EP1461344A1 - Verfahren zur herstellung von polyschwefelmonoorganooxysilanen - Google Patents

Verfahren zur herstellung von polyschwefelmonoorganooxysilanen

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Publication number
EP1461344A1
EP1461344A1 EP02799785A EP02799785A EP1461344A1 EP 1461344 A1 EP1461344 A1 EP 1461344A1 EP 02799785 A EP02799785 A EP 02799785A EP 02799785 A EP02799785 A EP 02799785A EP 1461344 A1 EP1461344 A1 EP 1461344A1
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European Patent Office
Prior art keywords
formula
metal
carried out
hal
reaction
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EP02799785A
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English (en)
French (fr)
Inventor
Nathalie La Clairière GUENNOUNI
Virginie Pevere
Bernard Vogin
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Priority claimed from FR0115768A external-priority patent/FR2833264B1/fr
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Priority to EP05021616A priority Critical patent/EP1621543B1/de
Publication of EP1461344A1 publication Critical patent/EP1461344A1/de
Withdrawn legal-status Critical Current

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    • 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

Definitions

  • the present invention relates to a new synthesis route for polysulphurized monoorganoxysilanes which is carried out from raw materials which are products available on an industrial scale, without the formation of harmful secondary products and with a practically quantitative sequence of the various stages constituting this new synthetic route.
  • R 1 identical or different, each represent a monovalent hydrocarbon group chosen from an alkyl radical, linear or branched, having from 1 to 15 carbon atoms and an alkoxyalkyl radical, linear or branched, having from 2 to 8 atoms carbon;
  • R 2 and R 3 identical or different, each represent a monovalent hydrocarbon group chosen from an alkyl radical, linear or branched, having from 1 to 6 carbon atoms and a phenyl radical;
  • the preferred radicals R 1 are chosen from the radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, CH 3 OCH 2 -, CH 3 OCH 2 CH 2 - and CH 3 OCH (CH 3 ) CH 2 -; more preferably, the radicals R 1 are chosen from the radicals: methyl, ethyl, n-propyl and isopropyl.
  • the preferred radicals R 2 and R 3 are chosen from the radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl and phenyl; more preferably, the radicals R 2 and R 3 are methyls.
  • the number x, whole or fractional, preferably ranges from 3 + 0.1 to 5 + 0.1, and more preferably from 3.5 + 0.1 to 4.5 + 0.1.
  • polysulphurized monoorganoxysilanes corresponding to formula (I) which are specially targeted by the present invention are those of formula:
  • the symbol x is an integer or fraction ranging from 1.5 ⁇ 0.1 to 5 ⁇ 0.1, preferably from 3 ⁇ 0.1 to 5 ⁇ 0.1, and more preferably from 3, 5 ⁇ 0.1 to 4.5 ⁇ 0.1.
  • this number is the average of the number of sulfur atoms per molecule of compound considered, insofar as the chosen synthetic route gives rise to a mixture of polysulphurized products each having a different number of sulfur atoms.
  • the synthesized polysulphurized monoorganoxysilanes in fact consist of a distribution of polysulphides, ranging from monosulphide to heavier polysulphides (such as for example S ⁇ 5 ), centered on an average value in moles (value of the symbol x) lying in the domains general (x ranging from 1.5 + 0.1 to 5 + 0.1), preferential (x ranging from 3 + 0.1 to 5 + 0.1) and more preferential (x ranging from 3.5 ⁇ 0, 1 to 4.5 + 0.1) mentioned above.
  • trialkoxysilylalkyl halides are obtained by alcoholysis in the usual manner from the corresponding trihalogenosilylalkyl halides.
