CA1144936A - Bis-(silyl-ethyl)-oligosulphides and a process for their production - Google Patents
Bis-(silyl-ethyl)-oligosulphides and a process for their productionInfo
- Publication number
- CA1144936A CA1144936A CA000342418A CA342418A CA1144936A CA 1144936 A CA1144936 A CA 1144936A CA 000342418 A CA000342418 A CA 000342418A CA 342418 A CA342418 A CA 342418A CA 1144936 A CA1144936 A CA 1144936A
- Authority
- CA
- Canada
- Prior art keywords
- silane
- vinyl
- ethoxy
- sulphur
- oligosulphide
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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 System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- 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 System
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
Abstract
ABSTRACT OF THE DISCLOSURE
Bis-(silyl-ethyl)-oligosulphide obtained by reacting a vinyl silane having the formula (CH2=CH)m-SiR?R4-(m+n) wherein R represents chlorine, iodine, C1-C3-alkoxy, 2-methoxy-ethoxy, 2-ethoxy-ethoxy or hydroxy, R1 represents C1-C3-alkyl, phenyl or C5-C7-cycloalkyl, n is 0, 1 or 2, m is 1 or 2 and m + n is 1, 2 or 3, with sulphur and, when required, with hydrogen sulphide in a molar ratio ranging from 1:2.5 to 1:10 and of vinyl silane to hydrogen sulphide from 1:0 to 0:5 at a temperature between approx-imately 100 and 200°C under a pressure ranging from 1 to 25 bars (total pressure at the reaction temperature) and in the presence of Sulphidation catalysts and when required hydrolysis or partial hydrolysis of the reaction product. The corresponding process of production and the use of a bis-(silyl-ethyl)-oligosulphide as a reinforcing additive (adhesion promoter) in a crosslinkable rubber mixture containing a silicate filler and when required carbon black as well as sulphur and other conventional mixture components are also disclosed.
Bis-(silyl-ethyl)-oligosulphide obtained by reacting a vinyl silane having the formula (CH2=CH)m-SiR?R4-(m+n) wherein R represents chlorine, iodine, C1-C3-alkoxy, 2-methoxy-ethoxy, 2-ethoxy-ethoxy or hydroxy, R1 represents C1-C3-alkyl, phenyl or C5-C7-cycloalkyl, n is 0, 1 or 2, m is 1 or 2 and m + n is 1, 2 or 3, with sulphur and, when required, with hydrogen sulphide in a molar ratio ranging from 1:2.5 to 1:10 and of vinyl silane to hydrogen sulphide from 1:0 to 0:5 at a temperature between approx-imately 100 and 200°C under a pressure ranging from 1 to 25 bars (total pressure at the reaction temperature) and in the presence of Sulphidation catalysts and when required hydrolysis or partial hydrolysis of the reaction product. The corresponding process of production and the use of a bis-(silyl-ethyl)-oligosulphide as a reinforcing additive (adhesion promoter) in a crosslinkable rubber mixture containing a silicate filler and when required carbon black as well as sulphur and other conventional mixture components are also disclosed.
Description
114~3;36 The present invention relates to bis(silylethyl)oligo-sulphides, their production and use as additives for rubber mix-tures containing silica.
It is known that bis-(alkoxysilylalkyl)-oligosulphides can be produced from the corresponding alkoxy silyl alkyl mercap-tan by direct reaction with sulphur (German Patent No. 2,405,758).
The same oligosulphidic silanes can be obtained even more simply and conveniently from the alkoxy silyl alkyl halides by a single reaction with, in particular, alkali metal hydrogen sulphides and sulphur. In this case, excess hydrogen sulphide is formed (Ger-man Offenlegungsschrift No. 2,542,534). It is also known that bis-(alkoxysilylalkyl)-oligosulphides can be produced from the corresponding disulphides by reaction with sulphur at temperatures in the range from 100 to 200C (German Offenlegungsschrift No.
It is known that bis-(alkoxysilylalkyl)-oligosulphides can be produced from the corresponding alkoxy silyl alkyl mercap-tan by direct reaction with sulphur (German Patent No. 2,405,758).
The same oligosulphidic silanes can be obtained even more simply and conveniently from the alkoxy silyl alkyl halides by a single reaction with, in particular, alkali metal hydrogen sulphides and sulphur. In this case, excess hydrogen sulphide is formed (Ger-man Offenlegungsschrift No. 2,542,534). It is also known that bis-(alkoxysilylalkyl)-oligosulphides can be produced from the corresponding disulphides by reaction with sulphur at temperatures in the range from 100 to 200C (German Offenlegungsschrift No.
2,360,~71). All the above-mentioned oligosulphides contain up to at most 6 sulphur atoms forming as it were a bridge between the two alkyl groups attached to the silicon, the alkyl groups containing from 1 to 10 carbon atoms. Finally, it is known that silyl alkyl thioethers can be obtained from vinyl silanes by reaction with hydrogen sulphide (German Auslegeschrift No.
1,000,817).
Oligosulphidic silanes have acquired considerable sig-nificance as additives in rubber mixtures containing silica filler inter alia for improving the mechanical properties of the vulcanisates (German Patent No. 2,255,577). It is also possible to introduce sulphur-free silanes containing unsaturated organic groups as ligand on the silicon atom into mixtures based on cer-tain rubbers. It is also known that silyl alkyl thioethers do not produce any advantageous rubber properties in vulcanisates and that, among other disadvantages, mercapto silanes give off an intense, very unpleasant odour.
The present invention provides a process for the pro-duction of sulphur-containing silanes which may be easily and effectively incorporated for example into rubber mixtures con-taining silicate fillers and which inter alia impart particu-larly favourable properties to the vulcanisates obtained there-from.
It has now keen found that bis-(silylethyl)-oligosul-phides containing up to more than 7 sulphur atoms in the molecule and corresponding to the average formula:
~R4 (m+n) Rn Si[CH2CH2]m~ 2Smx in which R represents chlorine, bromine, iodine, Cl-C3-alkoxy, 2-methoxy ethoxy, 2-ethoxy ethoxy or hydroxy, Rl represents Cl-C3-al]~yl, phenyl or C5-C7-cycloalkyl, n = 0, 1 or 2, _ = 1 or 2, _ + n = 1, 2 or 3, and x = 2.0 to 8.0, can be obtained by react-ing a vinyl silane corresponding to the following formula (CH2=CH)m~SiRnR4-(m+n) II
in which R, Rl, n and m are as defined above, wlth sulphur and in the absence or presence of hydrogen sulphide in molar ratio of vinyl silane to sulphur of from 1:2.5 to 1:10 vinyl silane to hydrogen sulphide of from 1:0 to 1:5 at temperatures in the range from about 100 to 200C under a pressure of from 1 to 25 bars (total pressure at the reaction temperature) and in the presence of sulphidation catalysts and when re~uired hydrolysis or partial hydrolysis of the reaction product.
It has been found that the products obtainéd by the process according to the invention are not identical with the known, above-mentioned oligosulphidic silanes (German Offenlegungs-schrift No. 2,542,534). Compared with the additives according to the above-mentioned German Patent No. 2,255,577, the silanes produced by the process according to the invention enable substan-4~3~36 tially the same outstanding and, in some cases, even better results to be obtained in rubber mixtures and their vulcanisates.
In general terms, the process effects the addition of sulphur with organosilanes containing ethylenically unsaturated organic groups and is preferably carried out under autogenous pressure and elevated temperature. During the reaction, which may even be carried out in the presence of hydrogen sulphide, the elemental sulphur is apparently incorporated into the organo-silane molecule in such a way that sulphur bridges containing more than one sulphur atom in the molecule, depending on the quantity of sulphur used, are formed.
