 g Si 69 (compound II with R = -CH 2 CH 3 , R 2 = -CH 2 CH 2 CH 2 -, X = S, n = 2, m = 1 to 10 and an average m of 3.8), and a four-fold molar amount of the corresponding alcohol with the stated amounts of catalyst is heated at 130 ° C. and the ethanol formed is distilled off within 120 min (Table 2). After cooling, a yellow to yellow-orange, highly viscous liquid of the formula I with R = -CH 2 CH 3 , R 2 = -CH 2 CH 2 CH 2 -, X = S with n = 2 and m = 1 to 10 is obtained ).
Die entsprechenden NMR-analytischen Ergebnisse sind in den Tabellen 1 und 2 aufgeführt.The corresponding NMR analytical results are in Tables 1 and 2 listed.
Die Ergebnisse der kernresonanzspektroskopischen Untersuchungen werden an einem DRX 500 NMR-Gerät der Firma Bruker gemäß den dem Fachmann bekannten Regeln und Bedienvorschriften erhalten. Die verwendeten Messfrequenzen sind 99,35 MHz für 29Si-Kerne und 500 MHz für 1H-Kerne.The results of the nuclear magnetic resonance spectroscopic investigations are obtained on a DRX 500 NMR device from Bruker in accordance with the rules and operating instructions known to the person skilled in the art. The measurement frequencies used are 99.35 MHz for 29 Si cores and 500 MHz for 1 H cores.
Als Referenz dient jeweils Tetramethylsilan (TMS).Tetramethylsilane (TMS) is used as a reference.
Der Umsatz wird als der Quotient aus dem 1H-NMR Integral (Si-O-CxHy) dividiert durch die Summe aus dem 1H-NMR Integral (Si-O-Et) und 1H-NMR Integral (Si-O- CxHy) × 0,66 definiert. Der Umsatz wird in % von 1 angegeben. 100% Umsatz bedeuten, daß 4 von 6 Äquivalenten EtO ausgetauscht sind und 2 Äquivalente EtO am Silizium verbleiben.The conversion is expressed as the quotient of the 1 H-NMR integral (Si-OC x H y ) divided by the sum of the 1 H-NMR integral (Si-O-Et) and 1 H-NMR integral (Si-O- C x H y ) × 0.66. The turnover is given in% of 1. 100% conversion means that 4 out of 6 equivalents of EtO have been exchanged and 2 equivalents of EtO remain on the silicon.
Die Menge an Oligomeren wird bestimmt mittels 29Si-NMR durch Vergleich der Integrale der Si(OEt)3 und der Si(OEt)2 -O-Si(OEt)2 Signale.The amount of oligomers is determined by means of 29 Si NMR by comparing the integrals of the Si (OEt) 3 and the Si (OEt) 2 -O-Si (OEt) 2 signals.
Der Umsatz der Umesterung des erfindungsgemäßen Verfahrens ist bei niedrigeren Temperaturen höher als bei dem aus DE 101 37 809.2 bekannten Verfahren, bei vergleichbarer oder sogar geringerer molarer Katalysatorkonzentration. Zusätzlich ist die Menge an gebildeten Oligomeren geringer. Wird als wasserfreies Äquivalent für p-Toluolsulfonsäuremonohydrat das p- Toluolsulfonsäure-Natriumsalz verwendet, ist auch bei hohen Katalysatormengen ein schlechterer Umsatz als bei der Verwendung von Titanalkoholaten festzustellen (Tabelle 2). Sales of the transesterification of the invention Process is higher than at lower temperatures in the method known from DE 101 37 809.2, comparable or even lower molar Catalyst concentration. In addition, the amount of formed oligomers lower. Is considered anhydrous Equivalent to p-toluenesulfonic acid monohydrate the p- Toluene sulfonic acid sodium salt is also used high amounts of catalyst a worse sales than at the use of titanium alcoholates (Table 2).