  • Hal represents a halogen atom chosen from chlorine, bromine and iodine atoms, the chlorine atom being preferred, the symbols R 2 and R 3 are as defined above,
  • - A represents a removable group chosen from: either a halogen atom Hal belonging to the chlorine, bromine and iodine atoms, the chlorine atom being preferred; or a para-R ° -C 6 H -SO 2 -0- radical where R ° is a linear or branched C1-C4 alkyl radical, the para-CH 3 -C 6 H 4 -S0 2 -0 tosylate radical - being prefer ; or a radical R ° -SO 2 -O- where R ° is as defined above, the mesylate radical CH 3 -S0 2 -O- being preferred; either a radical R ° -CO-O- where R ° is as defined above, the acetate radical CH 3 -CO-O- being preferred,
  • the reaction is carried out: • by reacting at a temperature ranging from -10 ° C to 200 ° C one mole of the diorganohalosilane of formula (V) with a stoichiometric molar quantity or different from the stoichiometry of the allyl derivative of formula ( VI) by operating, in a homogeneous or heterogeneous medium, in the presence of an initiator consisting of: - either in a catalytic activator consisting in: (i) at least one catalyst comprising at least one transition metal or a derivative of said metal, taken in the group formed by Co, Ru, Rh, Pd, Ir and Pt; and optionally (2i) at least one hydrosilylation reaction promoter, - either in a photochemical activator, consisting in particular in an appropriate ultraviolet radiation or in an appropriate ionizing radiation, • and optionally in isolating the diorganohalogenosilylpropyl derivative of formula (VII ) trained; B step (b) which takes place
  • reaction is carried out: • by reacting at a temperature ranging from -20 ° C to 200 ° C either the reaction medium obtained at the end of step (a), or the diorganohalososylpropyl derivative of formula (VII) taken alone after separation of said medium, with the alcohol of formula (VIII), using at least one mole of alcohol of formula (VIII) per mole of the reagent formula (VII), and optionally operating in the presence of a base and / or an organic solvent, • and optionally isolating the monoorganoxydiorganosilylpropyl derivative of formula (IX) formed; “ Step (c) which takes place according to the equation:
  • the process according to the present invention makes it possible to access bis- (monoorganoxysilylpropyl) polysulphides of formula (I) industrially starting from diorganohalogenosilanes of formula (V), in particular (CH 3 ) 2 HSiCI.
  • diorganohalogenosilanes of formula (V) can be prepared advantageously on an industrial scale by a process such as in particular that described in WO-A-99/31111.
  • step (a 1 ) which takes place according to the equation:
  • step (b ') which takes place according to the equation:
  • step (a ') By reacting either the reaction medium obtained at the end of step (a '), or the monoorganoxydiorganosilane of formula (X! Taken in isolation after separation of said medium, using a mole of silane of formula (XI) with a stoichiometric or different molar amount from the stoichiometry of the allyl derivative of formula (VI) and operating in a homogeneous or heterogeneous medium, in the presence of an initiator consisting of:
  • a catalytic activator consisting of: (i) at least one catalyst comprising at least one transition metal or a derivative of said metal, taken from the group formed by Co, Ru, Rh,
  • a photochemical activator consisting in particular in an appropriate ultraviolet radiation or in an appropriate ionizing radiation
  • step (c) according to the process of the invention can be carried out, as indicated above, starting, in addition to the reaction medium obtained at the end of step (b), from the reaction medium obtained at the end of step (b ') explained above.
  • the method which has just been described consists in linking either steps (a), (b) and (c), or steps (a '), (b') and (c), in the definition of which the removable group A corresponds to the symbol Hal representing a halogen atom chosen from chlorine, bromine and iodine atoms, and, preferably, a chlorine atom.
  • Step (a) consists in reacting the diorganohalosilane of formula (V) with the allyl derivative of formula (VI) in the presence of a chosen initiator.
  • (b ') consists in reacting the monoorganoxydiorganosilane of formula (XI) with the allyl derivative of formula (VI) in the presence also of this chosen initiator.
  • the initiator that is used includes all the initiators, corresponding to the types indicated above, which are effective in activating the reaction between a ⁇ SiH function and ethylenic unsaturation. According to a preferred arrangement concerning the initiator, the latter is chosen from catalytic activators.
