DE1173898B - Process for the preparation of organosilicon compounds containing thioether groups - Google Patents
Process for the preparation of organosilicon compounds containing thioether groupsInfo
- Publication number
- DE1173898B DE1173898B DEG37173A DEG0037173A DE1173898B DE 1173898 B DE1173898 B DE 1173898B DE G37173 A DEG37173 A DE G37173A DE G0037173 A DEG0037173 A DE G0037173A DE 1173898 B DE1173898 B DE 1173898B
- Authority
- DE
- Germany
- Prior art keywords
- organosilicon
- compounds containing
- preparation
- mercaptans
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 3
- 125000000101 thioether group Chemical group 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkylene radical Chemical class 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000003676 hair preparation Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/40—Organo-silicon compounds
-
- 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
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Silicon Polymers (AREA)
Description
BUNDESREPUBLIK DEUTSCHLAND DEUTSCHES ^IW PATENTAMT Internat. Kl.: C07fFEDERAL REPUBLIC OF GERMANY GERMAN ^ IW PATENT OFFICE Boarding school Class: C07f
AUSLEGESCHRIFTEDITORIAL
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:
Deutsche Kl.: 12 ο-26/03 German class: 12 ο -26/03
G 37173 IVb/12 ο
28. Februar 1963
16. Juli 1964G 37173 IVb / 12 ο
February 28, 1963
July 16, 1964
Es ist bekannt, daß man Mercaptogruppen enthaltende Verbindungen an Verbindungen mit olefinischen Doppelbindungen anlagern kann. Die Anlagerung von Mercaptanen, bei denen die Mercaptogruppe über eine Alkylengruppe an ein Siliciumatom gebunden ist, an Verbindungen mit olefinischer Doppelbindung wurde jedoch noch nicht beschrieben, Verbindungen, welche die StrukturIt is known that compounds containing mercapto groups can be linked to compounds with olefinic Can add double bonds. The addition of mercaptans in which the mercapto group is bonded to a silicon atom via an alkylene group, to compounds having an olefinic However, double bond has not yet been described, compounds showing the structure
=^Si — M — S — R= ^ Si - M - S - R
aufweisen, in welcher M eine Alkylengruppe ist, welche das Silicium- und Schwefelatom über mindestens drei Kohlenstoffatome miteinander verbindet und R ein Kohlenwasserstoffrest ist, besitzen überraschende wertvolle Eigenschaften, welche sie zum Einsatz in einer 1S Reihe von Industriezweigen geeignet machen.have, in which M is an alkylene group which links the silicon and sulfur atom via at least three carbon atoms with each other and R is a hydrocarbon radical, have surprising valuable properties which make them suitable for use in a 1 S number of industries.
Es wurde nun gefunden, daß man derartige Verbindungen in einfacher und glatter Reaktion dadurch herstellen kann, daß manIt has now been found that such compounds can be obtained in a simple and smooth reaction thereby can produce that one
a) siliciumorganische Mercaptane der allgemeinen Formela) organosilicon mercaptans of the general formula
i — MSHi - MSH
worin M ein Alkylenrest ist, der das Siliciumatom und das Schwefelatom über mindestens drei Kohlenstoffatome miteinander verbindet, z. B. der Propylen-, Butylen- und Isopropylenrest, R und R' ein niederer Alkyl-, Phenyl- oder Benzylrest sind, wobei α und b jeweils eine beliebige Zahl von O bis 3 bedeuten, deren Summe gleich 3 ist, oderwherein M is an alkylene radical which connects the silicon atom and the sulfur atom to one another via at least three carbon atoms, e.g. B. the propylene, butylene and isopropylene radical, R and R 'are a lower alkyl, phenyl or benzyl radical, where α and b are each any number from 0 to 3, the sum of which is 3, or
b) siliciumorganische Mercaptane der allgemeinen Formelb) organosilicon mercaptans of the general formula
RB(RO)mSi(MSH),,O2_ n+m+v R B (RO) m Si (MSH) ,, O 2 _ n + m + v
worin R und R' und M die angegebene Bedeutung haben, η und m eine beliebige Zahl von 0 bis 3 bedeuten, ν eine beliebige Zahl von 0,001 bis 1, vorzugsweise von 0,01 bis 1 ist, wobei die Summe n+m + v einen Wert zwischen 1 und 3 hat, mit einer eine olefinische Doppelbindung aufweisenden Verbindung in Gegenwart von Anlagerungskatalysatoren in an sich bekannter Weise umsetzt.where R and R 'and M have the meaning given, η and m are any number from 0 to 3, ν is any number from 0.001 to 1, preferably from 0.01 to 1, the sum n + m + v has a value between 1 and 3, with a compound having an olefinic double bond in the presence of addition catalysts in a manner known per se.