Claims (3)
wobei R eine Methyl- oder Ethyl-Gruppe ist,
R' gleich oder verschieden und eine C9-C30 verzweigte oder unverzweigte einbindige Alkyl- oder Alkenyl- Gruppe, Arylgruppe, Aralkylgruppe, verzweigte oder unverzweigte C2-C30 Alkylethergruppe, verzweigte oder unverzweigte C2-C30 Alkylpolyethergruppe oder R'''3Si, mit R''' gleich C1-C30 verzweigte oder unverzweigte Alkyl- oder Alkenyl-Gruppe, Aralkylgruppe oder Arylgruppe, ist,
R'' eine verzweigte oder unverzweigte, gesättigte oder ungesättigte, aliphatische, aromatische oder gemischt aliphatische/aromatische zweibindige C1-C30 Kohlenwasserstoffgruppe ist,
X ist NH(3-n) mit n = 1, 2, 3 und m = 1, O(C=O)-R''' mit n = 1 und m = 1, SH mit n = 1 und m = 1, S mit n = 2 und m = 1- 10 und Gemische davon, S(C=O)-R''' mit n = 1 und m = 1 oder H mit n = 1 und m = 1,
indem man Silane der allgemeinen Formel III
in der R, R'', X, m und n die oben angegebene Bedeutung aufweisen, mit Alkoholen der allgemeinen Formel R'-OH, in der R' die oben angegebene Bedeutung aufweist, unter Abspaltung von R-OH, umsetzt und R-OH durch Destillation kontinuierlich vom Reaktionsgemisch abtrennt, dadurch gekennzeichnet, daß man Metallverbindungen als Katalysator einsetzt.1. Process for the preparation of organosilicon compounds of the general formula I and / or II
where R is a methyl or ethyl group,
R 'the same or different and a C 9 -C 30 branched or unbranched monovalent alkyl or alkenyl group, aryl group, aralkyl group, branched or unbranched C 2 -C 30 alkyl ether group, branched or unbranched C 2 -C 30 alkyl polyether group or R''' 3 Si, with R''' being C 1 -C 30 branched or unbranched alkyl or alkenyl group, aralkyl group or aryl group,
R "is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C 1 -C 30 hydrocarbon group,
X is NH (3-n) with n = 1, 2, 3 and m = 1, O (C = O) -R '''with n = 1 and m = 1, SH with n = 1 and m = 1 , S with n = 2 and m = 1-10 and mixtures thereof, S (C = O) -R '''with n = 1 and m = 1 or H with n = 1 and m = 1,
by using silanes of the general formula III
in which R, R ″, X, m and n have the meaning given above, with alcohols of the general formula R′-OH, in which R ′ has the meaning given above, with elimination of R-OH, and R- OH continuously separated from the reaction mixture by distillation, characterized in that metal compounds are used as the catalyst.
Priority Applications (30)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10223073A DE10223073C1 (en) | 2002-05-24 | 2002-05-24 | Organosilicon compounds with one or two long-chain alkoxy groups attached to silicon, used as coupling agents for fillers in rubber mixtures, e.g. for tires or tubing are new |
| DE50205449T DE50205449D1 (en) | 2001-08-06 | 2002-07-09 | organosilicon |
| EP03023188A EP1394166B1 (en) | 2001-08-06 | 2002-07-09 | Organosilicon Compounds |
| ES02015228T ES2217229T3 (en) | 2001-08-06 | 2002-07-09 | ORGANOSILICIO COMPOUNDS. |
| AT03023189T ATE314381T1 (en) | 2001-08-06 | 2002-07-09 | ORGANOSILICON COMPOUNDS |
| ES03023188T ES2252606T3 (en) | 2001-08-06 | 2002-07-09 | ORGANOSILICIO COMPOUNDS. |
| EP02015228A EP1285926B1 (en) | 2001-08-06 | 2002-07-09 | Organosilicon compounds |
| ES03023189T ES2254847T3 (en) | 2001-08-06 | 2002-07-09 | ORGANOSILICIO COMPOUNDS. |
| DE50205120T DE50205120D1 (en) | 2001-08-06 | 2002-07-09 | organosilicon |
| DE50200431T DE50200431D1 (en) | 2001-08-06 | 2002-07-09 | organosilicon |
| AT03023188T ATE311396T1 (en) | 2001-08-06 | 2002-07-09 | ORGANOSILICON COMPOUNDS |
| AT02015228T ATE266669T1 (en) | 2001-08-06 | 2002-07-09 | ORGANOSILICON COMPOUNDS |
| EP03023189A EP1394167B1 (en) | 2001-08-06 | 2002-07-09 | Organosilicon compounds |
| TW091117191A TWI225064B (en) | 2001-08-06 | 2002-07-31 | Organosilicon compounds |
| BRPI0203045-4A BR0203045B1 (en) | 2001-08-06 | 2002-08-01 | Organosilicon compounds, their production process, their uses and rubber mixtures |
| CZ2002-2650A CZ304653B6 (en) | 2001-08-06 | 2002-08-01 | Organosilicon compounds, process for their preparation, rubber mix in which the compounds are comprised and use of these compounds |