  • catalytic activators include: - - as catalyst (s) (i): (i-1) at least one finely divided elementary transition metal; and / or (i-2) a colloid of at least one metal of transition; and / or (i-3) an oxide of at least one transition metal; and / or (i-4) a salt derived from at least one transition metal and from a mineral or carboxylic acid; and / or (i-5) a complex of at least one transition metal equipped with halogenated and / or organic ligand (s) which may have one or more heteroatom (s) and / or ligand ( s) organosilicon (s); and / or (i-6) a salt as defined above where the metal part is equipped with ligand (s) as defined also above; and / or (i-7) a metallic species chosen from the aforementioned species (elementary transition metal, oxide, salt, complex, complexed salt) where the transition metal is associated this time with at least one other metal chosen from the family elements of groups
  • a compound which may for example have the form of a ligand or of an ionic compound, taken in particular from the group formed by: an organic peroxide; a carboxylic acid; a carboxylic acid salt; a tertiary phosphine; a phosphite such as, for example, an optionally mixed alkyl and / or aryl phosphite; an amine; a friend of ; a linear or cyclic ketone; a trialkylhydrogenosilane; benzothriazole; phenothiazine; a compound of 03/048169
  • OCOCH 3 OCOCH 3 ; a lactone; a mixture of cyclohexanone with triphenylphosphine; an ionic compound such as, for example, an alkali metal or imidazolinium nitrate or borate, a phosphonium halide, a quaternary ammonium halide, a tin II halide.
  • an ionic compound such as, for example, an alkali metal or imidazolinium nitrate or borate, a phosphonium halide, a quaternary ammonium halide, a tin II halide.
  • the latter is chosen from the preferred catalytic activators mentioned above which comprise, as catalyst (s) (i), one and / or the other metallic species (i-1) to (i-9) where the transition metal belongs to the following subgroup: Ir and Pt.
  • the latter is chosen from the preferred catalytic activators mentioned above which comprise, as the catalyst (s) (i), one and / or the other of the metallic species (i-1) to (i-9) where the transition metal is Ir.
  • suitable Ir-based catalysts are in particular:
  • Ir-based catalysts which are even more suitable are taken from the group of iridium complexes of formula:
  • R 4 represents an unsaturated hydrocarbon ligand comprising at least one carbon ⁇ carbon double bond and / or at least one triple bond c ⁇ c, these unsaturated bonds being able to be conjugated or not conjugated, said ligand: being linear or cyclic (mono or polycyclic), having from 4 to 30 carbon atoms, having from 1 to 8 ethylenic and / or acetylenic unsaturations and optionally comprising one or more heteroatoms such as for example an oxygen atom and / or a silicon atom;
  • R 4 is chosen from butadiene-1, 3, hexadiene-1, 3, cyclohexadiene-1, 3, cyclooctadiene-1, 3, cyclooctadiene-1, 5, cyclododecatriene-1, 5 , 9 and norbornadiene, and the following compounds of formulas: 03/048169
  • Hal represents a chlorine atom.
  • iridium complexes which are even more suitable, mention may be made of the following catalysts: ⁇ -chlorobis (divinyltetramethyidisiloxane) diiridium, ⁇ -chlorobis ( ⁇ -1,5-hexadiene) diiridium, - ⁇ -bromobis ( ⁇ -1, 5-hexadiene) diiridium, - ⁇ -iodobis ( ⁇ -1, 5-hexadiene) diiridium, - ⁇ -chlorobis ( ⁇ -1, 5-cyclooctadiene) diiridium, - ⁇ -bromobis ( ⁇ -1, 5 -cyclooctadiene) diiridium, - ⁇ -iodobis ( ⁇ -1, 5-cyclooctadiene) diiridium, - ⁇ -chlorobis ( ⁇ -2,5-norbornadiene) diiridium, -
  • the catalyst can be used, and this is another preferred arrangement, in a homogeneous medium, as described in JP-B-2,938,731.