Beispiele für die Reste R und R' sind die Methyl-, Äthyl-, Propyl-, Isopropyl-, Hexyl-, Phenyl- und Benzylreste. M ist vorzugsweise eine — oder eineExamples of the radicals R and R 'are methyl, ethyl, propyl, isopropyl, hexyl, phenyl and Benzyl residues. M is preferably a - or a
— CH2 — CH — CH2-Gruppe.- CH 2 - CH - CH 2 group.
CH3 CH 3
Verfahren zur Herstellung von Thioäthergruppen enthaltenden siliciumorganischen VerbindungenProcess for the preparation of organosilicon compounds containing thioether groups
Anmelder:Applicant:
Th. Goldschmidt A. G.„ Essen, Söllingstr. 120Th. Goldschmidt A. G. “Essen, Söllingstr. 120
Als Erfinder benannt:Named as inventor:
Dr. Götz Koerner, Mülheim/RuhrDr. Götz Koerner, Mülheim / Ruhr
Die vorgenannten siliciumorganischen Verbindungen können z. B. entsprechend dem französischen Patent 1 356 552 dadurch hergestellt werden, daß man die entsprechenden siliciumorganischen Isothioroniumsalze alkalisch spaltet.The aforementioned organosilicon compounds can, for. B. according to the French patent 1,356,552 can be prepared by using the corresponding organosilicon isothioronium salts alkaline cleaves.
Als Verbindungen mit olefinischen Doppelbindungen werden vorzugsweise solche Verbindungen eingesetzt, welche eine Vinyl- oder Allylgruppe enthalten. Beispiele solcher Verbindungen sind Vinylchlorid, Vinylcyanid, Vinylacetat, Vinylidenchlorid, Vinylidencyanid, Allylchlorid, Allylacetat, Allylamin, Allylalkohol, Allylglycidäther, Allylmethacrylat, Acrolein oder Styrol. The compounds used with olefinic double bonds are preferably those compounds which contain a vinyl or allyl group. Examples of such compounds are vinyl chloride, vinyl cyanide, Vinyl acetate, vinylidene chloride, vinylidenecyanide, allyl chloride, allyl acetate, allylamine, allyl alcohol, Allyl glycidyl ether, allyl methacrylate, acrolein or styrene.
Die Umsetzung erfolgt in Gegenwart von bekannten Katalysatoren, wie organischen Peroxyden, z. B. Benzoylperoxyd, tert.-Butylperbenzoat. Die Anlagerung kann auch durch den Zusatz von anderen Radikalbildnern, wie Azodiisobuttersäurenitril, katalysiert werden. Auch durch Verwendung tertiärer Amine, ζ. B. Triäthylamin oder Triäthylendiamin, kann das erfindungsgemäße Verfahren durchgeführt werden. Ebenso sind Lewissäuren, z. B. Bortrifluorid, brauchbar. Als besondes geeignet haben sich des weiteren Schwermetallsalze, wie z. B. Kupfer(II)-acetat, erwiesen. Die Anlagerunsreaktion kann auch durch Bestrahlung in Gang gesetzt werden.The reaction is carried out in the presence of known catalysts such as organic peroxides, e.g. B. benzoyl peroxide, tert-butyl perbenzoate. The addition can also be caused by the addition of other radical formers, such as azodiisobutyronitrile, are catalyzed. Also by using tertiary amines, ζ. B. triethylamine or triethylenediamine, the inventive method can be carried out. Likewise, Lewis acids, e.g. B. boron trifluoride, useful. Furthermore, they have proven to be particularly suitable Heavy metal salts, such as B. copper (II) acetate, proven. The Anlageunsreaktion can also by Irradiation can be started.
