WO2002020534A1 - Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions - Google Patents
Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions Download PDFInfo
- Publication number
- WO2002020534A1 WO2002020534A1 PCT/US2001/028079 US0128079W WO0220534A1 WO 2002020534 A1 WO2002020534 A1 WO 2002020534A1 US 0128079 W US0128079 W US 0128079W WO 0220534 A1 WO0220534 A1 WO 0220534A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrocarbon
- polysulfide silane
- triethoxysilyl
- mercaptan
- filler
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic 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
-
- 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
- C07F7/18—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
Definitions
- compositions comprising novel polysulfide-silane coupling agents, referred to as hydrocarbon core polysulfide silanes, rubber compositions incorporating the novel polysulfide silanes, and methods of preparing the same.
- the hydrocarbon core polysulfide silanes of the present invention may be used in coupling mineral fillers within elastomeric compositions, particularly rubber, wherein specific characteristics of the polysulfide silanes may be tailored towards specific characteristics of the elastomeric composition.
- sulfur-containing coupling agents for mineral-filled elastomers involve silanes in which two alkoxysilyl groups are bound, each to one end of a chain of sulfur atoms.
- the chemical bond in these molecules between the two silicon atoms and sulfur is indirect, being mediated by two similar and, in most cases, identical hydrocarbon fragments.
- This general silane structure almost invariably relies on a chain of three methylene groups as the two mediating hydrocarbon units, and upon the use of two triethoxysilyl groups. In the most notable exceptions, the methylene chain is shorter, containing only one or two methylenes per chain.
- the rubber mixtures disclosed contain from 0.1 to 10 wt. % of the polysulphide polyether silane. When a mixture of oligomers of the polysulphide polyether silanes are used, the average molecular weight is about 800 to 10,000.
- the polyether portions of the molecules upon standing, may form peroxides which cause degradation of the resultant rubber compositions. Furthermore, the polyether portions of the silane compete with other rubber constituents.
- a further object of the invention is to provide a filled elastomeric composition, rubber composition and tire compositions containing a polysulfide silane having improved filler dispersion. It is yet another object of the present invention to provide a low rolling resistance tire having enhanced performance.
- X 1 , X 2 and X 3 are the same hydrolyzable functionalities with ethoxy being most preferred.
- X 1 , X 2 and X 3 may also each be different hydrolyzable functionalities.
- p is 3 to 6;
- x is 2 to 8;
- R is a hydrocarbon functionality selected from the group consisting of straight chain alkyl, alkenyl, aryl and aralkyl groups; and J is selected from the group consisting of methylene, ethylene, propylene, isobutylene, and diradicals obtained by loss of hydrogen atoms at a 2,4 or 2,5 position of norbornane, an alpha position of 2-norbornylethane, a beta position of 2-norbornylethane, a 4 position of 2-norbornylethane, or a 5 position of 2-norbornylethane.
- G is preferably glyceryl.
- G may be a hydrocarbon fragment obtained by removal of 3 hydrogen atoms from 2-norbornylethane.
- G may also be a hydrocarbon fragment obtained by removal of 3 hydroxyl groups from a trimethylolalkane.
- p is 4 and G is preferably pentaerythrityl.
- G may be a hydrocarbon fragment obtained by removal of 4 hydrogen atoms from 2-norbornylethane.
- G may be a hydrocarbon fragment obtained by removal of more then 4 hydrogen atoms from a hydrocarbon selected from the group consisting of cyclododecane, triethylcyclohexane, 2,6-dimethyloctane, and squalane. G may also contain a tertiary amine functionality or a cyano functionality.
- the present invention is directed to a polysulfide silane composition comprising one or more isomers of tetrakis-1 ,3 ,4,5-(3-triethoxysilyl-l-propyltetrathio)neopentane.
- the present invention is directed to a polysulfide silane composition comprising one or more isomers of tris-l,2,3-(3-triethoxysilyl-l- propyltetrathio)propane .
- the present invention is directed to a process of making a hydrocarbon core polysulfide silane having the formula
- the step of providing the mercaptan comprises providing a mercaptan having a formula X ⁇ X ⁇ i-J-SH wherein the mercaptan is most preferably selected from the group consisting of 3-mercapto-l-propyltriethoxysilane and 3 -mercapto- 1 -propylmethyldiethoxysilane .
- the step of providing the mercaptan comprises providing a mercaptan having a formula (HS x -) p G wherein the mercaptan is most preferably selected from the group consisting of
- the step of deprotonating the mercaptan may comprise deprotonating the mercaptan with a Bronsted base using p equivalents of the base for each mole of mercaptan or with an amine type base.
- the step of forming the reactive sulfur anion is sufficiently complete prior to introduction of the carbon containing substrate.
- the present invention is directed to an elastomeric composition
- the at least one hydrocarbon core polysulfide silane is one or more isomers of tetrakis-l,3,4,5-(3-triethoxysilyl-l-propyltetrathio)neopentane or tris-l,2,3-(3-triethoxysilyl-l-propyltetrathio)propane.
- the at least one hydrocarbon core polysulfide silane is present in an amount of about 0.05 to about 25 phr.
- the elastomeric composition preferably comprises a filler present in an amount of about 1 to about 85 wt.
- the present invention is directed to a method of making a rubber composition
- the filler has been pretreated with all or a portion of the at least one isomer of the hydrocarbon core polysulfide silane.
- the process may further include the step of adding curing agents to the rubber mixture in another thermomechanical mixing stage.
- the hydrocarbon core polysulfide silane is one or more isomers of tetrakis-l,3,4,5-(3-triethoxysilyl-l-propyltetrathio)neopentane or one or more isomers of tris-1 ,2,3-(3-triethoxysilyl-l-propyltetrathio)propane.
- the present invention is directed to a filler for dispersion in elastomeric compositions comprising: mineral particulates; and at least one hydrocarbon core polysulfide silane having the formula:
- X 1 (X 1 X 2 X 3 Si-J-S x -) p -G wherein p is 3 to 12, x is 2 to 20,
- the mineral particulates are siliceous particulates.
- the filler of this aspect may further comprise carbon black.
- the at least one hydrocarbon core polysulfide silane is one or more isomers of tetrakis-l,3,4,5-(3-triethoxysilyl-l-propyltetrathio)neopentane or one or more isomers of tris-1 ,2,3-(3-triethoxysilyl-l-propyltetrathio)propane.
- the present invention discloses novel hydrocarbon core polysulfide silanes which exhibit advantages as coupling agents for mineral-filled elastomers over prior art polysulfide silanes.
- the polysulfide silanes are advantageous over the prior art in that they have tailored characteristics to enhance their performance as a result of specific molecular structures.
- the present invention further relates to the method of preparing the novel hydrocarbon core polysulfide silanes, the novel elastomeric compositions, and a filler treated with the novel hydrocarbon core polysulfide silanes.