  • the reaction can be carried out either continuously, or semi-continuously, or discontinuously.
  • the reaction product is separated and collected by distillation from the reaction medium, and it is possible to recycle the catalyst by carrying out a new charge of reagents on a distillation pellet containing the catalyst resulting from the step of distillation of the product of the previous operation, with possible additional addition of new catalyst.
  • the recycling of the catalyst can be improved by also adding a small amount of ligand.
  • the catalyst can still be used in a heterogeneous medium.
  • This procedure calls in particular for the use of a catalyst which is supported on an inert solid support of the type of those defined above. This procedure makes it possible to carry out the reaction in a fixed bed reactor operating continuously, semi-continuously or discontinuously with recycling. It is also possible to carry out the reaction in a standard stirred reactor operating continuously, semi-continuously or discontinuously.
  • the reaction product is therefore separated and collected by distillation from the reaction medium, and it is possible to recover the catalytic metal contained in the liquid distillation pellet, said metal being in its original catalyst form or in a transformed form.
  • the liquid distillation pellet is brought into contact with an effective adsorbent quantity of a solid adsorbent agent.
  • the solid adsorbent is generally in the form of powder, extrusion, granule or grafted on a support such as cellulose for example.
  • carbon black As a solid adsorbent, it is more particularly recommended to use carbon black; activated carbon; molecular sieves which are most often synthetic zeolites, silicalites or metallic aluminosilicates; silicas; activated aluminas; adsorbent fillers based on diatomite and perlite; activated and ground clays based on bentonite and attapulgite; ion exchange resins; or amberlite or amberlyst type resins.
  • carbon black As a solid adsorbent, it is more particularly recommended to use carbon black; activated carbon; molecular sieves which are most often synthetic zeolites, silicalites or metallic aluminosilicates; silicas; activated aluminas; adsorbent fillers based on diatomite and perlite; activated and ground clays based on bentonite and attapulgite; ion exchange resins; or amberlite or amberlyst type resin
  • Adsorption can be implemented: batchwise (i.e. in batch) with powder-type compounds; continuously via a column or through a fixed bed.
  • the contact time can vary from 5 minutes to 10 hours, preferably between 30 minutes and 7 hours in batch.
  • the temperature can vary from 5 to 150 ° C, preferably from 10 to 30 ° C.
  • the quantity of adsorbent used for activated carbon, molecular sieves, silicas, aluminas and mineral adjuvants is strongly linked on the one hand to the specific adsorption capacity relating to each of the adsorbents that it is possible to 'use in the context of the invention and secondly to the implementation parameters such as the temperature and the presence or absence of a solvent.
  • the adsorption capacity (q) is expressed in number of moles of metal adsorbed per kilogram of adsorbent used. This quantity q is generally between 0.1 and 30, preferably between 0.5 and 20.
  • the resin is characterized by an exchange capacity value which is specific for each resin grade and which is related to the functionality carried by this resin. This exchange capacity is generally expressed in meq / g for a dry product or in meq./ml on a wet product.
  • These resins are preferably used so that the molar ratio between the function carried by the resin and the metal present in the solution to be treated is between 1 and 30, preferably between 1 and 15 and, more particularly, between 1 and 5.
  • the adsorption step can be carried out at atmospheric pressure or under reduced pressure, and, optionally in the presence of a solvent inert with respect to the hydrogen halide H-Hal present in trace amounts in the middle. It is recommended to use alkanes (preferably C 6 and C 7 ), and aromatic solvents (toluene, xylene or chlorobenzene).
  • the solid adsorbent on the surface of which the catalytic metal is adsorbed is separated from the distillation pellet by any suitable means of liquid / solid separation such as filtration, centrifugation or sedimentation. Metal is then separated from the adsorbent by any physicochemical means compatible with said adsorbent.
  • the recovery process further comprises, after step (1) during which the reaction medium is distilled in order to separate the product formed from a liquid distillation pellet comprising the by-products. and the catalytic metal or its derivatives, a step (2) of bringing the liquid pellet into contact with water in the presence, optionally, of an organic solvent inert with respect to H-Hal formed, in order to obtain an aqueous phase and an organic phase and hydrolyze said pellet.