Es kann von Vorteil sein, das erfindungsgemäße Verfahren bei erhöhten Temperaturen, z. B. bei Temperaturen zwischen 30 und 200° C, durchzuführen. Bei besonders reaktionsfähigen olefinischen Komponenten kann es aber auch günstig sein, die Reaktion durch Kühlung, z. B. auf +30 bis —50°C, unter Kontrolle zu halten. Sehr häufig erweist es sich als zweckmäßig, die olefinischen Komponenten zur Vermeidung einer Polymerisation oder Telomerisation zum vorgelegten Mercaptan-Katalysator-Gemisch zuzutropfen. Eine andere Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß man die olefinischen und die Mercaptankomponenten vorher mischt und zumIt can be advantageous to carry out the process according to the invention at elevated temperatures, e.g. B. at temperatures between 30 and 200 ° C. For particularly reactive olefinic components but it can also be advantageous to carry out the reaction by cooling, e.g. B. to +30 to -50 ° C, under control to keep. Very often it proves to be useful, the olefinic components to avoid a Add dropwise polymerization or telomerization to the initially charged mercaptan / catalyst mixture. One Another embodiment of the process according to the invention is that the olefinic and the mercaptan components mix beforehand and to
409 630/403409 630/403
vorgelegten Katalysator zutropft. Gegebenenfalls ist die Verwendung eines Lösungsmittels angezeigt.introduced catalyst is added dropwise. If necessary, the use of a solvent is indicated.
Durch Imprägnierung von Glasfasern mit den erfindungsgemäß hergestellten Produkten wird bei der anschließenden Kunstharzbeschichtung der Glasfasern eine wesentliche Verbesserung der Haftung zwischen der Glasfaser und dem Harz erzielt.By impregnating glass fibers with the products manufactured according to the invention, the subsequent synthetic resin coating of the glass fibers significantly improves the adhesion achieved between the fiberglass and the resin.
Die Reaktionsprodukte aus den siliciumorganischen Mercaptanen und Allylamin sowie auch Allylglycidäther erweisen sich als besonders gutes Glasfaserfinish für die nachfolgende Beschichtung mit Epoxyharzen, während die Reaktionsprodukte aus den siliciumorganischen Mercaptanen und Acrolein sowie Allylmethacrylat sich vor allem als Glasfaserfinish für die anschließende Beschichtung mit Polyesterharzen eignen anschließende Beschichtung mit Polyesterharzen eignen.The reaction products from the organosilicon mercaptans and allylamine as well as allyl glycidyl ether prove to be a particularly good glass fiber finish for the subsequent coating with epoxy resins, while the reaction products of the organosilicon mercaptans and acrolein and allyl methacrylate are particularly suitable as a glass fiber finish for subsequent coating with polyester resins subsequent coating with polyester resins are suitable.
Eine weitere Anwendungsmöglichkeit besteht in dem Einsatz der erfindungsgemäß hergestellten Produkte zum Schutz von Metalloberflächen, die, bedingt durch die Si-M-S-R-Gruppierung der Verfahrensprodukte, auf den Metallen, z. B. Silber, gute Haftung an der Oberfläche und Schutz vor oberflächlichem Angriff vermitteln.Another possible application is the use of the products produced according to the invention to protect metal surfaces which, due to the Si-M-S-R grouping of the process products, on the metals, e.g. B. silver, good adhesion to the surface and protection against superficial attack convey.
Die Verfahrensprodukte sind außerdem zur Herstellung kosmetischer Präparate, insbesondere zur Haarkosmetik, geeignet.The process products are also used for the production of cosmetic preparations, in particular for Hair cosmetics, suitable.
Darstellung von <w-MethyldiäthoxysilyI-4-thiaheptanal Representation of <w-MethyldiäthoxysilyI-4-thiaheptanal
56 g (1 Mol) Acrolein (mit Hydrochinon stabilisiert) und 0,5 g Kupfer(II)-acetat werden in einem Dreihalskolben mit aufgesetztem Rührer, Rückflußkühler und Tropftrichter vermischt. Unter Rühren und Kühlen gibt man durch den Tropftrichter 208 g (1 Mol) y-Mercaptopropylmethyldiäthoxysilan mit einer solchen Geschwindigkeit zu, daß die Innentemperatur 35 bis 400C beträgt. Danach läßt man 1 Stunde bei 370C nachreagieren und unterwirft anschließend das Reaktionsprodukt einer fraktionierten Destillation. Kp.o,! 120 bis 1300C. Ausbeute 180 g (68% der Theorie). Im IR-Spektrum ist bei 1740 cm^1 eine starke Bande vorhanden, die der C = O-Schwingung der Aldehyde entspricht.56 g (1 mol) of acrolein (stabilized with hydroquinone) and 0.5 g of copper (II) acetate are mixed in a three-necked flask with attached stirrer, reflux condenser and dropping funnel. While stirring and cooling are added through the dropping funnel 208 g (1 mol) of y-Mercaptopropylmethyldiäthoxysilan at a rate such that the internal temperature is 35 to 40 0 C. Then allowed 1 hour at 37 0 C after-react and subsequently subjecting the reaction product to fractional distillation. Kp.o ,! 120 to 130 ° C. Yield 180 g (68% of theory). In the IR spectrum there is a strong band at 1740 cm ^ 1 , which corresponds to the C = O oscillation of the aldehydes.