| MYPI20022904A MY127353A (en) | 2001-08-06 | 2002-08-02 | Organosilicon compounds |
| MXPA02007540A MXPA02007540A (en) | 2001-08-06 | 2002-08-05 | Organosilicon compounds. |
| UA2002086517A UA77155C2 (en) | 2001-08-06 | 2002-08-05 | Organosilicon compounds, a process for preparation and use thereof |
| KR1020020046089A KR100964805B1 (en) | 2001-08-06 | 2002-08-05 | Organosilicon compounds |
| IL176243A IL176243A0 (en) | 2001-08-06 | 2002-08-05 | Organosilicon compounds |
| IL176242A IL176242A0 (en) | 2001-08-06 | 2002-08-05 | Organosilicon compounds |
| IL151066A IL151066A (en) | 2001-08-06 | 2002-08-05 | Organosilicon compounds |
| PL355358A PL207554B1 (en) | 2001-08-06 | 2002-08-05 | Organic silicon compounds, method of obtaining them and rubber compound and application thereof |
| JP2002227312A JP4414638B2 (en) | 2001-08-06 | 2002-08-05 | Organosilicon compound, process for its production, rubber mixture containing said compound and use of said compound |
| HU0202572A HU230367B1 (en) | 2001-08-06 | 2002-08-05 | Organic silicon compounds |
| US10/212,220 US6849754B2 (en) | 2001-08-06 | 2002-08-06 | Organosilicon compounds |
| CNB021276501A CN1323083C (en) | 2001-08-06 | 2002-08-06 | Organic silicone compound, preparation method thereof and use |
| US10/902,572 US7323582B2 (en) | 2001-08-06 | 2004-07-30 | Organosilicon compounds |
| JP2009200409A JP4589444B2 (en) | 2001-08-06 | 2009-08-31 | Organosilicon compound, process for its production, rubber mixture containing said compound and use of said compound |
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| DE10223073A DE10223073C1 (en) | 2002-05-24 | 2002-05-24 | Organosilicon compounds with one or two long-chain alkoxy groups attached to silicon, used as coupling agents for fillers in rubber mixtures, e.g. for tires or tubing are new |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1460099A1 (en) * | 2003-03-21 | 2004-09-22 | Goldschmidt AG | Process for modifying polysiloxanes |
| WO2010125123A1 (en) | 2009-04-30 | 2010-11-04 | Dow Corning Corporation | Elastomer compositions modified by silanes |
| WO2012059529A1 (en) | 2010-11-03 | 2012-05-10 | Dow Corning Corporation | Epoxidised elastomer compositions modified by silanes |
| US8476375B2 (en) | 2008-07-03 | 2013-07-02 | Dow Corning Corporation | Polymers modified by silanes |
| US8569417B2 (en) | 2008-07-03 | 2013-10-29 | Dow Corning Corporation | Modified polyolefins |
| US9045578B2 (en) | 2010-01-06 | 2015-06-02 | Dow Corning Corporation | Process for forming crosslinked and branched polymers |
| US9181379B2 (en) | 2010-01-06 | 2015-11-10 | Dow Corning Corporation | Modified polyolefins |
| US9493615B2 (en) | 2010-01-06 | 2016-11-15 | Dow Corning Corporation | Organopolysiloxanes containing an unsaturated group |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500725A (en) * | 1981-07-30 | 1985-02-19 | Chisso Corporation | Silane derivative and fragrant article |
-
2002
- 2002-05-24 DE DE10223073A patent/DE10223073C1/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500725A (en) * | 1981-07-30 | 1985-02-19 | Chisso Corporation | Silane derivative and fragrant article |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1460099A1 (en) * | 2003-03-21 | 2004-09-22 | Goldschmidt AG | Process for modifying polysiloxanes |
| US8476375B2 (en) | 2008-07-03 | 2013-07-02 | Dow Corning Corporation | Polymers modified by silanes |
| US8569417B2 (en) | 2008-07-03 | 2013-10-29 | Dow Corning Corporation | Modified polyolefins |
| WO2010125123A1 (en) | 2009-04-30 | 2010-11-04 | Dow Corning Corporation | Elastomer compositions modified by silanes |
| US9045578B2 (en) | 2010-01-06 | 2015-06-02 | Dow Corning Corporation | Process for forming crosslinked and branched polymers |
| US9181379B2 (en) | 2010-01-06 | 2015-11-10 | Dow Corning Corporation | Modified polyolefins |
| US9493615B2 (en) | 2010-01-06 | 2016-11-15 | Dow Corning Corporation | Organopolysiloxanes containing an unsaturated group |
| WO2012059529A1 (en) | 2010-11-03 | 2012-05-10 | Dow Corning Corporation | Epoxidised elastomer compositions modified by silanes |
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