  • a step (2) of bringing the liquid pellet into contact with water in the presence, optionally, of an organic solvent inert with respect to H-Hal formed, in order to obtain an aqueous phase and an organic phase and hydrolyze said pellet.
  • Hydrolysis can be carried out in an acidic or basic medium. If the reaction is carried out in an acid medium, the aqueous solution used as reagent can be pre-acidified (with H-Hal for example) or consist only of demineralized water. The pH of the solution then changes during the reaction to values below 7. In this case, it is possible to neutralize the aqueous phase at the end of hydrolysis by adding a base.
  • the hydrolysis is preferably carried out in a basic medium so that all of the H-Hal is eliminated. It is recommended to pour the pellet on a foot of aqueous solution.
  • the hydrolysis can be carried out at temperatures ranging from -15 ° C to 80 ° C.
  • the reaction being exothermic, it is preferred to carry out the casting of the pellet at moderate temperatures of between -10 and 30 ° C. Temperature control may be necessary.
  • the water used for hydrolysis can be introduced in the form of ice or an ice / salt mixture.
  • the medium obtained is two-phase consisting of an organic phase and an aqueous phase.
  • the reaction is carried out in a wide range of temperatures preferably ranging from -10 ° C. to 100 ° C., operating under atmospheric pressure or under a pressure higher than atmospheric pressure which can reach or even exceed 20.10 5 Pa.
  • the amount of the allyl derivative of formula (VI) used is preferably from 1 to 2 moles per 1 mole of organosilicon compound.
  • the amount of catalyst (s) (i) expressed by weight of transition metal taken from the group formed by Co, Ru, Rh, Pd, Ir, and Pt it is in the range from 1 to 10,000 ppm, preferably ranging from 10 to 2000 ppm and more preferably ranging from 30 to 1000 ppm, based on the weight of organosilicon compound of formula (V) or (XI).
  • the quantity of promoter (s) (2i), when one or more is used, expressed in number of moles of promoter (s) per gram atom of transition metal taken from the group formed by Co, Ru, Rh, Pd , Ir and Pt, is in the range from 0.1 to 1000, preferably ranging from 0.5 to 500 and more preferably ranging from 1 to 300.
  • the diorganohalososilpropyl derivative of formula (VII) or the derivative of monoorganoxydiorganosilylpropyl of formula (IX) is obtained with a molar yield at least equal to 80% based on the starting organosilicon compound of formula (V) or (XI).
  • Step (b) consists in reacting the diorganohalogénosilylpropyle derivative of formula (VII) with the alcohol of formula (VIII).
  • Step (a ') consists in reacting the hydrogenosilane of formula (V) with the alcohol of formula (VIII).
  • each of these alkoxylation steps is carried out in a manner known per se according to an alcoholysis process such as that described for example in J. Amer.Chem.Soc.3601 (1960).
  • the reaction can be carried out, and this is a first implementation arrangement, in the presence of a base to neutralize the halogen acid formed.
  • a base to neutralize the halogen acid formed.
  • bases can be used, in particular tertiary amines such as, for example, trialkylamines; suitable bases of this type are for example triethylamine, tributylamine or diisopropylethylamine.
  • the base can be used either in stoichiometric quantities, or in excess when its elimination is then easy to carry out, or still in quantities which are less than stoichiometry.
  • the base used may advantageously make it possible to neutralize the residual amount of halogenated acid formed present in the reaction medium and which could not have been removed by the methods described below; in this particular context, in addition to tertiary amines, metal aikoxides derived from an alkali metal (such as sodium) and a lower C1-C4 aliphatic alcohol (such as methanol or ethanol).
  • the reaction can also be carried out in the presence of an organic solvent which can be, for example, a lower C1-C4 aliphatic alcohol and in particular the alcohol of formula (VIII) used to carry out the alcoholysis reaction.