MolgewichtMolecular weight
Si Si
S S.
C C.
H H
OC8H5 ....OC 8 H 5 ....
Analyseanalysis
berechnetcalculated
gefundenfound
264
10,6%264
10.6%
12,1%
50,0%12.1%
50.0%
9,1%
34,1 %9.1%
34.1%
275
10,4%275
10.4%
11,9%11.9%
49,5%49.5%
9,2%9.2%
33,5%33.5%
schung noch IV2 Stunden bei O0C. Das Reaktionsprodukt wird destilliert. Kp.0>3 130 bis 137°C. Ausbeute 90 g, entsprechend 68,7 7o der Theorie.Schung another IV 2 hours at 0 ° C. The reaction product is distilled. B.p. 0> 3130 to 137 ° C. Yield 90 g, corresponding to 68.7 70 of theory.
50,20%
9,51 7o
12,17%
5,32%
Beispiel10.64%
50.20%
9.51 7o
12.17%
5.32%
example
49,8%
8,9%
12,9%
4,9%10.7%
49.8%
8.9%
12.9%
4.9%
y-(/}-phenyläthylmercapto)-propylmethyldiäthoxysilan y - (/} - phenylethyl mercapto) propylmethyl diethoxysilane
Eine Mischung von 104,4 g y-Mercaptopropylmethyldiäthoxysilan (=0,5 Mol) und 52,1 g Styrol (= 0,5 Mol) läßt man unter Rühren innerhalb von 15 Minuten bei Raumtemperatur zu 1,5 g Benzoylperoxyd, gelöst in 20 cm3 Benzol, tropfen. Danach läßt man noch 1 Stunde bei Raumtemperatur undA mixture of 104.4 g of γ-mercaptopropylmethyldiethoxysilane (= 0.5 mol) and 52.1 g of styrene (= 0.5 mol) is allowed to give 1.5 g of benzoyl peroxide dissolved in 20 at room temperature over the course of 15 minutes cm 3 benzene, drip. Then left for 1 hour at room temperature and
as 3 Stunden bei 1300C Badtemperatur nachreagieren.Post-react as 3 hours at 130 0 C bath temperature.
Das Reaktionsprodukt wird destilliert. Kp.0>2 140 bisThe reaction product is distilled. Kp. 0> 2 140 to
145°C. Ausbeute 85 g (54,3 7„ der Theorie).'145 ° C. Yield 85 g (54.3% of theory).
61,55%
8,97%
10,5%8.97%
61.55%
8.97%
10.5%
gefundenilyse
found
62,0%
9,4%
10,28 70 8.55%
62.0%
9.4%
10.28 7 0
y-(/9-cyanäthylmercapto)-propylmethyldiäthoxysilan y - (/ 9-cyanoethyl mercapto) propylmethyl diethoxysilane
104,4 g y-Mercaptopropylmethyldiäthoxysilan (=0,5 Mol) werden in 200 cm3 Äthanol gelöst, die 1 g Natriumäthylat enthalten. Zu dieser Mischung läßt man unter Rühren und Kühlen bei einer Innentemperatur von —3 bis +50C 26,5 g Acrylnitril (= 0,5 Mol) zutropfen und beläßt danach die Mi104.4 g of y-mercaptopropylmethyl diethoxysilane (= 0.5 mol) are dissolved in 200 cm 3 of ethanol containing 1 g of sodium ethylate. Is added dropwise to this mixture under stirring and cooling at an internal temperature of -3 to +5 0 C, 26.5 g of acrylonitrile (= 0.5 mol) is added dropwise and then leaves the Mi
7-(j^-cyanäthylmercapto)-2-methylpropyltriäthoxysilan 7- (j ^ -cyanoethylmercapto) -2-methylpropyltriethoxysilane
126 g y-Mercapto-^-methylpropyltriäthoxysilan (= 0,5 Mol) werden in 200 g Äthanol gelöst, die 1 g Natriumäthylat enthalten. Zu dieser Mischung läßt man unter Rühren und Kühlen bei einer Innentemperatur von 0 bis 5°C 26,5 g Acrylnitril (= 0,5 Mol) zutropfen und beläßt danach die Mischung noch 1V2 Stunden bei O0C. Das Reaktionsprodukt wird destilliert. Kp.0,2 148 bis 1550C. Ausbeute 84 g (55% der Theorie).126 g of y-mercapto - ^ - methylpropyltriäthoxysilan (= 0.5 mol) are dissolved in 200 g of ethanol containing 1 g of sodium ethylate. Is added dropwise to said mixture under stirring and cooling at an internal temperature of 0 to 5 ° C 26.5 g of acrylonitrile (= 0.5 mol) is added dropwise and then leaving the mixture still 1V 2 hours at O 0 C. The reaction product is distilled. Kp. 0, 2148-155 0 C. Yield 84 g (55% of theory).
