MXPA98009467A - Process to reduce the length of the sulfate chain of bis (sililorganil) polisulfa - Google Patents
Process to reduce the length of the sulfate chain of bis (sililorganil) polisulfaInfo
- Publication number
- MXPA98009467A MXPA98009467A MXPA/A/1998/009467A MX9809467A MXPA98009467A MX PA98009467 A MXPA98009467 A MX PA98009467A MX 9809467 A MX9809467 A MX 9809467A MX PA98009467 A MXPA98009467 A MX PA98009467A
- Authority
- MX
- Mexico
- Prior art keywords
- process according
- formula
- tetrasulfan
- group
- alq
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title 1
- 229910000057 polysulfane Inorganic materials 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000003457 sulfones Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 229910052801 chlorine Chemical group 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 230000003009 desulfurizing Effects 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- KBMBVTRWEAAZEY-UHFFFAOYSA-N Trisulfane Chemical compound SSS KBMBVTRWEAAZEY-UHFFFAOYSA-N 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N Sulfur trioxide Chemical group O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003014 reinforcing Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
Abstract
The present invention relates to: This invention relates to a process for reducing the length of the sulfone chain of bis (siliorganyl) polysulfanes, in which these compounds are reacted with an anhydrous sulphide and a haloacylsil compound
Description
PROCESS TO REDUCE THE LENGTH OF THE SULPHAN CHAIN OF bis (SILILORGANIL) POLYSULPHANES
This invention relates to a process for reducing the length of the sulphan chain of bis (silyl-organyl) polysulfanes by reacting these compounds with a sulfide and a haloalkylsilane.
Polysulfanes of this type have been widely known (DE-PS 2255577) and are widely used as reinforcing additives in rubber vulcanizates containing silica, in particular in the tire sector. Bis (triethoxysilylpropyl) tetrasulfan (Si 69, Degussa AG) in particular has become established in such applications (c.f. Wolff, 129th Meeting of the Rubber Division, American Chemical Society, April 8-11, 1996, NY).
The processing advantages of the corresponding disulfins have recently been described in several publications. These compounds should be incorporated into the rubber compositions as the purest compounds possible according to EP-A-0732 362 (US Pat. No. 5,580,919) or alternatively in the form of mixtures (DE-OS 197 0246.1).
REF .: 028819 However, according to the prior art, disulfins are produced under non-pleasing conditions such as mercaptosilanes which must be oxidized with manganese dioxide (EP-A 0718 302).
The object of the invention is to provide a process which produces the desired product without developing this phenomenon.
The present invention provides a process for reducing the length of the bis (silylorganyl) polysulfanes sulfone chain, characterized in that an organosilicon compound of the general formula
Z-Alq-Sx-Alq-Z (I)
in which Z represents the groupings
wherein R 1 represents a straight or branched chain alkyl group having 1 to 5 carbon atoms, a cycloalkyl residue having 5 to 8 carbon atoms, the benzyl residue or the phenyl residue optionally substituted by methyl, ethyl or chlorine, R 2 represents an alkoxy group having a straight or branched carbon chain having 1 to 5 carbon atoms or a cycloalkoxy group having 5 to 8 carbon atoms, the phenoxy group or the benzyl group, wherein R 1 and R 2 could have each identical or different meanings,
Alk represents a monounsaturated or saturated divalent linear or branched hydrocarbon residue having 1-10 C atoms, in particular 1 to 4 C atoms or the group
x represents an integer from 3 to 8, in particular from 4 to 6 and
n represents an integer from 1 to 4 reacts with an anhydrous sulphide of the general formula
Me2S (II),
wherein Me represents an alkali metal, in particular sodium or an equivalent of an alkaline earth metal or zinc or ammonium atom, and an organosilicon compound of the general formula
A-Alq-Y (III)
in which Z and Alq have the meanings stated above and Y means Cl, Br,
wherein the molar ratio of polysulfane and Me2S is selected according to the desired sulfur content of the polysulfane to be partially desulfurized.
In a particular modality, x represents a statistical means, as the corresponding pure polysulfane could frequently be produced are only difficulty.
By appropriate adjustment of the molar ratios, it is possible to produce mixtures of different polysulfanes, in which for example the disulfones predominate (DE-OS 19702046) or also very pure polysulfanes, as used according to US Pat. No. 5,580,919.
The reaction ratios are in general selected such that the compound of the formula (II) is added to the reaction mixture in an amount (mol) which is at least completely sufficient to react with the Sy groups newly formed by the sulfur fraction. of the desulphurisation and the Na2S added to produce the compounds of the formula (I), wherein and < x = 1 corresponds to the length of the sulfur chain formed by the desulfurization.
The reaction preferably proceeds in an organic solvent, preferably polar which is inert under the test conditions. Such solvents include, in particular, aliphatic alcohols having 1 to 2 carbon atoms, ethers having C 2 -C 12 atoms, amides, such as, for example, dimethylformamide, sulfoxides, such as, for example, dimethyl sulfoxide.
The reaction generally proceeds at temperatures of 50 ° C to the reflux temperature of the solvent used, optionally under the pressure that is established at this temperature.
The product obtained in particular has a chain length Sy where y = 2.
A tetrasulfan is preferably used to reduce the length of the sulfan chain.
It is applicable in part to the bis (triethoxysilylpropyl) tetrasulfan readily available.