  • reaction can also be carried out, and this is a second implementation provision, in the absence of a basis.
  • This second arrangement is preferred.
  • the elimination of the halogenated acid formed from the reaction medium will be favored by suitable methods which may consist of:
  • reaction can optionally be carried out in an inert organic solvent, of the aprotic type and slightly polar, such as aliphatic and / or aromatic hydrocarbons; solvents of this type which are suitable are linear or cyclic alkanes, such as for example pentane, hexane, cyclohexane, and aromatic hydrocarbons such as for example toluene, xylenes.
  • solvents of this type which are suitable are linear or cyclic alkanes, such as for example pentane, hexane, cyclohexane, and aromatic hydrocarbons such as for example toluene, xylenes.
  • the reaction is carried out over a wide range of temperatures, preferably from 0 ° C. to 160 ° C.
  • the alcohol molar ratio of formula (VIII) / silica compound of formula (VII) or silane of formula (V) is preferably:
  • reaction temperature is advantageously situated in a temperature range from 60 ° C to 160 ° C, and the alcohol molar ratio of formula (VIII) / compound silicic acid of formula (VII) or silane of formula (V) is advantageously situated in the range from 3 to 23.
  • reaction temperature is meant the boiling temperature of the reaction medium.
  • This temperature depends on the composition of the medium and is regulated, in a manner known per se, by the heating power supplied to the medium and by the flow rate of the alcohol of formula (VIII) entering the reaction medium.
  • the starting reaction medium containing all the ingredients except the alcohol of formula (VIII), can be preheated to a temperature ranging from 60 ° C. to 160 ° C. or to a higher temperature.
  • the heating power is adjusted so that the temperature equilibrates to a value situated in the temperature zone mentioned above which allows on the one hand to bring the alcohol to the boil and on the other hand, by bringing this alcohol out of the medium, to entrain the halogen acid formed.
  • the flow rate and the duration of introduction of the alcohol of formula (VIII) are adjusted so as to allow a progressive elimination of the halogen acid from the medium, thus giving the reaction the time it needs to take place.
  • the duration of introduction of the alcohol of formula (VIII) is between 30 minutes and 10 hours.
  • an alcohol of formula (VIII) is used in the anhydrous state, that is to say an alcohol whose water content is less than 1000 ppm and ranges from preferably in the range of 10 to 600 ppm.
  • the reaction is carried out in the absence of a base, at a 03/048169
  • step (b) or (a ′) can be carried out without disadvantage by using, as the starting alcohol of formula (VIII), an alcohol reagent consisting in all or part of the alcohol-based distilled mixture of formula (VIII) and of halogenic acid resulting from the discontinuous production of a previous operation, with possible additional addition of alcohol of formula (VIII) new. It is also possible to carry out the reaction in a reactor operating continuously, semi-continuously or discontinuously.
  • the monoorganoxydiorganosilylpropyl derivative of formula (IX) or the monoorganoxydiorganosilane of formula (XI) is obtained with a molar yield at least equal to 60%, based on the reagent of formula (VII) or the starting halosilane of formula (V) .
  • Step (c) consists in directly reacting the monoorganoxydiorganosilylpropyl derivative of formula (IX) with a metal polysulfide of formula (X).
  • the anhydrous metal polysulphides of formula (X) are prepared by reaction of an alkaline sulphide, optionally containing water of crystallization, of formula 2 S (XIII) where the symbol M has the meaning given above ( alkali metal), with elemental sulfur, operating at a temperature ranging from 60 ° C to 300 ° C, optionally under pressure and optionally still in the presence of an anhydrous organic solvent.
  • the alkali sulfide M 2 S used is the industrially available compound which is generally in the form of a hydrated sulfide; an alkali sulfide of this type which is very suitable is the commercially available sulfide Na 2 S which is a hydrated sulfide containing 55 to 65% by weight of Na 2 S.