- alkyl includes straight, branched and cyclic alkyl groups
- alkenyl includes straight, branched and cyclic alkenyl groups containing one or more carbon-carbon double bonds
- alkynyl includes straight, branched, and cyclic alkynyl groups containing one or more carbon-carbon triple bonds and optionally also one or more carbon-carbon double bonds as well
- aryl includes aromatic hydrocarbons
- aralkyl includes aliphatically substituted aromatic hydrocarbons.
- Specific alkyls include methyl, ethyl, propyl, isobutyl, specific aryls include phenyl, and specific aralkyls include tolyl and phenethyl.
- cyclic alkyl also include bicyclic, tricyclic, and higher cyclic structures, as well as the aforementioned cyclic structures further substituted with alkyl, alkenyl, and/or alkynyl groups.
- Representative examples of the aforementioned cyclic structures include norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl, and cyclododecatrienyl.
- hydrocarbon core polysulfide silanes of the present invention are represented by the following general formula:
- G includes, but is not limited to, branched, straight-chain, cyclic, and/or poly cyclic aliphatic hydrocarbon fragments.
- G may contain a tertiary amine functionality via nitrogen atoms each bound to three separate carbon atoms and/ or cyano (CN) groups; aromatic hydrocarbons; and arenes derived by substitution of the aforementioned aromatics with branched or straight chain alkyl, alkenyl, alkynyl, aryl and/or aralkyl groups.
- Representative examples of X 1 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy, chloro, and acetoxy. Methoxy, ethoxy, and isopropoxy are preferred. Ethoxy is most preferred.
- Representative examples of X 2 and X 3 include the representative examples listed above for X 1 as well as hydrogen, methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, vinyl, cyclohexyl, and higher straight-chain alkyl, such as butyl, hexyl, octyl, lauryl, and octadecyl.
- Methoxy, ethoxy, isopropoxy, methyl, ethyl, phenyl, and the higher straight-chain alky Is are preferred for X 2 and X 3 .
- Ethoxy, methyl and phenyl are most preferred.
- X 1 , X 2 and X 3 are the same alkoxy groups with ethoxy being most ideal.
- J include the terminal straight-chain alkyls further substituted terminally at the other end, such as -CH 2 -, -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, and -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, and their beta-substituted analogs, such as -CH 2 (CH 2 ) m CH(CH 3 )-, where m is zero to 17; -CH 2 CH 2 C(CH 3 ) 2 CH 2 -; the structure derivable from methallyl chloride, -CH 2 CH(CH 3 )CH 2 -; any of the structures derivable from divinylbenzene, such as -CH 2 CH 2 (C 6 H 4 )CH 2 CH 2 - and -CH 2 CH 2 (C 6 H 4 )CH(CH 3 )-, where the notation C 6 H 4 denotes a disubstituted benzene ring; any of the structures derivable from but
- J The preferred structures for J are -CH 2 -, -CH 2 CH 2 - -CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, and any of the diradicals obtained by 2,4 or 2,5 disubstitution of the norbornane-derived structures listed above. -CH 2 CH 2 CH 2 - is most preferred.
- tridentate G include any of the structures derivable from nonconjugated terminal diolefins, such as -CH 2 (CH 2 ) q+1 CH(CH 2 -)- and -CH(CH 3 )(CH 2 ) q CH(CH 2 -)-, in which q is zero to 20; any of the structures derivable from divinylbenzene, such as -CH 2 CH 2 (C 6 H 4 )CH(CH 2 -)- and -CH(CH 3 )(C 6 H 4 )CH(CH 2 -)-, where the notation C 6 H 4 denotes a disubstituted benzene ring; any of the stractures derivable from butadiene, such as -CH 2 (CH- )CH 2 CH 2 - and -CH(CH 3 )CH(CH 2 -)-; any of the structures derivable from piperylene, such as -CH 2 (CH-)(CH-)CH 2 CH
- any of the structures derivable from limonene such as -CH 2 CH(CH 3 )[4-methyl-l-C 6 H 8 (-) 2 CH 3 ], -(CH 3 ) 2 C[4-methyl-l-C 6 H 8 (-) 2 CH 3 ], and -CH 2 (C-)(CH 3 )[(4-methyl-l-C 6 H 9 -)CH 3 ], where the notation C 6 H 9 denotes isomers of the trisubstituted cyclohexane ring lacking substitution in the 2 position and where C 6 H g denotes the 1,4 disubstituted cyclohexene ring; any of the vinyl-containing structures derivable from trivinylcyclohexane, such as -CH 2 (CH-)(vinylC 6 H 9 )CH 2
- any of the saturated stractures derivable from myrcene such as
- tridentate G include any of the structures derivable from vinylnorbornene and vinylcyclohexene, such as -CH 2 CH 2 -norbornyl(-) 2 , -CH(CH 3 )-norbornyl(-) 2 , -CH 2 (CH-)-norbornyl-,
- any of the saturated structures derivable from trivinylcyclohexane such as (-CH 2 CH 2 ) 3 C 6 H 9 , (-CH 2 CH 2 ) 2 C 6 H 9 CH(CH 3 )-, -CH 2 CH 2 C 6 H 9 [CH(CH 3 )-] 2 , and C 6 H 9 [CH(CH 3 )-] 3 , where the notation C 6 H 9 denotes any isomer of the trisubstituted cyclohexane ring; any of the trisubstituted cyclododecane structures; any of the saturated stractures derivable from myrcene, such as
- glyceryl the structures derivable from trimethylolalkanes, such as CH 3 CH 2 C(CH 2 -) 3 and CH 3 C(CH 2 -) 3 ; and any of the structures derivable from vinylnorbornene, such as -CH 2 CH 2 -norbornyl(-) 2 , -CH(CH 3 )-norbornyl(-) 2 , and -CH 2 (CH-)-norbornyl-.
- trimethylolalkanes such as CH 3 CH 2 C(CH 2 -) 3 and CH 3 C(CH 2 -) 3
- vinylnorbornene such as -CH 2 CH 2 -norbornyl(-) 2 , -CH(CH 3 )-norbornyl(-) 2 , and -CH 2 (CH-)-norbornyl-.
- tetradentate G include any of the structures derivable from nonconjugated terminal diolefins, such as -CH(CH 2 X(IH 2 ) q CH(CH 2 )-, in which q is from 1 to 20; any of the structures derivable from divinylbenzene, such as -CH 2 (CH-)(C 6 H 4 )CH(CH 2 -)-, where the notation C 6 H 4 denotes a disubstituted benzene ring; any of the structures derivable from butadiene, such as -CH 2 (CH-)(CH-)CH 2 -; any of the stractures derivable from piperylene, such as -CH 2 (CH-)(CH-)CH 2 (CH 3 )-; any of the stractures derivable from isoprene, such as -CH 2 (C-)(CH 3 )(CH-)CH 2 -; any of the structures derivable from vinyl
- tetradentate G includes pentaerythrityl and any of the structures derivable from vinylnorbornene, such as -CH 2 (CH-)-norbornyl(-) 2 .