It is assumed that, where in particular, relatively large quantities of sulphur are used, some of the sulphur is incorporated in the form of chain branching of the sulphur bridge between the silyl alkyl groups. Even if hydrogen sulphide is not additionally used, sulphur-containing compounds and compound mixtures are evidently formed and, by comparison with known oligo-sulphidic silanes, produce equally good and, in some cases, even better processing properties of rubber moulding compositions and also rubber properties of vulcanisates produced therefrom, the reactions both with and also without hydrogen sulphide being carried out under pressure and a temperature which is generally above the boiling temperature of the corresponding silane start-ing compounds.
It is possible by the process according to the invention to produce silanes containing up to 8 sulphur atoms in the mole-cule, even if only one unsaturated organic group is available per silane starting molecule. However, it has been found that the quantity of sulphur used can reach an optimum in terms of practi-cal application. In general, this optimum quantity amounts to approximately 7.5 moles of elemental sulphur per mole of silane used and is governed to some extent by the particular silane ~1~4~36 reacted. A quantity of sulphur distinctly in excess of this optimum quantity does not afford any significant advantages in texms of rubber technology, but only makes the reaction mixtures difficult to work up because the unreacted sulphur or the sul-phur which is separated again after cooling of the reaction products has to be removed, for example by filtration.
Of the total sulphur content of the synthesised com-pounds, the analytically determinable polysulphidical~y bound sulphur is particularly effective in terms of practical applica-tion, particularly in rubber technology.
NMR-spectra were recorded from the silanes produced in accordance with the invention. Their evaluation suggests the conclusion that, in consequence of the reaction without hydrogen sulphide, the arrangement of the sulphur atoms in the silanes is far less defined and established than where the alternative reaction is adopted, in respect of which it is assumed that the addition of hydrogen sulphide with the double bond of the unsatur-ated compounds with primary formation of the corresponding mer-captan takes place in a first stage and the following addition of the mercaptan primarily formed with a double bond of another molecule with simultaneous incorporation of elemental sulphur into the chain takes place in a second stage.
It has been found that, even at greatly increased temp-erature and pressure, the above-mentioned reactions do not take place to any significant extent or at a sufficient velocity or in such a favourable direction in terms of rubber technology if they are carried out in the absence of a catalyst. It has been found that basically acting substances, such as alkalis, amines, quaternary ammonium compounds and, above all, sodium ethylate, potassium ethylate, sodium methylate, sodium isopropylate, etc., are particularly suitable catalysts. Even where hydroquinones are used as catalysts, equally good results are obtained, particu-larly where hydroquinone itself is used.
~1~4~36 The temperature may be varied within relatively wide limits of from about 100 to 210C without adversely affecting the quality of the reaction products and, as usual, is related to the reaction time. A combination of a reaction temperature of 150C and a reaction time of 7 hours has proved to be particu-larly advantageous. selow a temperature of about 100C, the reaction gives a product with no value in terms of rubber tech-nology. At reaction temperatures distinctly above 200C, for example at around 250C, the reaction products begin to decompose.
The reaction pressure, i.e. the total pressure pre-vailing at the particular reaction temperature, can also vary within wide limits, i.e. between about 1 and 25 bars. It may be adjusted for example by the introduction of hydrogen sulphide under pressure. In general, the autogenous pressure is sufficient.
The molar ratio of silane to sulphur is selected accord-ing to the required amount of sulphur in the molecule of the silane according to the invention and amounts to between 1:2.5 and 1:10.
Where hydrogen sulphide is additionally used, the molar ratio of vinyl silane to hydrogen sulphide may amount to between about 1:0.1 (1:0 signifies the absence of H2S and 1:5.
During the reaction, it is particularly important to ensure, by using suitable apparatus, that the elemental sulphur which is liquid at the elevated reaction temperature is more effectively reacted with the silane by intensive mixing. On completion of the reaction, the reaction mixture is left to cool with continued stirring and further process in the same way as described in the Examples.
The following are examples of vinyl silanes correspond-ing to formula II: vinyl trichlorosilane, vinyl methyl dichloro-silane, vinyl phenyl dichlorosilane, vinyl diphenyl chlorosilane, vinyl dimethyl chlorosilane, vinyl trimethoxy silane, vinyl ~ 1~4~336 triethoxy silane, vinyl tripropoxy silane, vinyl-tris-l-propoxy silane, vinyl-tris-(2-methoxyethoxy)-silane, divinyl dichloro-silane, divinyl dibromosilane and diiodosilane, divinyl diethoxy silane, divinyl dimethoxy silane, divinyl-di-i-propoxy silane, divinyl-di-_-propoxy silane, vinyl methyl dimethoxy silane, vinyl ethyl diethoxy silane, vinyl methyl-di-(2-ethoxy-ethoxy)-silane, vinyl diethyl ethoxy silane, vinyl dimethyl methoxy silane, vinyl diethyl-2-methoxy ethoxy silane, vinyl phenyl diethoxy silane, vinyl diphenyl methoxy silane, vinyl cyclohexyl diethoxy silane, vinyl cyclopentyl diethoxy silane and vinyl cycloheptyl dimethoxy silane. It is preferred to use monovinyl silanes.
The optional hydrolysis or partial hydrolysis of the reaction products obtained in accordance with the invention is carried out by methods known per se, hydrolysable groups R
being converted into hydroxy groups.
The present invention will be further illustrated, by way of the following Examples, in conjunction with the accompanying drawings, in which:
Figs. 1 to 6 are NMR-spectra of the production of the Examples.
All the 60 MHz H -NMR-spectra reproduced in the Figures were recorded under the following conditions: solvent CDC13~; temperature 37C; filter band width 4 Hz; R.F. field 0.02 mG; recording time 250 s; recording range 500 Hz; spectrum amplitude 8. The internal standard was tetramethyl silane (~ - value = 0). The curve of the NMR-spectrum includes the integration curve which is also reproduced.
EXAMPLE. 1 In a 1.5 litre capacity stirrer-equipped vessel, 300 g of sulphur in powder form (corresponding to 9.37 moles) are dispersed in 238 g of vinyl triethoxy silane (1.25 moles~
1~4~36 by means of a blade stirrer. The resulting dispersion is introduced into a 2-liter capacit~ pressure vessel equipped with an automatic stirrer. Following the addition of 12 g of hydroquinone as catalysts, the pressure vessel is closed and its contents heated to 150C over a period of 30 minutes during which the pressure rises to around 5 bars. The reaction is continued under these condi-- 6a -tions for 7 hours with intensive stirring. The reaction mixture is then cooled and the contents of thevessel relieved of pressure.
The unreacted sulphur is filtered off. The residual reaction product is a pale reddish-brown, clear slightly oily liquid which has a total sulphur content of 39.1% by weight and a polysulphur content of 24.9% by weight. Unsaturated carbon atoms emanating from the vinyl groups can no longer he detected.
Practical testing as in Example 7 of the reaction pro-duct in a styrene-butadiene rubber test mixture conkaining a silica filler both with conventional crosslinking with sulphur and also with elemental-sulphur-free crosslinking with the sulphur-containing reaction product revealed a considerable increase in tensile strength by comparison with a conventional oligosulphidic silane, coupled with equally good or improved moduli and dis-tinctly increased crosslinking kinetics.