  • an alkali sulfide of this type which is very suitable is the commercially available sulfide Na 2 S which is a hydrated sulfide containing 55 to 65% by weight of Na 2 S.
  • the anhydrous metal polysulfides of formula (X) are prepared beforehand from an alkali sulfide M 2 S in the form of a hydrated sulfide, according to a process which consists in linking the following operating phases (1) and (2): • phase (1), where the hydrated alkaline sulphide is dehydrated by applying the appropriate method which makes it possible to eliminate the water of crystallization while retaining the alkali sulfide in the solid state, for the duration of the dehydration phase;
  • phase (2) where a mole of dehydrated alkali sulfide obtained is then brought into contact with n (x-1) moles of elemental sulfur, operating at a temperature ranging from 20 ° C. to 120 ° C. , optionally under pressure and possibly also in the presence of an anhydrous organic solvent, the aforementioned factor n being in the range from 0.8 to 1.2, and the symbol x being as defined above.
  • phase (1) As the dehydration protocol which is well suited, mention will be made in particular of the drying of the hydrated alkali sulfide, operating under a partial vacuum ranging from 1.33 ⁇ 10 2 Pa to 40 ⁇ 10 2 Pa and bringing the compound to dry at a temperature ranging from 70 ° C to 85 ° C at the start of drying, then gradually raising the temperature during drying from 70 ° C to 85 ° C until the zone reaches from 125 ° C to 135 ° C, following a program providing for a first temperature rise from + 10 ° C to + 15 ° C after a first period varying from 1 hour to 6 hours, followed by a second rise at a temperature of + 20 ° C to + 50 ° C after a second period varying from 1 hour to 4 hours.
  • phase (2) as the sulfurization protocol which is very suitable, mention will be made of carrying out this reaction in the presence of an anhydrous organic solvent; suitable solvents are in particular anhydrous lower C1-C4 aliphatic alcohols, for example methanol or anhydrous ethanol.
  • suitable solvents are in particular anhydrous lower C1-C4 aliphatic alcohols, for example methanol or anhydrous ethanol.
  • step (c) To return to carrying out step (c), the latter is carried out over a wide range of temperatures preferably ranging from 50 ° C. to 90 ° C., preferably still operating in the presence of an organic solvent and, in this context, use will advantageously be made of the alcohols mentioned above with regard to the conduct of phase (2).
  • the product M-A, and in particular the halide -Hal, formed during the reaction is generally eliminated at the end of the stage, for example by filtration.
  • the bis- (monoorganoxydiorganosilylpropyl) polysulphide of formula (I) formed is obtained with a molar yield at least equal to 80%, based on the starting monoorganoxydiorganosilylpropyl derivative of formula (IX).
  • This example describes the preparation of bis (monoethoxydimethylsilylpropyl) tetrasulfide of form (III) in which the number x is centered on 4.
  • the temperature of the mixture is adjusted to 20 ° C. using the thermal fluid circulating in the double jacket.
  • the reaction mixture is then distilled under vacuum (approximately 35.10 2 Pa) at approximately 40 ° C to obtain two main fractions: ⁇ the light (allyl chloride 2 and traces of dimethylhydrogenochlorosilane 1, accompanied essentially by chloropropyldimethylchlorosilane 3; ⁇ chloropropyldimethylchlorosilane 3, with a molar purity greater than 98%, a distillation residue consisting of heavier products and catalyst remains: molar yield: 85%.
  • the amount of water removed is 17.2 g, which corresponds to a humidity of 39.5% by weight.
  • the dried Na 2 S (26 g), according to the protocol described above, is suspended in 400 ml of ethanol, and transferred, by suction, to a stirred glass reactor of one liter, double wrapped, equipped with a condenser with possibility of reflux.
  • 31 g of sulfur and 200 ml of anhydrous ethanol are introduced into this reactor.
  • the temperature of the mixture is brought to approximately 80 ° C. (low boiling of the ethanol), and it is stirred at 600 rpm.