y-^-AcetoxyäthylmercaptoJ-propylmethyldiäthoxysilan y - ^ - AcetoxyethylmercaptoJ-propylmethyldiethoxysilane
20,8 g (0,1 Mol y-Mercaptopropylmethyldiäthoxysilan und 8,6 g (0,1 Mol) Vinylacetat (frisch destilliert) werden vermischt. 10 Vo dieses Gemisches werden zu20.8 g (0.1 mol of γ-mercaptopropylmethyldiethoxysilane and 8.6 g (0.1 mol) vinyl acetate (freshly distilled) are mixed. 10 Vo of this mixture become
0,4 g Benzoylperoxyd gegeben und der Rest innerhalb von 4 Stunden bei einer Temperatur von 940C unter Rückfluß und Rühren tropfenweise zugegeben. Danach läßt man 3 Tage bei 110° C nachreagieren. Die Reaktion wird unter Stickstoff ausgeführt. Das Reaktionsprodukt wird destilliert. Kp.0f2 110 bis 114°C. Ausbeute 14,0 g (47 70 der Theorie).'0.4 g of benzoyl peroxide and the rest period of 4 hours at a temperature of 94 0 C under reflux with stirring was added dropwise. The reaction is then allowed to continue for 3 days at 110.degree. The reaction is carried out under nitrogen. The reaction product is distilled. B.p. 0f2 110 to 114 ° C. Yield 14.0 g (47 7 0 of theory). '
Molgewicht ..Molecular weight ..
Si Si
C C.
H H
S S.
OC2H5 OC 2 H 5
Analyseanalysis
berechnetcalculated
294294
9,54 0/0
48,9%
8,84%9.54 0/0
48.9%
8.84%
11,7%
30,7%11.7%
30.7%
gefundenfound
285285
9,7%
48,4%9.7%
48.4%
8,9%
11,7%
30,8%8.9%
11.7%
30.8%
y-(^-Acetoxyäthylmercapto)-propylmethylpolysiloxan y - (^ - acetoxyethyl mercapto) propylmethylpolysiloxane
Zu 208 g (1 Mol) y-Mercaptopropylmethyldiäthoxysilan läßt man innerhalb von 2 Stunden unter Rühren zu 400 cm3 5%iger Salzsäure zutropfen und erwärmt anschließend unter weiterem Rühren 1 Stunde lang auf 80°C. Die Ölphase wird abgetrennt, zuerst mit destilliertem Wasser und danach mit gesättigter NaHCO3-Lösung gewaschen und mit Toluol durch azeotrope Destillation getrocknet. Nach Abdestillieren des Toluols verbleiben 129 g (96,3% der Theorie) y-MercaptopropylmethylpolysiloxanCViskosität: 85cP).To 208 g (1 mol) of γ-mercaptopropylmethyldiethoxysilane is added dropwise to 400 cm 3 of 5% hydrochloric acid over a period of 2 hours while stirring, and the mixture is then heated to 80 ° C. for 1 hour while stirring. The oil phase is separated off, washed first with distilled water and then with saturated NaHCO 3 solution and dried with toluene by azeotropic distillation. After the toluene has been distilled off, 129 g (96.3% of theory) of γ-mercaptopropylmethylpolysiloxane (viscosity: 85 cP) remain.