The procedure was as in Example l, except that, before l heating, hydrogen sulphide was introduced into the autoclave up ~;
to a pressure of lO bars. The reaction time and temperature were the same. The total sulphur content of thefiltered, clear reaction product now amounted to 27.6% by weight and the content of polysulphidic sulphur to 17.6% by weight. The NMR-spectrum of the reaction product is shown in Figure l.
Practical rubber testing in accordance with Example 7 showed that, again by comparison with a conventional oligosul-phidic silane, the reaction product produced with the additional use of H2S brings about a distinct increase in the crosslinking kinetics both where vulcanisation is carried out with sulphur and where crosslinking is carried out in the absence of elemental sulphur. At the same time, the tensile strength (DIN 53 504) of the vulcanisate or crosslinked product is distinctly increased whereas the measured values for the moduli, shock elasticity (ASTM D 624) and tear propagation resistance (DIN 53 507) reach or almost reach the already very good values of the comparison silane.
If the procedure of Example 1 is repeated under the same conditions, but with vinyl silaneand sulphur in a molar ratio of 1:10, a reaction product is obtained which contains 33.~ by weight of total sulphur and 18.8% by weight of polysulphidic sulphur and of which the NMR-spectrum is shown in Figure 2. The practical rubber testing of this reaction product in accordance with Example 7 again shows improved test values by comparison with the known oligosulphidic silane. The increase in thecross-linking kinetics and a reduction in the incubation time by the reaction product both with sulphur-containing and with sulphur-free crosslinking of the shape rubber compositions are again remarkable.
If the procedure of Example 3 is repeated with only the reaction time being increased (to 21 hours), a reaction product is obtained which has an increased content of polysulphidic sul-phur (20.1% by weight), but a lower total sulphur content (30.7~
by weight). The NMR-spectrum of this product is shown in Figure
1,000,817).
Oligosulphidic silanes have acquired considerable sig-nificance as additives in rubber mixtures containing silica filler inter alia for improving the mechanical properties of the vulcanisates (German Patent No. 2,255,577). It is also possible to introduce sulphur-free silanes containing unsaturated organic groups as ligand on the silicon atom into mixtures based on cer-tain rubbers. It is also known that silyl alkyl thioethers do not produce any advantageous rubber properties in vulcanisates and that, among other disadvantages, mercapto silanes give off an intense, very unpleasant odour.
The present invention provides a process for the pro-duction of sulphur-containing silanes which may be easily and effectively incorporated for example into rubber mixtures con-taining silicate fillers and which inter alia impart particu-larly favourable properties to the vulcanisates obtained there-from.
It has now keen found that bis-(silylethyl)-oligosul-phides containing up to more than 7 sulphur atoms in the molecule and corresponding to the average formula:
~R4 (m+n) Rn Si[CH2CH2]m~ 2Smx in which R represents chlorine, bromine, iodine, Cl-C3-alkoxy, 2-methoxy ethoxy, 2-ethoxy ethoxy or hydroxy, Rl represents Cl-C3-al]~yl, phenyl or C5-C7-cycloalkyl, n = 0, 1 or 2, _ = 1 or 2, _ + n = 1, 2 or 3, and x = 2.0 to 8.0, can be obtained by react-ing a vinyl silane corresponding to the following formula (CH2=CH)m~SiRnR4-(m+n) II
in which R, Rl, n and m are as defined above, wlth sulphur and in the absence or presence of hydrogen sulphide in molar ratio of vinyl silane to sulphur of from 1:2.5 to 1:10 vinyl silane to hydrogen sulphide of from 1:0 to 1:5 at temperatures in the range from about 100 to 200C under a pressure of from 1 to 25 bars (total pressure at the reaction temperature) and in the presence of sulphidation catalysts and when re~uired hydrolysis or partial hydrolysis of the reaction product.
It has been found that the products obtainéd by the process according to the invention are not identical with the known, above-mentioned oligosulphidic silanes (German Offenlegungs-schrift No. 2,542,534). Compared with the additives according to the above-mentioned German Patent No. 2,255,577, the silanes produced by the process according to the invention enable substan-4~3~36 tially the same outstanding and, in some cases, even better results to be obtained in rubber mixtures and their vulcanisates.
In general terms, the process effects the addition of sulphur with organosilanes containing ethylenically unsaturated organic groups and is preferably carried out under autogenous pressure and elevated temperature. During the reaction, which may even be carried out in the presence of hydrogen sulphide, the elemental sulphur is apparently incorporated into the organo-silane molecule in such a way that sulphur bridges containing more than one sulphur atom in the molecule, depending on the quantity of sulphur used, are formed.
It is assumed that, where in particular, relatively large quantities of sulphur are used, some of the sulphur is incorporated in the form of chain branching of the sulphur bridge between the silyl alkyl groups. Even if hydrogen sulphide is not additionally used, sulphur-containing compounds and compound mixtures are evidently formed and, by comparison with known oligo-sulphidic silanes, produce equally good and, in some cases, even better processing properties of rubber moulding compositions and also rubber properties of vulcanisates produced therefrom, the reactions both with and also without hydrogen sulphide being carried out under pressure and a temperature which is generally above the boiling temperature of the corresponding silane start-ing compounds.
It is possible by the process according to the invention to produce silanes containing up to 8 sulphur atoms in the mole-cule, even if only one unsaturated organic group is available per silane starting molecule. However, it has been found that the quantity of sulphur used can reach an optimum in terms of practi-cal application. In general, this optimum quantity amounts to approximately 7.5 moles of elemental sulphur per mole of silane used and is governed to some extent by the particular silane ~1~4~36 reacted. A quantity of sulphur distinctly in excess of this optimum quantity does not afford any significant advantages in texms of rubber technology, but only makes the reaction mixtures difficult to work up because the unreacted sulphur or the sul-phur which is separated again after cooling of the reaction products has to be removed, for example by filtration.
Of the total sulphur content of the synthesised com-pounds, the analytically determinable polysulphidical~y bound sulphur is particularly effective in terms of practical applica-tion, particularly in rubber technology.
NMR-spectra were recorded from the silanes produced in accordance with the invention. Their evaluation suggests the conclusion that, in consequence of the reaction without hydrogen sulphide, the arrangement of the sulphur atoms in the silanes is far less defined and established than where the alternative reaction is adopted, in respect of which it is assumed that the addition of hydrogen sulphide with the double bond of the unsatur-ated compounds with primary formation of the corresponding mer-captan takes place in a first stage and the following addition of the mercaptan primarily formed with a double bond of another molecule with simultaneous incorporation of elemental sulphur into the chain takes place in a second stage.
It has been found that, even at greatly increased temp-erature and pressure, the above-mentioned reactions do not take place to any significant extent or at a sufficient velocity or in such a favourable direction in terms of rubber technology if they are carried out in the absence of a catalyst. It has been found that basically acting substances, such as alkalis, amines, quaternary ammonium compounds and, above all, sodium ethylate, potassium ethylate, sodium methylate, sodium isopropylate, etc., are particularly suitable catalysts. Even where hydroquinones are used as catalysts, equally good results are obtained, particu-larly where hydroquinone itself is used.
~1~4~36 The temperature may be varied within relatively wide limits of from about 100 to 210C without adversely affecting the quality of the reaction products and, as usual, is related to the reaction time. A combination of a reaction temperature of 150C and a reaction time of 7 hours has proved to be particu-larly advantageous. selow a temperature of about 100C, the reaction gives a product with no value in terms of rubber tech-nology. At reaction temperatures distinctly above 200C, for example at around 250C, the reaction products begin to decompose.