- Pentaerythrityl is most preferred.
- Representative examples of polydentate G include any of the structures derivable from trivinylcyclohexane, such as -CH 2 CH 2 C 6 H 9 [(CH-)CH 2 -] 2 ,
- C 6 H 9 denotes any isomer of the trisubstituted cyclohexane ring; any structure derivable by pentasubstitution or hexasubstitution of cyclododecane; any of the structures derivable from myrcene, such as -C(CH 3 )(-CHCH 2 -)CH 2 CH 2 (CH-)C(CH 3 ) 2 -, -CH 2 CH(-CHCH 2 -)CH 2 CH 2 (CH-)C(CH 3 ) 2 -, -CH 2 (C-)(CH 2 CH 2 -)CH 2 CH 2 (CH-)C(CH 3 ) 2 -, -CH 2 (C-)(-CHCH 3 )CH 2 CH 2 (CH-)C(CH 3 ) 2 -, -CH 2 (C-)(-CHCH 3 )CH 2 CH 2 (CH-)C(CH 3 ) 2 -, -CH 2 (C-)(-CHCH 3 )CH
- hydrocarbon core polysulfide silanes of the present invention may be classified according to how many silyl groups branch out from their hydrocarbon cores. Thus, three silyl groups from a tridentate core, four silyl groups from a tetradentate core, and so forth.
- hydrocarbon-core polysulfide silanes of the present invention with a tridentate core, include any of the isomers of tris-1, 2, 3-(2-triethoxysilyl-l- ethylnorborny ltetrathio)propane , tris-1,1,l-(2-triethoxysilyl-l- ethylnorbornyltetrathiomethyl)propane, tris-1,1,l-(2-triethoxysilyl-l- ethylnorbornyltetrathiomethyl)ethane, tris-1,2,3- (triethoxysilylnorbornyltetrathio)propane, tris-1,1,1- (triethoxysilylnorbornyltetrathiomethyl)propane, tris-1,1,1- (triethoxysilylnorbornyltetrathiomethyl)propane, tris-1,1,1- (trie
- hydrocarbon-core polysulfide silanes of the present invention with a tetradentate core, include any of the isomers of tetrakis- 1,3,4,5 -(2-triethoxy silyl- 1 -ethylnorbornyltetrathio)neopentane , tetrakis-1 ,3,4,5- (triethoxysilylnorbornyltetrathio)neopentane, tetrakis-1 ,3 ,4,5 ⁇ (3-triethoxysilyl-l- propyltetrathio)neopentane, tetrakis-1 ,3 ,4,5-(2-triethoxysilyl-l- ethyltetrathio)neopentane, tetrakis-1 ,3 ,4,5-triethoxysilylmethyltetrathioneopentane, tetrakis- 1 , 3
- hydrocarbon-core polysulfide silanes of the present invention with a polydentate core, include any of the isomers of pentakis(2- triethoxysilyl- 1 -ethylnorborny ltetrathioethy l)cyclohexane , pentakis(2-triethoxysilyl- 1 -ethylnorbornyltetrathio)cyclododecane , 2 , 6-dimethylpentakis (2-triethoxysilyl- 1 - ethylnorborny ltetrathio)octane , pentakis (triethoxy sily lnorborny ltetrathioethy l)cyclohexane , pentakis(triethoxysilylnorbornyltetrathio)cyclododecane, 2 , 6-dimethylpentakis (trieth
- compositions comprising at least one of any of the isomers of tris-1, 2, 3-(2-triethoxysilyl-l- ethylnorbornyltetrathio)propane, tris-1 , 1 , l-(2-triethoxysilyl-l- ethylnorbornyltetrathiomethyl)propane, tris-1 , 1 , 1 -(2-triethoxysilyl- 1- ethy lnorborny ltetrathiomethyl)ethane , tris- 1,2,3-
- triethoxy sily lmethy ltetrathiomethy l)ethane tris (2-triethoxysilyl- 1 - ethy lnorborny ltetrathio)cyclododecane , 2 , 6-dimethyltris(2-triethoxy silyl- 1 - ethylnorbornyltetrathio)octane, 2-ethyl-6-methyltris(2-triethoxysilyl-l- ethy lnorborny ltetrathio)heptane ,
- compositions comprising at least one of the isomers of tris-1, 2,3-(3-triethoxysilyl-l- propyltetrathio)propane, tris-1 , 1 , l-(3-triethoxysilyl-l- propyltetrathiomethyl)propane, tris-1 , 1 , l-(3-triethoxysilyl-l- propyltetrathiomethyl)ethane, tetrakis-1 ,3 ,4,5-(3-triethoxysilyl-l- propyltetrathio)neopentane, and tetrakis-1 ,3 ,4,5-(2-triethoxysilyl-l- ethyltrithio)neopentane. Tetrakis-1 ,3 ,4,5-(3-triethoxysilyl-l- propyltetrathio)neopentane. Tetrakis-1
- partial hydrolyzates and condensates of the above referenced hydrocarbon core polysulfide silanes may be present in an amount of up to about 10 wt. % of the polysulfide silanes. Higher amounts of hydrolyzates or condensates will work but usually with reduced efficacy in comparison to the monomers.
- a general method of preparing the hydrocarbon core polysulfide silanes of the present invention may be categorized by the type of base used to deprotonate a mercaptan starting material and how the silicon functionality is introduced into the final composition.
- Equation sequence 1 illustrates the reactions to form the hydrocarbon core polysulfide silanes of the present invention wherein the silyl group is introduced via the mercaptan. Equation Sequence 1:
- Equation 1A BI " + X'X 2 X 3 Si-J-SH ⁇ B1H + X'X ⁇ Si-J-S " or
- Equation IB B2 + X'X 2 X 3 Si-J-SH ⁇ B2H + + X'X 2 X 3 Si-J-S "
- Equation 1C Equation 1C:
- Category I reactions involve an anionic base, BI " , which functions as a Bronsted base and includes alkoxides. Bronsted bases are those bases which accept one or more protons.
- Category II reactions involve neutral Bronsted bases or non-ionic Bronsted bases such as amines.
- the silyl group is introduced via the mercaptan while the hydrocarbon core is introduced via the substrate L p G or X'X 2 X 3 Si-J-L, the substrate containing carbon and the leaving group L which is reactive with sulfur anions.
- Equation sequence 2 illustrates how the hydrocarbon core polysulfide silanes of the present invention are formed when the silicon functionality is introduced via the substrate.