67 g dieses Polysiloxans werden mit 1,12 g (0,01 Mol) Triäthylendiamin versetzt und in einem Dreihalskolben unter einem schwachen Strom sauerstofffreien Stickstoffs auf 400C gebracht. Dann läßt man unter Rühren 50 g (0,5 Mol) Acrylsäureäthylester so zutropfen, daß die Temperatur im Dreihalskolben 500C nicht überschreitet. Danach wird noch eine weitere Stunde bei 500C gerührt. Aus dem Reaktionsprodukt läßt sich bei einer Badtemperatur von 180° C und Anwendung von Vakuum kein Acrylsäureäthylester mehr abdestillieren. Ausbeute 116 g (99,2 70 der Theorie). Viskosität: 318 cP.67 g of this polysiloxane are mixed with 1.12 g (0.01 mol) of triethylenediamine and brought to 40 ° C. in a three-necked flask under a weak stream of oxygen-free nitrogen. Then allowed under stirring, 50 g (0.5 mol) of ethyl acrylate are added dropwise so that the temperature in the three-necked flask does not exceed 50 0 C. The mixture is then stirred at 50 ° C. for a further hour. Ethyl acrylate can no longer be distilled off from the reaction product at a bath temperature of 180.degree. C. and using a vacuum. Yield 116 g (99.2 7 0 of theory). Viscosity: 318 cP.
j gefundenanalysis
j found
46,16%
7,69%
13,67%11.96%
46.16%
7.69%
13.67%
45,970
7,47ο
13,87ο11.3%
45.97 0
7.47ο
13.87ο
kühlt. Unter Stickstoff werden bei 0 bis +5° C 29,2 g (0,55 Mol) Acrylnitril zugetropft. Danach wird das Produkt auf Raumtemperatur gebracht und über Nacht stehengelassen. Das Natriumäthylat wird mit Salzsäure neutralisiert, Äthanol und überschüssiges Acrylnitril zuletzt im Vakuum abdestilliert und der Rückstand filtriert. Ausbeute 87 g (93 70 der Theorie).cools. 29.2 g (0.55 mol) of acrylonitrile are added dropwise at 0 to + 5 ° C. under nitrogen. The product is then brought to room temperature and left to stand overnight. The sodium ethylate is neutralized with hydrochloric acid, ethanol and excess acrylonitrile are finally distilled off in vacuo and the residue is filtered. Yield 87 g (93 7 0 of theory).
44,927ο
6,957ο
17,127ο
7,497ο14.977ο
44.927ο
6,957ο
17,127ο
7,497ο
gefundenilyse
found
43,87ο
6,77ο
17,87ο
6,97ο15.27ο
43.87ο
6.77ο
17.87ο
6.97ο
Das IR-Spektrum dieses Silikonöles ist nahezuThe IR spectrum of this silicone oil is almost
identisch mit dem IR-Spektrum eines Öles, das durchidentical to the IR spectrum of an oil that passes through
ao eine analog Beispiel 6 durchgeführte Hydrolyse des y-(^-Cyanäthylmercapto)-propylmethyldiäthoxysilans (Beispiel 2) erhalten wurde.ao a hydrolysis of y - (^ - Cyanäthylmercapto) propylmethyl diethoxysilane carried out analogously to Example 6 (Example 2) was obtained.
Claims (2)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEG37173A DE1173898B (en) | 1963-02-28 | 1963-02-28 | Process for the preparation of organosilicon compounds containing thioether groups |
| US344217A US3392182A (en) | 1963-02-28 | 1964-02-12 | Novel organosilicon compounds and process for their preparation |
| GB8066/64A GB1018311A (en) | 1963-02-28 | 1964-02-26 | Organosilicon compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEG37173A DE1173898B (en) | 1963-02-28 | 1963-02-28 | Process for the preparation of organosilicon compounds containing thioether groups |
| FR959958A FR1378791A (en) | 1964-01-10 | 1964-01-10 | Process for the preparation of organosilicon compounds containing thioether groups |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1173898B true DE1173898B (en) | 1964-07-16 |
Family
ID=25978503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEG37173A Pending DE1173898B (en) | 1963-02-28 | 1963-02-28 | Process for the preparation of organosilicon compounds containing thioether groups |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1173898B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8252862B2 (en) | 2007-09-13 | 2012-08-28 | Basf Se | Silane coupling agents for filled rubbers |
-
1963
- 1963-02-28 DE DEG37173A patent/DE1173898B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8252862B2 (en) | 2007-09-13 | 2012-08-28 | Basf Se | Silane coupling agents for filled rubbers |
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