The reaction pressure, i.e. the total pressure pre-vailing at the particular reaction temperature, can also vary within wide limits, i.e. between about 1 and 25 bars. It may be adjusted for example by the introduction of hydrogen sulphide under pressure. In general, the autogenous pressure is sufficient.
The molar ratio of silane to sulphur is selected accord-ing to the required amount of sulphur in the molecule of the silane according to the invention and amounts to between 1:2.5 and 1:10.
Where hydrogen sulphide is additionally used, the molar ratio of vinyl silane to hydrogen sulphide may amount to between about 1:0.1 (1:0 signifies the absence of H2S and 1:5.
During the reaction, it is particularly important to ensure, by using suitable apparatus, that the elemental sulphur which is liquid at the elevated reaction temperature is more effectively reacted with the silane by intensive mixing. On completion of the reaction, the reaction mixture is left to cool with continued stirring and further process in the same way as described in the Examples.
The following are examples of vinyl silanes correspond-ing to formula II: vinyl trichlorosilane, vinyl methyl dichloro-silane, vinyl phenyl dichlorosilane, vinyl diphenyl chlorosilane, vinyl dimethyl chlorosilane, vinyl trimethoxy silane, vinyl ~ 1~4~336 triethoxy silane, vinyl tripropoxy silane, vinyl-tris-l-propoxy silane, vinyl-tris-(2-methoxyethoxy)-silane, divinyl dichloro-silane, divinyl dibromosilane and diiodosilane, divinyl diethoxy silane, divinyl dimethoxy silane, divinyl-di-i-propoxy silane, divinyl-di-_-propoxy silane, vinyl methyl dimethoxy silane, vinyl ethyl diethoxy silane, vinyl methyl-di-(2-ethoxy-ethoxy)-silane, vinyl diethyl ethoxy silane, vinyl dimethyl methoxy silane, vinyl diethyl-2-methoxy ethoxy silane, vinyl phenyl diethoxy silane, vinyl diphenyl methoxy silane, vinyl cyclohexyl diethoxy silane, vinyl cyclopentyl diethoxy silane and vinyl cycloheptyl dimethoxy silane. It is preferred to use monovinyl silanes.
The optional hydrolysis or partial hydrolysis of the reaction products obtained in accordance with the invention is carried out by methods known per se, hydrolysable groups R
being converted into hydroxy groups.
The present invention will be further illustrated, by way of the following Examples, in conjunction with the accompanying drawings, in which:
Figs. 1 to 6 are NMR-spectra of the production of the Examples.
All the 60 MHz H -NMR-spectra reproduced in the Figures were recorded under the following conditions: solvent CDC13~; temperature 37C; filter band width 4 Hz; R.F. field 0.02 mG; recording time 250 s; recording range 500 Hz; spectrum amplitude 8. The internal standard was tetramethyl silane (~ - value = 0). The curve of the NMR-spectrum includes the integration curve which is also reproduced.
EXAMPLE. 1 In a 1.5 litre capacity stirrer-equipped vessel, 300 g of sulphur in powder form (corresponding to 9.37 moles) are dispersed in 238 g of vinyl triethoxy silane (1.25 moles~
1~4~36 by means of a blade stirrer. The resulting dispersion is introduced into a 2-liter capacit~ pressure vessel equipped with an automatic stirrer. Following the addition of 12 g of hydroquinone as catalysts, the pressure vessel is closed and its contents heated to 150C over a period of 30 minutes during which the pressure rises to around 5 bars. The reaction is continued under these condi-- 6a -tions for 7 hours with intensive stirring. The reaction mixture is then cooled and the contents of thevessel relieved of pressure.
The unreacted sulphur is filtered off. The residual reaction product is a pale reddish-brown, clear slightly oily liquid which has a total sulphur content of 39.1% by weight and a polysulphur content of 24.9% by weight. Unsaturated carbon atoms emanating from the vinyl groups can no longer he detected.
Practical testing as in Example 7 of the reaction pro-duct in a styrene-butadiene rubber test mixture conkaining a silica filler both with conventional crosslinking with sulphur and also with elemental-sulphur-free crosslinking with the sulphur-containing reaction product revealed a considerable increase in tensile strength by comparison with a conventional oligosulphidic silane, coupled with equally good or improved moduli and dis-tinctly increased crosslinking kinetics.
The procedure was as in Example l, except that, before l heating, hydrogen sulphide was introduced into the autoclave up ~;
to a pressure of lO bars. The reaction time and temperature were the same. The total sulphur content of thefiltered, clear reaction product now amounted to 27.6% by weight and the content of polysulphidic sulphur to 17.6% by weight. The NMR-spectrum of the reaction product is shown in Figure l.
Practical rubber testing in accordance with Example 7 showed that, again by comparison with a conventional oligosul-phidic silane, the reaction product produced with the additional use of H2S brings about a distinct increase in the crosslinking kinetics both where vulcanisation is carried out with sulphur and where crosslinking is carried out in the absence of elemental sulphur. At the same time, the tensile strength (DIN 53 504) of the vulcanisate or crosslinked product is distinctly increased whereas the measured values for the moduli, shock elasticity (ASTM D 624) and tear propagation resistance (DIN 53 507) reach or almost reach the already very good values of the comparison silane.
If the procedure of Example 1 is repeated under the same conditions, but with vinyl silaneand sulphur in a molar ratio of 1:10, a reaction product is obtained which contains 33.~ by weight of total sulphur and 18.8% by weight of polysulphidic sulphur and of which the NMR-spectrum is shown in Figure 2. The practical rubber testing of this reaction product in accordance with Example 7 again shows improved test values by comparison with the known oligosulphidic silane. The increase in thecross-linking kinetics and a reduction in the incubation time by the reaction product both with sulphur-containing and with sulphur-free crosslinking of the shape rubber compositions are again remarkable.
If the procedure of Example 3 is repeated with only the reaction time being increased (to 21 hours), a reaction product is obtained which has an increased content of polysulphidic sul-phur (20.1% by weight), but a lower total sulphur content (30.7~
by weight). The NMR-spectrum of this product is shown in Figure
3.
Testing of the reaction product in accordance with Example 7 in rubber moulding compositions and vulcanisates again shows good results, such as in particular an increase in the cross-linking velocity and an increase in the tensile strengths after vulcanisation (sulphur~free and sulphur-containing) and, for example, an increase in tear propagation resistance ~DIN 53 507) after sulphur-free crosslinking.
A reaction product is again prepared under the same ~14~936 conditions and using the same quantities as in Examples 1 and 3, but with a ratio of vinyl triethoxy silane to sulphur of 1:5.
It has a total sulphur content of 36.6~ by weight and a polysul-phidic sulphur content of 22.9% by weight. The NMR-spectrum of this reaction product is shown in Figure 4. The high sulphur content of both types gives particularly advantageous results in practical rubber testing (see Example 7): a distinctly increased crosslinking velocity by comparison with the results obtained with the known oligosulphidic silane S;69; also a more favourable crosslinking conversion, particularly where vulcanisation is carried out with sulphur, a distinctly improved tensile strength (DIN 53 504), at least equally good moduli and tear propagation resistances (DIN 53 507) and slight increases in Shore A hardness.
Following the procedure of Example 2, a reaction pro-duct was produced with the following modifications, hydrogen sulphide being additionally used: H2S-pressure 11 bars, reaction temperature 200C (reaction time: 7 hours), vinyl triethoxy silane and sulphur in a molar ratio of 1:10. The reaction pro-duct had a total sulphur content of 25.2 and a polysulphidicsulphur content of 14.5% by weight. Its NMR-spectrum is shown in Figure 5.