- Equation 2D pX'X 2 X 3 Si-J-L + ( " S X -) P G ⁇ + pL "
- Category III reactions utilize an anionic Bronsted base while Category IV reactions involve non-ionic Bronsted bases such as amines.
- Equation sequences 1 and 2 start with a desired mercaptan such as X'X ⁇ Si-J-SH or (HS-) P G; a base capable of deprotonating the mercaptan; elemental sulfur to react with the deprotonated mercaptan X'X 2 X 3 Si-J-S " or ( " S-) P G to form the reactive sulfur anion X ⁇ X ⁇ i-J-S * " or ( " S X -) P G, (the sulfur nucleophile); and a substrate to couple with the sulfur nucleophile.
- the base extracts a single proton from the mercaptan.
- bases capable of extracting multiple protons may also be used in which case the stoichiometry is adjusted accordingly.
- the desired amount of base involves p equivalents of BI " or B2 for each mole of mercaptan (HS-) P G used to which is added a quantity of p(x-l) atoms of sulfur as elemental sulfur and p moles of substrate X'X ⁇ Si-J-L.
- Preferred cationic counterions for BI " are the alkali metals, with sodium usually most preferred. Potassium ion may be preferred when using very hindered alcohols and/or alkoxides are used as the base and/or solvent (e.g. tert-butoxy). In cases involving ether solvents, lithium ion may be preferred.
- the values of x and p, as well as the structures X 1 , X 2 , X 3 , J and G are those specified in Formula I.
- L may be any group whose anion, L " , is a viable leaving group.
- L " include, but are not limited to, chloride, bromide, iodide, sulfate, trifluoroacetate, and any of the sulfonates including tosylate, benzenesulfonate, and triflate.
- Chloride is preferable due to its commercial availability. Bromide is preferable in cases wherein enhanced reactivity relative to the chloride is desired, such as in aromatic halogen substitutions, which require more rigorous conditions.
- the preferred solvents for the preparation of the hydrocarbon core polysulfide silanes of the present invention typically are protic solvents, such as alcohols and amines because they readily dissolve and/or promote the formation of the sulfur anions, mediate the chemical reactions readily, and lead to anionic coproducts which are most easily removed from the product.
- suitable protic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, _.ec-butanol, t-butanol, butylamine, ethylene diamine, diethylene triamine, and the like.
- Aprotic solvents may be used as well including ethers, tetrahydrofuran, poly ethers, glyme, diglyme and higher glymes, aromatic solvents such as toluene and xylene provided that the sulfur anion is sufficiently soluble, dimethylformamide, dimethylsulf oxide, N-methylpyrrolidinone, and tertiary amines such as triethylamine. N-methylpyrrolidinone is preferred for substitutions directly on aromatic rings. In some cases, solventless systems may also be used.
- An advantage of alcoholic solvents is that the preparation of the hydrocarbon core polysulfide silanes of the present invention can also be coupled with a transesterification of the alkoxy group present on the starting silane by using or substituting the solvent with another alcohol at any step prior to solvent removal.
- the distillation of the alcohol from the mixture can be accompanied by an exchange of the alkoxy group on silicon in which it is replaced by the alkoxy group corresponding to the alcohol solvent introduced.
- less volatile alcohols readily displace alkoxy groups corresponding to the more volatile alcohol groups.
- the reverse can also be accomplished, but requires at least two coupled distillations.
- An example would be the use of 3 -mercapto-1 -propy ltrimethoxy silane with methanolic sodium methoxide, sulfur, and pentaerythritol tetrachloride in ethanol, removing the solvent by fractional distillation and generating an ethoxy hydrocarbon core polysulfide silane.
- Suitable conditions for preparation of the hydrocarbon core polysulfide silanes of the present invention include reaction temperatures of about 0°C to the reflux temperature of the solvent depending upon the concentration of reagents and pressure employed.
- the reaction temperature may be as high as about 190°C or even about 200°C if, for example, solvents such as dimethylsulfoxide or ⁇ -methylpyrrolidinone are used.
- Reaction temperatures between 30°C and 80°C are more typical conditions. Ambient pressures are generally preferred.
- the logistics for preparation of the hydrocarbon core polysulfide silanes of the present invention are generally aimed at completing the formation of the polysulfidic sulfur anion from the deprotonated mercaptan prior to the introduction of the substrate.
- strong bases such as alkoxides
- a preferred order of addition of raw materials to the reactor typically begins with an initial charge of base and mercaptan, followed by introduction of the elemental sulfur.
- the base and mercaptan are preferably stirred to a homogeneous solution before the elemental sulfur is introduced. Since the dissolution and reaction of the elemental sulfur to form the polysulfidic sulfur anion is not instantaneous, but occurs over a period of time, it is advantageous to use a powdered form of elemental sulfur and elevate the temperature of the mixture with continuous stirring to accelerate the dissolution process.
- a preferable method involves stirring the base, mercaptan and elemental sulfur at temperatures of about 40°C to about 80°C, which typically brings about complete dissolution of powdered elemental sulfur in a few hours or less.
- the substrate is then added to this solution, preferably with stirring and at a controlled rate, to control the resulting exothermic reaction.
- Precipitated co-products are then removed by such processes as centrifiigation, filtration, decantation, and the like. Any solvents present may then be removed by an evaporative process, such as distillation, stripping, rotary evaporation, etc.
- any base strong enough to deprotonate the mercaptan can be used, it is preferable to use an alkali metal alkoxide, more preferably sodium alkoxide, wherein the alkoxide corresponds to the silane alkoxy group of the desired final product.
- an alkali metal alkoxide more preferably sodium alkoxide, wherein the alkoxide corresponds to the silane alkoxy group of the desired final product.
- an alkali metal alkoxide more preferably sodium alkoxide
- the alkoxide corresponds to the silane alkoxy group of the desired final product.
- the alkali metal alkoxide could be added to the mercapto-functional silane, it is preferable to initially prepare an alcoholic solution of the alkali metal alkoxide, to which the mercapto-functional silane is then added.
- the alcoholic solution of the alkali metal alkoxide can be prepared by directly reacting a suitable sodium compound with the alcohol, for example sodium metal, sodium hydride, etc., or by dissolving the alkali metal alkoxide in the alcohol.
- An alternative method would involve the addition of the aforementioned sodium compound, sodium metal, or sodium alkoxide directly to an alcoholic solution of the mercapto-functional silane. In either case, the deprotonation of the mercapto-functional silane is complete upon complete mixing with the base. Elemental sulfur is now added to the deprotonated mercapto- functional silane forming the desired reactive nucleophile. After heating and stirring the mixture to accelerate the dissolution process as much as possible, the substrate is then added to this solution and the reaction worked up accordingly to remove precipitated salts and solvents.
- Category II preparations wherein the silyl group is introduced via the mercaptan involve a non-anionic base such as an amine to direct the deprotonation of a mercapto-functional silane or a deprotonation coupled with a sulfur anion displacement reaction.