  • the mixture is maintained at 80 ° C for 2 hours. Gradually, the solids (Na 2 S and sulfur) disappear and the mixture changes from yellow to orange, then to brown.
  • the mixture is homogeneous at 80 ° C.: approximately 58 g of anhydrous Na 2 S 4 (0.33 mol) are available in 600 ml of ethanol
  • the filtrate is reintroduced into the reactor to be distilled there under reduced pressure (approximately 20 ⁇ 10 2 Pa) in order to remove the ethanol, and any light products.
  • 114 g of pellet are recovered, which corresponds to bis- (monoethyoxydimethylsilylpropyl) tetrasulfide, dosed at 97% purity (molar).
  • a mass yield of bis- (monoethyoxy-dimethylsilylpropyl) tetrasulfide is obtained of 87%.
  • a check by 1 H NMR, by 29 NMR and by 13 C NMR makes it possible to verify that the structure obtained complies with formula (III) given in the description.
  • Example 1 The operating conditions of Example 1, part 2) were reproduced, but starting from ethanol, the water content of which is of the order of 1600 ppm. We obtain: a conversion rate of chloropropyldimethylchlorosilane 3 of
  • This example describes a step (b) in which the alcohol molar ratio of formula (VIII) / silicic compound of formula (VII) is lowered.
  • This example describes a step (b) in which the alcohol molar ratio of formula (VIII) / silica compound of formula (VII) is further lowered.
  • EXAMPLE 5 This example describes a step (b) in which part of the unreacted alcohol is reused for a new batch operation.
  • the second phase we continue to introduce ethanol recycled from the previous operation until stocks are exhausted, but the unreacted ethanol is kept for recycling during the next operation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Silicon Polymers (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP02799785A 2001-12-06 2002-12-06 Verfahren zur herstellung von polyschwefelmonoorganooxysilanen Withdrawn EP1461344A1 (de)

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FR0115768A FR2833264B1 (fr) 2001-12-06 2001-12-06 Procede d'obtention de monoorganoxysilanes polysulfures
FR0115768 2001-12-06
FR0210145A FR2833265B1 (fr) 2001-12-06 2002-08-09 Procede d'obtention de monoorganoxysilane polysulfures
FR0210145 2002-08-09
PCT/FR2002/004204 WO2003048169A1 (fr) 2001-12-06 2002-12-06 aROCEDE D'OBTENTION DE MONOORGANOXYSILANES POLYSULFURES.

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FR2863614B1 (fr) * 2003-12-12 2006-04-28 Rhodia Chimie Sa Procede de preparation d'organo alcoxydialkylsilane
FR2871802B1 (fr) * 2004-06-16 2006-07-21 Rhodia Chimie Sa Procede de preparation d'un omega-halogenoalkyl dialylhalogenosilane
US8580994B2 (en) 2008-03-06 2013-11-12 Dow Corning Corporation Process for the preparation of haloalkylalkoxysilanes and haloalkylhalosilanes
JP2021178786A (ja) * 2020-05-13 2021-11-18 信越化学工業株式会社 ジメチルクロロシラン化合物の製造方法
EP4112625A1 (de) 2021-06-30 2023-01-04 LANXESS Deutschland GmbH Organosilylpolysulfide und diese enthaltende kautschukmischungen
EP4112624A1 (de) 2021-06-30 2023-01-04 LANXESS Deutschland GmbH Organosilylpolysulfide und diese enthaltende kautschukmischungen

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EP1621543B1 (de) 2009-03-25
US20110105780A1 (en) 2011-05-05
ATE426608T1 (de) 2009-04-15
DE60231759D1 (de) 2009-05-07
JP4090993B2 (ja) 2008-05-28
FR2833265B1 (fr) 2006-02-10
FR2833265A1 (fr) 2003-06-13
AU2002364429A1 (en) 2003-06-17
EP1621543A1 (de) 2006-02-01
WO2003048169A1 (fr) 2003-06-12
JP2005511700A (ja) 2005-04-28

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