The corresponding trisulfan is produced from a tetrasulfan by adjusting the molar ratios of the tetrasulfan, Me2S reagents and the compounds of the formula (II) to 1: 0.4 to 0.6: 0.9 to 1.1.
The ratios from 1: 1.8 to 2.2: 2.5 to 3.5 are required for the production of disulfan from tetrasulfan.
The preferably used compounds of the formula (II) are those that give rise to a symmetric polysulfane molecule.
Ejeptplos
Example 1: Reduction of the average chain length from 4 to 2.
67. 4 g (0.13 mol) of bis (3-triethoxysilylpropyl) -tetrasulfane and 15.5 g (0.24 mol) of sodium sulfide in 120 ml of ethanol were introduced under protective N2 gas into a 500 ml three-necked flask with a condenser of reflux and magnetic stirrer. 108.7 g (0.45 mol) of 3-chloro-propyltriethoxysilane were added thereto at room temperature and then the reaction mixture was maintained at the reflux temperature for 2.5 hours. After cooling to room temperature, the precipitate was filtered and the residue of the filtration was washed three times with 30 ml of ethanol. The filtrates collected were evaporated in a rotary evaporator at 100 ° C under a final vacuum of 40 mbar. 153.1 g of a yellow liquid were obtained which, according to the spectroscopic analysis -RMN, comprises a mixture of polysulfane having an average polysulfane chain length of 2.
Performance: 90%.
Example 2: Reduction of the average chain length from 4 to 3.
100 g (0.19 mol) of bis (3-triethoxysilylpropyl) -tetrasulfane and 7.8 g (0.1 mol) of sodium sulphide in 100 ml of ethanol were introduced under protective N2 gas into a 500 ml three-necked flask with a condenser of reflux (condenser drip) and magnetic stirrer and refluxed for 1 hour. 48.2 g (0.2 mol) of 3-chloropropyltriethoxysilane were added thereto and the reaction mixture was maintained at reflux temperature for 2.5 hours. After cooling to room temperature, the precipitate was filtered and the residue of the filtration was washed three times with 30 ml of ethanol. The filtrates collected were evaporated in a rotary evaporator at 110 ° C under a final vacuum of 40 mbar. 144.9 g of a red-brown liquid were obtained which, according to the spectroscopic analysis -R N, comprises a mixture of polysulfane having an average polysulfane chain length of 3.
Yield: 98%.
It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.
Having described the invention as above, the content of the following is claimed as property.
Claims (8)
1. Process for reducing the length of the bis (silylorganyl) polysulfanes sulfone chain, characterized in that an organosilicon compound of the general formula Z-Alq-Sx-Alq-Z (I) in which Z represents the groupings R ~ R *] wherein R1 represents a straight or branched chain alkyl group having 1 to 5 carbon atoms, a cycloalkyl residue having 5 to 8 carbon atoms, the benzyl residue or the phenyl residue optionally substituted by methyl, ethyl or chlorine, R2 represents an alkoxy group having a straight or branched carbon chain having 1 to 5 carbon atoms or a cycloalkoxy group having 5 to 8 carbon atoms, the phenoxy group or the benzyl group, wherein R1 and R2 could have each identical or different meanings, Alk represents a monounsaturated or saturated divalent linear or branched hydrocarbon residue having 1-10 C atoms, in particular 1 to 4 C atoms or the group x represents an integer from 3 to 8, in particular from 4 to 6 and n represents an integer from 1 to 4 reacts with an anhydrous sulfide of the general formula Me2S (II), wherein Me represents an alkali metal, in particular sodium or an equivalent of an alkaline earth metal or zinc or ammonium atom, and an organosilicon compound of the general formula Z -Alq-Y (III) in which Z and Alq have the meanings stated above and Y means Cl, Br, wherein the molar ratio of polysulfane and Me.S is selected according to the desired sulfur content of the polysulfane to be partially desulfurized and of the desired product, and the desulfurized polysulfane is obtained pure or in the form of a mixture with other polysulfanes .
2. The process according to claim 1, characterized in that the compound of the formula (II) is added to the reaction solution in an amount (mol) which is at least completely sufficient to react with the Sy groups newly formed by the fraction of sulfur from the desulphurisation and the Na2S added to produce the compounds of the formula (I), wherein and < x = 1 corresponds to the length of the sulfur chain formed by the desulfurization.
3. The process according to claim 1 or 2, characterized in that an organic, inert and preferably polar solvent is used.
4. The process according to claim 3, characterized in that the reaction is carried out at a temperature of 50 ° C up to the reflux temperature of the solvent.
5. The process according to claim 1 to 4, characterized in that x in the formula (I) and correspondingly and correspond to a statistical means.
6. The process according to claim 1 to 5, characterized in that a bis (silylorganyl) tetrasulfan is desulfurized.
7. The process according to claim 6, characterized in that a trisulfane is produced from the tetrasulfan by adjusting the molar ratios of the tetrasulfan, Me2S reagents and the compounds of the formula (III) to 1: 0.4 to 0.6: 0.9 to 1.1.
8. The process according to claim 6, characterized in that a disulfan is produced from tetrasulfan by adjusting the molar ratios of the reagents of tetrasulfan, Me2S and the compounds of the formula (III) to 1: 1.8 to 2.2: 2.5 to 3.5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19750503.1 | 1997-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA98009467A true MXPA98009467A (en) | 1999-09-20 |
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