The practical rubber testing in accordance with Example 7 of this reaction product shows that the measured values are at the same level as the corresponding values of Example 2, being more favourable in some instances (crosslinking kinetics, tear propagation resistance) and less favourable in others (tensile strength, moduli).
The values of x in the oligosulphides produced in the Examples are as follows:
Examples 1 2 3 4 5 6 .
total sul~hur content 1 39.1 27.6 33.4 30.7 36.6 25.2 x (computed)2) 7 63) 4 5 6.0 5.2 6.9 4.0 1) determined in ~ by analysis 2) sulphur content of -Sx-3) probably mixture of compounds with e.g. -S7- and -Sg-It is emphasized that said values for x are computed values, which result from the total content obtained on the one hand and from the formula I (with the sulphur bridge in the centre of the molecule) on the other.
For the use of the silanes according to the invention and to illustrate their superior effect the following rubber mix-tures and the vulcanizates and crosslinked products produced therefrom were tested as shown in the following Table I and Table II.
3~
. o o ~ ~ , , , , , , ~ ~
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v~ O ~J h Ql ~ ~ ~ O
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,~
ra .c ~ O ~
a~ ~ ~
3 ~, ~ ~D
:>~ ~ o ~ E 3 U~ ~q o O ~ ~ I ~ I I I I ~ ~ o ~ ~ ~1 ~,~ o C~
,a), o ~ ~ ~ ~ I I I I I ~, o o o ~ ~ I I I I I I ~ I ~ c~
o ~J Z o CJ
,1 o o ~ ~ I I II I ~ I
C) C~
~ o o ~1 ~ I I I I ~ I I I ~1 ~`I
X ~ ,C
.~ u E
X ~ o o ~ C~ I I I ~ I I I I
o ~ ~, W ~1 U b~
W V~ ~
C`i o ~ ~ ~ I I ~ I I I I I ~ ~ ~ .c E~ W ~ ~ u .,_1 rl o o ~ ~ I ~ I I I I I I ~ ~ rr w o ~ a ~ oo . O O ~ ~ ~ I I I I I I I ~ ~
~ ,1 ~ ~ o _ ....
,~ o ` ~
c~ - o ~-1 ~1 ~ ~~1 ~1 ~ I ~rl O
E E ~ E E E ~ I ~ o a~ N ~1 V' XXXXX
W W ~1 W W W ~ X ~ U~
~d O O O O o o rl ~ U aJ
JJ .~ O ~, ~ o C ~ ~400 ~00 e~ ~) Z rl U ~,~
~ . v v r~ rt~r-l rl ~ 1 Z P. U a~
.~ h1-~ ~D r.~J
V ~ rl~D O O O O O O ~ V~ ~ E ~ v V~ :~ ~ ~13) U U U U U U U ~ ~r-l N ta Va ~ g ~ U~ ~ 0 ~ ~U~ U~ u ~ ~ ~
a~ u Lt~ X u E E ~ ~ ~ ~5 E l O
~ C ~ r.~ O ,1 ~ r~ r~ d v r~:: O ~1 0 ~r~
0~ ~ ~ ,U~ U 0 ~ a a a a a a ~ ~ o ~ .
E 7, ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ z O V ~ V ~ r u ~) ~0--' V~ N U~ ~n u~ n ~n v~ ~n z ~ ,Q v~ v~
The first half of the rubber mixtures with control mix-ture Vl. according to the prior art and the mixtures according to the invention (use of the silanes of the present invention) in rubber mixtures) El.l to E6.1 with the silanes of Examples 1 to 6 were vulcanized in a conventional manner with sulphur and accelerators. The second half of the rubber mixtures with the control mixture V2. according to a more recent state of the art (see, for example, German Patent 2,536,674, British Patent 1,524,077 or French Patent No. 7,526,913) and with the rubber mixtures according to the present invention El.2 to E6.2 contain-ing the silanes according to the Examples 1 to 6 were cross-linked-without elemental sulphur with the aid of the oligosul-phidic silanes in the presence of accelerators.
The rubber mixtures were tested (for example, for the kinetics of cross-linking) according to DIN 53529 (preliminary standard of October 1972) entitled "Vulkametric" (also known as rheometer testing) (deformation amplitude : 3, testing frequency 3 cycles per minute, testing temperature : 155 C, rheometer of the firm of Monsanto, type MP~). In these tests t 10% represents the reaction time (vulcanizing time) up to a reaction of 10% in minutes and t 90% represents the reaction time up to a corres-ponding reaction of 90%. The aifference t 90% - t 10% is a criterion of the reaction kinetics, shorter times indicating a greater amount of kinetics.
The measurements of the tensile strengths and moduli (both measured in kp per sq cm) of the vulcanizates and cross- `
linking products were carried out according to DIN 53504 (vul-canization and cross-linking temperature 155C). The measurements of the tear propagation resistances and of the Shore A hardnesses were carried out according to DIN 53505. The results are shown in Table II hereinafter.
oo CO
,~
C~l ~ oo ~
U~ ~ ,_ ~ o~ ,`
IY
U~ ~D
~ ~ ~ ~ ~ n ~ o o~ , ~ J ~o CO C~l U~
~ U~ o U~
C~
~D
~i ~ O r~
r ~ ~D
oo ,~
~ o~
P ~ U~
~n~D ,i 1~ 1` o H ~ ~
u~ ~ ~ O~
~ ~ ~ ~ U~
H S~ H t`~
~J a) a) ~ c~
X ~ ~ ~ ,~
JJ
E~ O ~ ~ c~
u~ ~a .
U~ ~ ~ Ul ~C~ ~ GO
~1 ~ ~1 EH ~I c~
~i OD 00 ~ ~ r~, . o~ ~
~ oo ~ ~ ~ ~
C~
, s~
U~ ~ o O ~ ~ JJ 0 ,1 o J- ~ ~10 00 ~ ~ J- O ~ ~
~ o t~ E I a)~ h~:
U~ O i~ rlH ~) JJ JJ O U~~ h~1 0 O~ Cr~ O
~ ~ ~ ~ E aJ u~
Testing of the reaction product in accordance with Example 7 in rubber moulding compositions and vulcanisates again shows good results, such as in particular an increase in the cross-linking velocity and an increase in the tensile strengths after vulcanisation (sulphur~free and sulphur-containing) and, for example, an increase in tear propagation resistance ~DIN 53 507) after sulphur-free crosslinking.
A reaction product is again prepared under the same ~14~936 conditions and using the same quantities as in Examples 1 and 3, but with a ratio of vinyl triethoxy silane to sulphur of 1:5.
It has a total sulphur content of 36.6~ by weight and a polysul-phidic sulphur content of 22.9% by weight. The NMR-spectrum of this reaction product is shown in Figure 4. The high sulphur content of both types gives particularly advantageous results in practical rubber testing (see Example 7): a distinctly increased crosslinking velocity by comparison with the results obtained with the known oligosulphidic silane S;69; also a more favourable crosslinking conversion, particularly where vulcanisation is carried out with sulphur, a distinctly improved tensile strength (DIN 53 504), at least equally good moduli and tear propagation resistances (DIN 53 507) and slight increases in Shore A hardness.
Following the procedure of Example 2, a reaction pro-duct was produced with the following modifications, hydrogen sulphide being additionally used: H2S-pressure 11 bars, reaction temperature 200C (reaction time: 7 hours), vinyl triethoxy silane and sulphur in a molar ratio of 1:10. The reaction pro-duct had a total sulphur content of 25.2 and a polysulphidicsulphur content of 14.5% by weight. Its NMR-spectrum is shown in Figure 5.