- a non-anionic base such as an amine
- these preparations may be done in any of the solvents as described above. It is preferred that the preparations be done under nearly anhydrous conditions, most preferably under strictly anhydrous conditions. Neat systems, where no solvents are used or systems using an excess of the amine base as the solvent are also viable.
- the solvents are chosen which minimize the solubility of the protonated amine salts co-produced in the process.
- ethers such as glyme and tetrahydrofuran would be preferred.
- Alcohols may also be used, but an additional step may be needed to precipitate residual amine salts remaining in the product by using a less polar co-solvent, such as the aforementioned ethers or perhaps toluene.
- the substrate be added only after the elemental sulfur has had a chance to substantially react with or at least reach equilibrium with a mixture of the mercapto-functional silane and the base.
- a powdered form of the elemental sulfur is preferred with stirring at elevated temperatures of the mixture to accelerate the dissolution process as much as possible.
- Any resulting ionic phase is then removed by centrifugation, filtration, and/or decantation. Any remaining solvent and/or excess base is then removed by an evaporative process, such as distillation, stripping, rotary evaporation, and the like. Any amine salts which were carried in solution prior to the evaporative removal of solvent and/or excess base and which subsequently separated during the evaporative process are then removed by a second centrifugation, filtration, and/or decantation.
- Category III preparations wherein the silyl group is introduced via the substrate, which involve the deprotonation of a mercaptan using an anionic base, are preferably done in an alcohol corresponding to the desired silane alkoxy group in the final product. Strictly anhydrous conditions are not necessary. Water may be present in small to modest amounts, up to about 10 wt. %, preferably no more than 5 wt. % , prior to the addition of the silicon-containing substrate. However, it is preferred that any water present be removed from the system prior to the addition of the silicon-containing substrate. Although any base strong enough to deprotonate the mercaptan may be used, an alkali metal alkoxide is preferred, more preferably the sodium alkoxide.
- alkali metal hydroxides may also be used as the base. If an alkoxide is used, it should correspond to the silane alkoxy group ; of the desired final product. For example, if an ethoxy silane product is desired, one would preferably deprotonate the starting mercaptan with ethanolic sodium ethoxide. Although the alkali metal alkoxide or hydroxide may be added to the mercaptan, it is preferable to initially prepare an alcoholic solution thereof, to which the mercaptan is then added.
- the alcoholic solution of the alkali metal alkoxide may be prepared by directly reacting a suitable sodium compound with the alcohol, for example sodium metal, sodium hydride, etc., or by dissolving the alkali metal alkoxide in the alcohol.
- a suitable sodium compound for example sodium metal, sodium hydride, etc.
- an alcoholic solution of the alkali metal hydroxide may be prepared by simply dissolving the hydroxide in the alcohol.
- Another method would involve the addition of the aforementioned sodium compound, sodium metal, sodium alkoxide, or sodium hydroxide directly to an alcoholic solution of the mercaptan. In either case, the deprotonation of the mercaptan is complete upon complete mixing with the base.
- Powdered elemental sulfur is now added to form the desired reactive nucleophile with heated stirring to bring about complete dissolution of powdered elemental sulfur in a few hours or less. Any water present in the system should be removed at this point according to known methods in the art.
- the silicon-containing substrate is then added to this solution, preferably with stirring and at a controlled rate so as to control the resulting exothermic reaction. The reaction mixture is again worked up accordingly.
- Category IV preparations wherein the silyl group is introduced via the substrate involve the direct deprotonation of a mercaptan or a deprotonation coupled with a sulfur anion displacement reaction, in either case, using a non-anionic base such as an amine.
- a non-anionic base such as an amine.
- solvents may be used as described above. Strictly anhydrous conditions are not necessary. Water may be present in small to modest amounts, up to about 10 wt. % , preferably no more than 5 wt. % , prior to the addition of the silicon-containing substrate. However, any water present must be removed from the system prior to the addition of the silicon-containing substrate. Neat systems, where no solvents are used or systems using an excess of the amine base as the solvent are also viable.
- solvents which minimize the solubility of the protonated amine salts co-produced in the process such as ethers, e.g., glyme, and tetrahydrofuran. Alcohols may also be used, but an additional step may be needed to precipitate residual amine salts remaining in the product by using a less polar co-solvent such as the aforementioned ethers or toluene. It is preferred that the substrate be added only after the elemental sulfur has had a chance to substantially react with or at least reach equilibrium with a mixture of the mercapto-functional silane and the base. Thus, it is preferable to add the silicon-containing substrate last.
- a powdered form of the elemental sulfur is preferred with continuous stirring at elevated temperatures to accelerate the dissolution process as much as possible. Any water present in the system should be removed at this point according to known methods in the art. If the amine base has a boiling point below about 100°C, the water removal process may remove the amine, thereby necessitating its replacement.
- the silicon-containing substrate is then added to the resulting solution, preferably with stirring and at a controlled rate so as to control the resulting exothermic reaction. The reaction is worked up as previously described.
- Elastomers useful with the hydrocarbon core polysulfide silanes of the present invention include sulfur vulcanizable rubbers having conjugated diene homopolymers and copolymers, and copolymers of at least one conjugated diene and aromatic vinyl compound.
- SSBR solution-prepared styrene-butadiene rabber
- This solution-prepared SSBR preferably has a bound styrene content in a range of about 5 to about 50% , more preferably about 9 to 36% .
- Other useful polymers include styrene-butadiene rubber (SBR), natural rubber (NR), ethylene-propylene copolymers and terpolymers (EP, EPDM), acrylonitrile-butadiene rabber (NBR), polybutadiene (BR), and so forth.
- SBR styrene-butadiene rubber
- NR natural rubber
- EP, EPDM ethylene-propylene copolymers and terpolymers
- NBR acrylonitrile-butadiene rabber
- BR polybutadiene
- the rubber composition is preferably comprised of at least one diene-based elastomer, or rubber.
- Suitable conjugated dienes are isoprene and 1,3-butadiene and suitable vinyl aromatic compounds are styrene and alpha methyl styrene.
- Polybutadiene may be characterized as existing primarily, typically about 90 wt. %, in the cis-1,4- butadiene form.
- the rubber is a sulfur curable rabber.
- diene based elastomer, or rubber may be selected, for example, from at least one of cis- 1,4-polyisoprene rubber (natural and/or synthetic, preferably natural), natural rubber, emulsion polymerization prepared styrene/butadiene copolymer rubber, organic solution polymerization prepared styrene/butadiene rubber, 3,4-polyisoprene rabber, isoprene/butadiene rabber, styrene/isoprene/butadiene terpolymer rubber, cis-l,4-polybutadiene, medium vinyl polybutadiene rubber (about 35 to about 50% vinyl), high vinyl polybutadiene rubber (about 50 to about 75% vinyl), styrene/isoprene copolymers, emulsion polymerization prepared styrene/butadiene/acrylon
- an emulsion polymerization derived styrene/butadiene (E-SBR) having a relatively conventional styrene content of about 20 to about 28% bound styrene, or an E-SBR having a medium to relatively high bound styrene content of about 30 to about 45% may be used.
- Emulsion polymerization prepared styrene/butadiene/acrylonitrile terpolymer rubbers containing about 2 to about 40 wt. % bound acrylonitrile in the terpolymer are also contemplated as diene based rubbers for use in this invention.
- a particulate filler may also be added to the crosslinkable elastomer compositions of the present invention including siliceous fillers, carbon black, and the like.
- the filler materials useful herein include, but are not limited to, carbon black, metal oxides such as silica (pyrogenic and precipitated), titanium dioxide, aluminosilicate and alumina, clays and talc, and so forth. Particulate, precipitated silica may also be used for such purpose, particularly when the silica is used in conjunction with a silane. In some cases, a combination of silica and carbon black is utilized for reinforcing fillers for various rubber products, including treads for tires.
- Alumina can be used either alone or in combination with silica.
- the term, alumina is defined herein as aluminum oxide, or Al 2 O 3 .
- the alumina fillers may be hydrated or in anhydrous form.
- the hydrocarbon core polysulfide silanes may be premixed or pre-reacted with the filler particles, or added to the rubber mix during the rubber and filler processing, or mixing stages. If the hydrocarbon core polysulfide silanes and filler are added separately to the rubber mix during the rabber and filler mixing, or processing stage, it is considered that the hydrocarbon core polysulfide silane(s) then combine in an in-situ fashion with the filler.
- the polysulfide silanes of the present invention may be carried on low reactivity fillers such as carbon black.
- the resultant vulcanized rabber composition having the hydrocarbon core polysulfide silanes of the present invention preferably contain a sufficient amount of filler to exhibit a reasonably high modulus and high resistance to tear.
- the combined weight of the filler may be as low as about 5 to about 100 parts per hundred rubber (phr), more preferably from about 25 to about 85 phr.
- At least one precipitated silica is utilized as a filler.
- the silica may be characterized by having a BET surface area, as measured using nitrogen gas, preferably in the range of about 40 to about 600 m 2 /g, and more preferably in a range of about 50 to about 300 m 2 /g.
- the BET method of measuring surface area is described in the Journal of the American Chemical Society. Volume 60, page 304 (1930).
- the silica typically may also be characterized by having a dibutylphthalate (DBP) absorption value in a range of about 100 to about 350, and more preferably from about 150 to about 300.
- DBP dibutylphthalate
- the silica as well as the aforesaid alumina and aluminosilicate, may be expected to have a CTAB surface area in a range of about 100 to about 220.
- the CTAB surface area is the external surface area as evaluated by cetyl trimethylammonium bromide with a pH of 9. The method is described in ASTM D 3849.
- Mercury porosity surface area is the specific surface area determined by mercury porosimetry. Using this method, mercury is penetrated into the pores of the sample after a thermal treatment to remove volatiles. Set up conditions may be suitably described as using a 100 mg sample; removing volatiles during 2 hours at 105°C and ambient atmospheric pressure; ambient to 2000 bars pressure measuring range. Such evaluation may be performed according to the method described in Winslow, Shapiro in ASTM bulletin, p.39 (1959) or according to DIN 66133. For such an evaluation, a CARLO-ERBA Porosimeter 2000 might be used. The preferred average mercury porosity specific surface area for the silica is about 100 to about 300 m 2 /g.
- a suitable pore size distribution for the silica, alumina and aluminosilicate according to such mercury porosity evaluation is considered herein to be such that about 5% or less of its pores have a diameter of less than about 10 nm, about 60 to 90% of its pores have a diameter of about 10 to about 100 nm, about 10 to 30% of its pores have a diameter of about 100 to about 1000 nm, and about 5 to 20% of its pores have a diameter of greater than about 1000 nm.
- the silica may have an average ultimate particle size, for example, in the range of about 10 to 50 nm as determined by an electron microscope, although the silica particles may be even smaller, or possibly larger, in size.
- Various commercially available silicas may be considered for use in this invention, for example, HI-SILTM 210, 243, etc. from PPG Industries of Pittsburgh, Pennsylvania; ZEOSILTM 1165MP from Rhodia, Inc. of Cranbury, New Jersey, amongst others.
- the compositions may comprise a filler mix of about 15 to about 98 wt.
- the weight ratio may range from about 3:1 to about 30:1 for siliceous fillers to carbon black. More typically, it is desirable to use a weight ratio of siliceous fillers to carbon black of at least about 3: 1, and preferably at least about 10:1.
- the filler can be comprised of about 60 to about 95 wt. % silica, alumina and/or aluminosilicate and, correspondingly, about 40 to about 5 wt. % carbon black.
- the siliceous filler and carbon black may be pre-blended or blended together during manufacture of the vulcanized rubber. Alternately, a portion ofthe carbon black may be a grade having an extremely high surface area up to about 800m 2 /g.
- one or more of the hydrocarbon core polysulfide silanes of the present invention are mixed with the organic polymer before, during or after the compounding of the filler into the organic polymer. It is preferable to add at least a portion of the hydrocarbon core polysulfide silanes before or during the compounding of the filler into the organic polymer, because these silanes facilitate and improve the dispersion of the filler.
- the total amount of hydrocarbon core polysulfide silane present in the resulting combination should be about 0.05 to about 25 phr; more preferably 1 to 10 phr. Fillers may be used in quantities ranging from about 5 to about 100 phr, more preferably from 25 to 80 phr.
- a novel rubber composition utilizing the hydrocarbon core polysulfide silane of the present invention may therefore comprise about 100 parts of at least one sulfur vulcanizable rabber and copolymers of at least one conjugated diene and aromatic vinyl compound, about 5 to 100 phr, preferably about 25 to 80 phr of at least one particulate filler, up to about 5 phr of a curing agent, and about 0.05 to about 25 phr of at least one hydrocarbon core polysulfide silane.
- the filler preferably comprises from about 1 to about 85 wt. % carbon black based on the total weight of the filler, and about 0.1 to about 20 wt. % of at least one hydrocarbon core polysulfide silane based on the total weight of the filler.
- a rubber composition of the present invention may be prepared by blending rubber, filler and hydrocarbon core polysulfide silane in a thermomechanical mixing step to a temperature of about 140 °C to about 190-200°C for about 2 to 20 minutes, preferably about 4 to 15 minutes. Additional thermomechanical mixing steps may be performed with intermittent cooling of the rubber which may be accomplished by removing the rabber from the mixer.
- the filler may be pretreated with all or a portion of the hydrocarbon core polysulfide silane prior to a first thermomechanical mixing stage.