The practical rubber testing in accordance with Example 7 of this reaction product shows that the measured values are at the same level as the corresponding values of Example 2, being more favourable in some instances (crosslinking kinetics, tear propagation resistance) and less favourable in others (tensile strength, moduli).
The values of x in the oligosulphides produced in the Examples are as follows:
Examples 1 2 3 4 5 6 .
total sul~hur content 1 39.1 27.6 33.4 30.7 36.6 25.2 x (computed)2) 7 63) 4 5 6.0 5.2 6.9 4.0 1) determined in ~ by analysis 2) sulphur content of -Sx-3) probably mixture of compounds with e.g. -S7- and -Sg-It is emphasized that said values for x are computed values, which result from the total content obtained on the one hand and from the formula I (with the sulphur bridge in the centre of the molecule) on the other.
For the use of the silanes according to the invention and to illustrate their superior effect the following rubber mix-tures and the vulcanizates and crosslinked products produced therefrom were tested as shown in the following Table I and Table II.
3~
. o o ~ ~ , , , , , , ~ ~
~ o ~r C~ ~o . o o ~ ~ , , i , , ~ , ~
v~ O ~J h Ql ~ ~ ~ O
O O ~ ~ I I I I ~ I I
,~
ra .c ~ O ~
a~ ~ ~
3 ~, ~ ~D
:>~ ~ o ~ E 3 U~ ~q o O ~ ~ I ~ I I I I ~ ~ o ~ ~ ~1 ~,~ o C~
,a), o ~ ~ ~ ~ I I I I I ~, o o o ~ ~ I I I I I I ~ I ~ c~
o ~J Z o CJ
,1 o o ~ ~ I I II I ~ I
C) C~
~ o o ~1 ~ I I I I ~ I I I ~1 ~`I
X ~ ,C
.~ u E
X ~ o o ~ C~ I I I ~ I I I I
o ~ ~, W ~1 U b~
W V~ ~
C`i o ~ ~ ~ I I ~ I I I I I ~ ~ ~ .c E~ W ~ ~ u .,_1 rl o o ~ ~ I ~ I I I I I I ~ ~ rr w o ~ a ~ oo . O O ~ ~ ~ I I I I I I I ~ ~
~ ,1 ~ ~ o _ ....
,~ o ` ~
c~ - o ~-1 ~1 ~ ~~1 ~1 ~ I ~rl O
E E ~ E E E ~ I ~ o a~ N ~1 V' XXXXX
W W ~1 W W W ~ X ~ U~
~d O O O O o o rl ~ U aJ
JJ .~ O ~, ~ o C ~ ~400 ~00 e~ ~) Z rl U ~,~
~ . v v r~ rt~r-l rl ~ 1 Z P. U a~
.~ h1-~ ~D r.~J
V ~ rl~D O O O O O O ~ V~ ~ E ~ v V~ :~ ~ ~13) U U U U U U U ~ ~r-l N ta Va ~ g ~ U~ ~ 0 ~ ~U~ U~ u ~ ~ ~
a~ u Lt~ X u E E ~ ~ ~ ~5 E l O
~ C ~ r.~ O ,1 ~ r~ r~ d v r~:: O ~1 0 ~r~
0~ ~ ~ ,U~ U 0 ~ a a a a a a ~ ~ o ~ .
E 7, ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ z O V ~ V ~ r u ~) ~0--' V~ N U~ ~n u~ n ~n v~ ~n z ~ ,Q v~ v~
The first half of the rubber mixtures with control mix-ture Vl. according to the prior art and the mixtures according to the invention (use of the silanes of the present invention) in rubber mixtures) El.l to E6.1 with the silanes of Examples 1 to 6 were vulcanized in a conventional manner with sulphur and accelerators. The second half of the rubber mixtures with the control mixture V2. according to a more recent state of the art (see, for example, German Patent 2,536,674, British Patent 1,524,077 or French Patent No. 7,526,913) and with the rubber mixtures according to the present invention El.2 to E6.2 contain-ing the silanes according to the Examples 1 to 6 were cross-linked-without elemental sulphur with the aid of the oligosul-phidic silanes in the presence of accelerators.
The rubber mixtures were tested (for example, for the kinetics of cross-linking) according to DIN 53529 (preliminary standard of October 1972) entitled "Vulkametric" (also known as rheometer testing) (deformation amplitude : 3, testing frequency 3 cycles per minute, testing temperature : 155 C, rheometer of the firm of Monsanto, type MP~). In these tests t 10% represents the reaction time (vulcanizing time) up to a reaction of 10% in minutes and t 90% represents the reaction time up to a corres-ponding reaction of 90%. The aifference t 90% - t 10% is a criterion of the reaction kinetics, shorter times indicating a greater amount of kinetics.
The measurements of the tensile strengths and moduli (both measured in kp per sq cm) of the vulcanizates and cross- `
linking products were carried out according to DIN 53504 (vul-canization and cross-linking temperature 155C). The measurements of the tear propagation resistances and of the Shore A hardnesses were carried out according to DIN 53505. The results are shown in Table II hereinafter.
oo CO
,~
C~l ~ oo ~
U~ ~ ,_ ~ o~ ,`
IY
U~ ~D
~ ~ ~ ~ ~ n ~ o o~ , ~ J ~o CO C~l U~
~ U~ o U~
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~D
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r ~ ~D
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~ o~
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u~ ~ ~ O~
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~J a) a) ~ c~
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E~ O ~ ~ c~
u~ ~a .
U~ ~ ~ Ul ~C~ ~ GO
~1 ~ ~1 EH ~I c~
~i OD 00 ~ ~ r~, . o~ ~
~ oo ~ ~ ~ ~
C~
, s~
U~ ~ o O ~ ~ JJ 0 ,1 o J- ~ ~10 00 ~ ~ J- O ~ ~
~ o t~ E I a)~ h~:
U~ O i~ rlH ~) JJ JJ O U~~ h~1 0 O~ Cr~ O
~ ~ ~ ~ E aJ u~
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A bis-(silylethyl)-oligosulphide corresponding to the following average formula:
{R4-(m+n) R? Si[CH2CH2]m}2Smx I
in which R represents chlorine, bromine, iodine, C1-C3-alkoxy, 2-methoxy ethoxy, 2-ethoxy ethoxy or hydroxy, R1 represents C1-C3-alkyl, phenyl or C5-C7-cycloalkyl, n = 0, 1 or 2, m = 1 or 2, m +
n = 1, 2 or 3, and x = 2.0 to 8.0 obtained by reacting a vinyl silane corresponding to the following formula (CH2=CH)m-SiR?R4-(m+n) II
in which R, R1, n and m are as defined above, with sulphur and in the absence or presence of a hydrogen sulphide in a molar ratio of vinyl silane to sulphur of from 1:2.5 to 1:10 vinyl silane to hydrogen sulphide of from 1:0 to 1:5 at a temperature in the range from about 100 to 200°C, under a pressure of from 1 to 25 bars (total pressure at the reaction temperature) and in the presence of sulphidation catalysts and when required hydrolysis or partial hydrolysis of the reaction product.