- a curing agent is then added in a separate thermomechanical mixing step at a temperature of about 50°C for about 1 to about 30 minutes.
- a tire assembly with tread may be prepared accordingly and cured or vulcanized at about 130°C to 200°C.
- Optional ingredients may be added to the rubber compositions of the present invention including curing agents, i.e., sulfur compounds, including activators, retarders and accelerators, processing additives such as oils, plasticizers, tackifying resins, silicas, other fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants, peptizing agents, reinforcing materials, i.e., carbon black, and the like.
- Such additives are selected based upon the intended use and on the sulfur vulcanizable material selected for use, and such selection is within the knowledge of one skilled in the art, as are the required amounts of such additives.
- the examples presented below demonstrate significant advantages of the silanes described herein relative to those of prior art coupling agents in silica-filled rubber.
- An apparatus was set up which consisted of a two-neck 5-liter flask, of which one neck was fitted to a condenser and the other neck was fitted to a dropping funnel which had a vapor bypass tube for pressure equalization.
- the dropping funnel was capable of delivering a variable and controllable flow of liquid.
- the top of the condenser was fitted to a nitrogen bubbler.
- Heat was supplied to the flask using an electric heating mantle regulated by a variable voltage controller.
- the voltage controller was coupled to an electronic temperature regulator responsive to the height of mercury in a mercury thermometer.
- the thermometer was inserted directly into the contents of the 5-liter flask. Stirring was accomplished using a Teflon-coated stir bar.
- the system was maintained under an atmosphere of nitrogen using a nitrogen bubbler.
- Solids were removed from the reaction products, prior to the removal of solvent, by gravity filtration through a sintered glass frit in a vessel equipped to maintain its contents under inert atmosphere. Solvent was removed from the product by distillation at reduced pressure using a rotary evaporator. Smaller amounts of solids which formed during the solvent removal were removed from the product by decantation.
- Example 2 An apparatus similar to that of Example 1 was used. The entire apparatus was placed and kept under an atmosphere of dry nitrogen throughout the following procedure. Anhydrous sodium ethoxide (299g, 4.39 moles) in the form of a 21 wt. % solution (1423g, 1639mL) in anhydrous ethanol was added to the flask. 3- Mercapto-1 -propyltriethoxysilane (107 lg, 4.49 moles) was subsequently added with stirring. Then, powdered elemental sulfur (“flowers of sulfur”) was added (432g, 13.5 moles) to the flask with continued stirring.
- the mixture was brought to a gentle reflux and maintained at a gentle reflux for about 40 hours to insure that the sulfur had completely dissolved, resulting in a dark red-brown solution.
- a quantity of 1,2,3-trichloropropane (221g, 1.50 moles) was then added to the dropping funnel. This content of the dropping funnel was then added to the stirred contents of the flask. The rate of addition was adjusted so as to maintain a vigorous, but controlled rate of reflux from the resulting exothermic reaction. It was noted that a salt precipitate had already begun to form at the completion of the addition of the contents of the dropping funnel.
- hydrocarbon core polysulfide silanes prepared in Examples 1 and 2 were used as the coupling agent to prepare a low rolling resistance tire tread formulation.
- the rabber composition used was the following, where the figures listed under the
- PHR heading indicate the mass of the corresponding ingredient used relative to 100 total mass units of polymer (in this case, SSBR and polybutadiene) used: PHR Ingredient
- hydrocarbon core polysulfide silanes prepared by the procedures described in Examples 1 and 2 were used to prepare the rubber compositions described in Examples 3 and 4.
- a control was run side by side with Examples 3 and 4 to provide a meaningful basis of comparison for the performance as a coupling agent in silica-filled rabber of the representative examples presented herein of the hydrocarbon core polysulfide silanes.
- the silane used in the control was the current industry standard coupling agent for rabber for silica-filled tire treads, the nominal bis(3-triethoxysilyl-l-propyl)tetrasulfide (TESPT).
- TESPT nominal bis(3-triethoxysilyl-l-propyl)tetrasulfide
- the silane loading levels used were also identical with respect to the loadings of silicon delivered. This necessitated the use of slightly different loading levels on an actual mass (i.e., weight) basis due to molecular weight differences among the silanes evaluated.
- the samples were prepared using a Model B BANBURY (Farrell Corp.) mixer with a 103 cu. in. (1690 cc) chamber volume. A rubber masterbatch was prepared in a two step procedure. The mixer was set at 120 rpm with the cooling water on full. The rabber polymers were added to the mixer while running and ram down mixed for 30 seconds.
- silica about 35-40 g
- EVA ethylvinyl acetate
- the remaining silica and the oil (in an EVA bag) were then added and ram down mixed for 30 seconds.
- the mixer throat was dusted down three times and the mixture ram down mixed for 15 seconds each time.
- the mixing speed was increased to between about 160-240 rpm as required to raise the temperature of the rubber masterbatch to between about 160 and 165°C in approximately 1 minute.
- the masterbatch was removed from the mixer and using this composition, a sheet was then formed on a roll mill set at about 50 to 60°C, and then allowed to cool to ambient temperature.
- the masterbatch was then again added to the mixer with the mixer at 120 rpm and cooling water turned on full and ram down mixed for 30 seconds. The remainder of the ingredients were then added and ram down mixed for 30 seconds.
- the mixer throat was dusted down, and the mixer speed was increased to about 160- 240 rpm in order to increase the temperature of the mix to about 160-165°C in approximately 2 minutes.
- the rabber composition was mixed for 8 minutes with adjustments to the mixer speed in order to maintain the temperature between about 160-165°C.
- the composition was removed from the mixer and a sheet about ⁇ A inch thick was formed on a 6 x 12 inch roll mill set at about 50 to 60°C. This sheet was then allowed to cool to ambient temperature.
- the resulting rubber composition was subsequently mixed with the curatives on a 6 in. x 13 in. (15 cm X 33 cm) two roll mill that was heated to between 50 and 60°C.
- the sulfur and accelerators were then added to the composition and thoroughly mixed on the roll mill and allowed to form a sheet.
- the sheet was cooled to ambient conditions for 24 hours before it was cured.
- the rheological properties of the rabber compound so prepared were measured on a Monsanto R-100 Oscillating Disk Rheometer and a Monsanto M1400 Mooney Viscometer.
- a Rheometrics ARES was used for dynamic mechanical analysis.
- the specimens for measuring the mechanical properties were cut from 6 mm plaques cured for 35 minutes at 160 °C or from 2 mm plaques cured for 25 minutes at 160 °C.
- the hydrocarbon core polysulfide silanes whose preparation was described in Examples 1 and 2, were compounded into the tire tread formulation according to the above procedure. In Example 3, the hydrocarbon core polysulfide silane prepared in Example 1 was used, and in Example 4, the hydrocarbon core polysulfide silane prepared in Example 2 was used.