{R4-(m+n) R? Si[CH2CH2]m}2Smx I
in which R represents chlorine, bromine, iodine, C1-C3-alkoxy, 2-methoxy ethoxy, 2-ethoxy ethoxy or hydroxy, R1 represents C1-C3-alkyl, phenyl or C5-C7-cycloalkyl, n = 0, 1 or 2, m = 1 or 2, m +
n = 1, 2 or 3, and x = 2.0 to 8.0 obtained by reacting a vinyl silane corresponding to the following formula (CH2=CH)m-SiR?R4-(m+n) II
in which R, R1, n and m are as defined above, with sulphur and in the absence or presence of a hydrogen sulphide in a molar ratio of vinyl silane to sulphur of from 1:2.5 to 1:10 vinyl silane to hydrogen sulphide of from 1:0 to 1:5 at a temperature in the range from about 100 to 200°C, under a pressure of from 1 to 25 bars (total pressure at the reaction temperature) and in the presence of sulphidation catalysts and when required hydrolysis or partial hydrolysis of the reaction product.
2. An oligosulphide as claimed in claim 1 in which R
is C1-C3 alkoxy.
is C1-C3 alkoxy.
3. An oligosulphide as claimed in claim 1 in which R
is ethoxy.
is ethoxy.
4. An oligosulphide as claimed in claim 1, 2 or 3 in which n is 0 and m is 1.
5. An oligosulphide as claimed in claim 1 in which R
is chlorine.
is chlorine.
6. A crosslinkable rubber mixture containing a silicate filler which also contains a bis-(silylethyl)-oligosulphide as claimed in claim 1, 2 or 3 as a reinforcing additive (adhesion promoter).
7. A process for producing a bis-(silylethyl)-oligosul-phide corresponding to average formula I
{R4-(m+n) R? Si[CH2CH2]m}2Smx I
in which R represents chlorine, bromine, iodine, C1-C3-alkoxy, 2-methoxy ethoxy, 2-ethoxy ethoxy or hydroxy, R1 represents C1-C3-alkyl, phenyl or C5-C7-cycloalkyl, n = 0, 1 or 2, m = 1 or 2, m +
n = 1, 2 or 3, and x = 2.0 to 8.0 which comprises reacting a vinyl silane corresponding to the following formula (CH2=CH)m-SiR?R4-(m+n) II
in which R, R1, n and m are as defined above, with sulphur and in the absence or presence of hydrogen sulphide in a molar ratio of vinyl silane to sulphur of from 1:2.5 to 1:10 and vinyl silane to hydrogen sulphide of from 1:0 to 1:5 at a temperature in the range from about 100 to 200°C under a pressure of from 1 to 25 bars (total pressure at the reaction temperature) and in the pre-sence of sulphidation catalysts.
{R4-(m+n) R? Si[CH2CH2]m}2Smx I
in which R represents chlorine, bromine, iodine, C1-C3-alkoxy, 2-methoxy ethoxy, 2-ethoxy ethoxy or hydroxy, R1 represents C1-C3-alkyl, phenyl or C5-C7-cycloalkyl, n = 0, 1 or 2, m = 1 or 2, m +
n = 1, 2 or 3, and x = 2.0 to 8.0 which comprises reacting a vinyl silane corresponding to the following formula (CH2=CH)m-SiR?R4-(m+n) II
in which R, R1, n and m are as defined above, with sulphur and in the absence or presence of hydrogen sulphide in a molar ratio of vinyl silane to sulphur of from 1:2.5 to 1:10 and vinyl silane to hydrogen sulphide of from 1:0 to 1:5 at a temperature in the range from about 100 to 200°C under a pressure of from 1 to 25 bars (total pressure at the reaction temperature) and in the pre-sence of sulphidation catalysts.
8. A process as claimed in claim 7 in which the reac-tion products are at least partially hydrolysed.
9. A process as claimed in claim 7 or 8 in which the vinyl silane is selected from vinyl trichlorosilane, vinyl methyl dichlorosilane, vinyl phenyl dichlorosilane, vinyl diphenyl chloro-silane, vinyl dimethyl chlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl-tris-i-propoxy silane, vinyl-tris-(2-methoxyethoxy)-silane, divinyl di-chlorosilane, divinyl dibromosilane and diiodosilane, divinyl diethoxy silane, divinyl dimethoxy silane, divinyl-di-i-propoxy silane, divinyl-di-n-propoxy silane, vinyl methyl dimethoxy silane, vinyl ethyl diethoxy silane, vinyl methyl-di-(2-ethoxy-ethoxy)-silane, vinyl diethyl ethoxy silane, vinyl dimethyl methoxy silane, vinyl diethyl-2-methoxy ethoxy silane, vinyl phenyl diethoxy silane, vinyl diphenyl methoxy silane, vinyl cyclohexyl diethoxy silane, vinyl cyclopentyl diethoxy silane and vinyl cycloheptyl dimethoxy silane.
10. A process as claimed in claim 7 or 8 in which the vinyl silane is a monovinyl silane.
11. A process as claimed in claim 7 or 8 in which the vinyl silane is a (C1-C3 alkoxy) vinyl silane.
12. A process as claimed in claim 7 or 8 in which the vinyl silane is trimethoxy vinyl silane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782856229 DE2856229A1 (en) | 1978-12-27 | 1978-12-27 | BIS- (SILYLAETHYL) -OLIGOSULFIDES AND METHOD FOR THE PRODUCTION THEREOF |
| DEP2856229.0-42 | 1978-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1144936A true CA1144936A (en) | 1983-04-19 |
Family
ID=6058431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000342418A Expired CA1144936A (en) | 1978-12-27 | 1979-12-20 | Bis-(silyl-ethyl)-oligosulphides and a process for their production |
Country Status (14)
| Country | Link |
|---|---|
| US (3) | US4408064A (en) |
| JP (1) | JPS5589290A (en) |
| BE (1) | BE880869A (en) |
| BR (1) | BR7908417A (en) |
| CA (1) | CA1144936A (en) |
| CH (1) | CH642377A5 (en) |
| DD (2) | DD147945A5 (en) |
| DE (1) | DE2856229A1 (en) |
| ES (2) | ES486091A1 (en) |
| FR (1) | FR2445336A1 (en) |
| GB (1) | GB2038858B (en) |
| IT (1) | IT1207020B (en) |
| MY (1) | MY8500457A (en) |
| NL (1) | NL188288C (en) |
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| DE3226093A1 (en) * | 1982-07-13 | 1984-01-19 | Degussa Ag, 6000 Frankfurt | ORGANOPOLYSILOXANES CONTAINING SULFONATE GROUPS, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3226091C2 (en) * | 1982-07-13 | 1986-11-20 | Degussa Ag, 6000 Frankfurt | Polymeric di-, tri- or tetrasulfides, process for their preparation and use |
| DE3311340A1 (en) * | 1983-03-29 | 1984-10-11 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING SULFURIZED ORGANOSILICIUM COMPOUNDS |
| DE3346910C1 (en) * | 1983-12-24 | 1985-05-02 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of mercaptoalkylsilanes |
| US4652664A (en) * | 1986-01-03 | 1987-03-24 | Ppg Industries, Inc. | Addition products prepared from mercapto-functional polyhydric alcohols and vinyl-type silanes containing hydrolyzable groups |
| DE3604278C1 (en) * | 1986-02-12 | 1987-06-25 | Teroson Gmbh | Sealant and adhesive |
| DD299589A7 (en) * | 1990-07-13 | 1992-04-30 | Nuenchritz Chemie | PROCESS FOR PREPARING OLIGO [4- (2-ORGANO-ORGANOOXYSILYL ALKYL) -CYCLOHEXAN-1,2-DIYL] -BIS OLIGOSULFIDES |
| US5399739A (en) * | 1994-04-18 | 1995-03-21 | Wright Chemical Corporation | Method of making sulfur-containing organosilanes |
| US5468893A (en) * | 1994-07-08 | 1995-11-21 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| US5405985A (en) * | 1994-07-08 | 1995-04-11 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| ATE225354T1 (en) * | 1996-07-18 | 2002-10-15 | Degussa | MIXTURES OF ORGANILANE POLYSULFANES AND A METHOD FOR PRODUCING RUBBER MIXTURES CONTAINING THESE MIXTURES |
| US5663396A (en) * | 1996-10-31 | 1997-09-02 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| US6403693B2 (en) * | 1999-06-18 | 2002-06-11 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
| JP4663869B2 (en) * | 1999-12-08 | 2011-04-06 | 東レ・ダウコーニング株式会社 | Organic rubber composition |
| JP4663868B2 (en) * | 1999-12-08 | 2011-04-06 | 東レ・ダウコーニング株式会社 | Sulfur-containing organosilicon compound and method for producing the same |
| US6452034B2 (en) | 2000-01-04 | 2002-09-17 | Crompton Corporation | Low-sulfur polysulfide silanes and process for preparation |
| US6518335B2 (en) | 2000-01-05 | 2003-02-11 | Crompton Corporation | Sulfur-containing silane coupling agents |
| US6359046B1 (en) | 2000-09-08 | 2002-03-19 | Crompton Corporation | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
| DE10044989A1 (en) | 2000-09-11 | 2002-03-21 | Bayer Ag | Liquid sulfur-containing oligosiloxanes and their use in rubber compounds |
| US6635700B2 (en) | 2000-12-15 | 2003-10-21 | Crompton Corporation | Mineral-filled elastomer compositions |
| US6433206B1 (en) | 2001-11-05 | 2002-08-13 | Crompton Corporation | Process for preparing silylorganomercaptans |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
| US7687558B2 (en) | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968634B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
| US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
| US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| KR101250300B1 (en) | 2011-04-29 | 2013-04-03 | 한국과학기술연구원 | Functional reinforcing fillers modified with alkenylalkoxysilane and preparing method of the same |
| US9127167B2 (en) | 2011-04-29 | 2015-09-08 | Korea Institute Of Science And Technology | Functional reinforcing fillers modified with alkenylalkoxysilane and preparing method of the same |
| JP2021529871A (en) * | 2018-07-19 | 2021-11-04 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎ Ｖｅｎｎｏｏｔｓｈａｐ | Process for preparing sulfur-containing organic silane polymers |
| JP2022518753A (en) * | 2019-01-25 | 2022-03-16 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Electric energy storage device |
| CN113956376B (en) * | 2021-10-29 | 2023-06-13 | 北京化工大学 | Coupling agent for modifying liquid rubber, preparation method, application and modified white carbon black |
| CN113980366B (en) * | 2021-11-02 | 2022-11-29 | 华南理工大学 | Preparation method of sulfur-containing silane copolymer modified white carbon black-rubber composite material |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1000817B (en) * | 1954-12-15 | 1957-01-17 | Bayer Ag | Process for the preparation of silyl mercaptans and silyl thioethers |
| US3530160A (en) * | 1968-02-09 | 1970-09-22 | Exxon Research Engineering Co | (organo- or hydrolyzable group substituted)3silyl (unsubstituted chloro- or sulfenyl chloride substituted hydrocarbylene) sulfenyl chlorides |
| US3769315A (en) * | 1969-11-19 | 1973-10-30 | Rohm & Haas | Preparation of 3,3'-polythiodipropionic acids and their derivatives |
| US3686326A (en) * | 1970-02-11 | 1972-08-22 | Exxon Research Engineering Co | Allylic sulfide reaction products |
| US3873489A (en) * | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
| BE787691A (en) * | 1971-08-17 | 1973-02-19 | Degussa | ORGANOSILICIC COMPOUNDS CONTAINING SULFUR |
| DE2145057C2 (en) * | 1971-09-09 | 1973-10-25 | Robert Bosch Gmbh, 7000 Stuttgart | Device for the machine filling of spark plug brick blanks into saggars and saggers for the device |
| US3768537A (en) * | 1972-11-09 | 1973-10-30 | Ppg Industries Inc | Tire |
| DE2360471A1 (en) * | 1973-12-05 | 1975-06-12 | Dynamit Nobel Ag | PROCESS FOR THE PRODUCTION OF ALKYLALCOXISILANES CONTAINING POLYSULPHIDE BRIDGES |
| SU580840A3 (en) * | 1974-02-07 | 1977-11-15 | Дегусса (Фирма) | Method of preparing sulfur-containing silicones |
| DE2542534C3 (en) * | 1975-09-24 | 1979-08-02 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the preparation of sulfur-containing organosilicon compounds |
-
1978
- 1978-12-27 DE DE19782856229 patent/DE2856229A1/en active Granted
-
1979
- 1979-09-17 NL NLAANVRAGE7906920,A patent/NL188288C/en not_active IP Right Cessation
- 1979-11-19 ES ES486091A patent/ES486091A1/en not_active Expired
- 1979-12-07 DD DD79217462A patent/DD147945A5/en not_active IP Right Cessation
- 1979-12-07 DD DD223824A patent/DD153885A5/en not_active IP Right Cessation
- 1979-12-19 GB GB7943675A patent/GB2038858B/en not_active Expired
- 1979-12-20 CA CA000342418A patent/CA1144936A/en not_active Expired
- 1979-12-21 BR BR7908417A patent/BR7908417A/en not_active IP Right Cessation
- 1979-12-24 BE BE6/4707A patent/BE880869A/en not_active IP Right Cessation
- 1979-12-24 IT IT7951193A patent/IT1207020B/en active
- 1979-12-25 JP JP16773779A patent/JPS5589290A/en active Pending
- 1979-12-26 US US06/106,862 patent/US4408064A/en not_active Expired - Lifetime
- 1979-12-27 CH CH1147379A patent/CH642377A5/en not_active IP Right Cessation
- 1979-12-27 FR FR7931854A patent/FR2445336A1/en active Granted
-
1980
- 1980-02-07 ES ES488326A patent/ES488326A1/en not_active Expired
-
1981
- 1981-07-13 US US06/282,949 patent/US4384132A/en not_active Expired - Fee Related
-
1983
- 1983-01-27 US US06/461,432 patent/US4444936A/en not_active Expired - Fee Related
-
1985
- 1985-12-30 MY MY457/85A patent/MY8500457A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2445336A1 (en) | 1980-07-25 |
| BE880869A (en) | 1980-06-24 |
| GB2038858B (en) | 1983-04-13 |
| DE2856229C2 (en) | 1987-07-23 |
| DE2856229A1 (en) | 1980-07-03 |
| DD153885A5 (en) | 1982-02-10 |
| ES486091A1 (en) | 1980-05-16 |
| NL188288C (en) | 1992-05-18 |
| FR2445336B1 (en) | 1982-05-21 |
| JPS5589290A (en) | 1980-07-05 |
| BR7908417A (en) | 1980-09-23 |
| IT7951193A0 (en) | 1979-12-24 |
| ES488326A1 (en) | 1980-09-16 |
| NL7906920A (en) | 1980-07-01 |
| US4408064A (en) | 1983-10-04 |
| US4384132A (en) | 1983-05-17 |
| IT1207020B (en) | 1989-05-17 |
| CH642377A5 (en) | 1984-04-13 |
| DD147945A5 (en) | 1981-04-29 |
| MY8500457A (en) | 1985-12-31 |
| US4444936A (en) | 1984-04-24 |
| GB2038858A (en) | 1980-07-30 |
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