- ODR Oscillating Disc Rheometer
- Silane Type and Amount Silane 1 Silane 2 TESPT
- Table I above presents performance parameters of the hydrocarbon core polysulfide silanes of the present invention and of TESPT, the prior art silane which is the current industry standard.
- the levels of the dynamic properties at low strain of rubber compounded with Silane 1 are consistently and substantially below those of TESPT. These values lie at 0.60, 0.22, and 0.13 for delta G', G" max , and the maximum tan delta value, respectively for Silane 1, whereas the corresponding values for TESPT are 1.00, 0.29, and 0.165, respectively. This trend is similar, although less dramatic, with Silane 2.
- the lower values for these parameters in Silanes 1 and 2 relative to TESPT are a clear indication to one skilled in the art that Silanes 1 and 2 do a better job of dispersing the filler than the industry standard.
- the hydrocarbon core polysulfide silanes of the present invention provide multiple silyl groups without ether linkages to provide enhanced performance in filled elastomer compositions, rubber compositions, and use in tire compositions.
- the non-collinear structure of the hydrocarbon core polysulfide silanes provide enhanced dispersibility of the filler within an elastomer composition.
- Use of the hydrocarbon core polysulfide silanes of the present invention result in low rolling resistance tires having enhanced performance characteristics.
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01966637A EP1315734B1 (en) | 2000-09-08 | 2001-09-04 | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
DK01966637T DK1315734T3 (en) | 2001-09-04 | 2001-09-04 | Polysulfide silane coupling agents with the hydrocarbon core for filled elastomeric compositions |
DE60104131T DE60104131T2 (en) | 2000-09-08 | 2001-09-04 | Silicon-containing coupling reagents with a hydrocarbon core for filled elastomer mixtures |
PL36099701A PL360997A1 (en) | 2000-09-08 | 2001-09-04 | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
JP2002525155A JP4200002B2 (en) | 2000-09-08 | 2001-09-04 | Hydrocarbon core polysulfide silane coupling agent for filled elastomer compositions |
CA2419986A CA2419986C (en) | 2000-09-08 | 2001-09-04 | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
AT01966637T ATE270299T1 (en) | 2000-09-08 | 2001-09-04 | SILICON-CONTAINING COUPLING REAGENTS WITH A HYDROCARBON CORE FOR FILLED ELASTOMER MIXTURES |
KR1020037003411A KR100850110B1 (en) | 2000-09-08 | 2001-09-04 | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
BR0113741-7A BR0113741A (en) | 2000-09-08 | 2001-09-04 | Polysulfide silane composition, hydrocarbon core polysulfide silane making process, elastomeric composition, rubber compounding process, charge for dispersion in elastomeric compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/657,934 | 2000-09-08 | ||
US09/657,934 US6359046B1 (en) | 2000-09-08 | 2000-09-08 | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002020534A1 true WO2002020534A1 (en) | 2002-03-14 |
Family
ID=24639240
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/028079 WO2002020534A1 (en) | 2000-09-08 | 2001-09-04 | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
Country Status (15)
Country | Link |
---|---|
US (1) | US6359046B1 (en) |
EP (1) | EP1315734B1 (en) |
JP (1) | JP4200002B2 (en) |
KR (1) | KR100850110B1 (en) |
CN (1) | CN1222530C (en) |
AT (1) | ATE270299T1 (en) |
BR (1) | BR0113741A (en) |
CA (1) | CA2419986C (en) |
CZ (1) | CZ2003641A3 (en) |
DE (1) | DE60104131T2 (en) |
ES (1) | ES2223003T3 (en) |
PL (1) | PL360997A1 (en) |
PT (1) | PT1315734E (en) |
TR (1) | TR200401890T4 (en) |
WO (1) | WO2002020534A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1247812A1 (en) * | 2001-04-06 | 2002-10-09 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compounds and preparation processes |
WO2008085453A1 (en) * | 2006-12-28 | 2008-07-17 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
WO2008085450A2 (en) * | 2006-12-28 | 2008-07-17 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
WO2008085454A1 (en) * | 2006-12-28 | 2008-07-17 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
WO2008085455A1 (en) | 2006-12-28 | 2008-07-17 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compostions |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7799856B2 (en) * | 2001-10-05 | 2010-09-21 | Bridgestone Corporation | Rubber composition |
US6887835B1 (en) | 2002-07-09 | 2005-05-03 | Crompton Corporation | Silane additives for lubricants and fuels |
JP4203718B2 (en) * | 2002-10-31 | 2009-01-07 | 東レ・ダウコーニング株式会社 | Method for producing silicon-containing polysulfide polymer |
US7531588B2 (en) * | 2004-07-30 | 2009-05-12 | Momentive Performance Materials Inc. | Silane compositions, processes for their preparation and rubber compositions containing same |
US7928258B2 (en) * | 2004-08-20 | 2011-04-19 | Momentive Performance Materials Inc. | Cyclic diol-derived blocked mercaptofunctional silane compositions |
US7718819B2 (en) * | 2006-02-21 | 2010-05-18 | Momentive Performance Materials Inc. | Process for making organofunctional silanes and mixtures thereof |
US7504456B2 (en) * | 2006-02-21 | 2009-03-17 | Momentive Performance Materials Inc. | Rubber composition containing organofunctional silane |
US7510670B2 (en) * | 2006-02-21 | 2009-03-31 | Momentive Performance Materials Inc. | Free flowing filler composition based on organofunctional silane |
US7919650B2 (en) * | 2006-02-21 | 2011-04-05 | Momentive Performance Materials Inc. | Organofunctional silanes and their mixtures |
US20070244016A1 (en) * | 2006-04-13 | 2007-10-18 | Buck William H | Low sap engine lubricant containing silane and zinc dithiophosphate lubricant additive and composition |
US8008519B2 (en) * | 2006-08-14 | 2011-08-30 | Momentive Performance Materials Inc. | Process for making mercapto-functional silane |
US7550540B2 (en) * | 2006-08-14 | 2009-06-23 | Momentive Performance Materials Inc. | Rubber composition and articles therefrom both comprising mercapto-functional silane |
US8097744B2 (en) * | 2006-08-14 | 2012-01-17 | Momentive Performance Materials Inc. | Free flowing filler composition comprising mercapto-functional silane |
US7368584B2 (en) * | 2006-08-14 | 2008-05-06 | Momentive Performance Materials Inc. | Mercapto-functional silane |
US7781606B2 (en) * | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
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 |
US7968636B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
US7968635B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7968633B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7816435B2 (en) * | 2007-10-31 | 2010-10-19 | Momentive Performance Materials Inc. | Halo-functional silane, process for its preparation, rubber composition containing same and articles manufactured therefrom |
US8182626B2 (en) * | 2008-10-30 | 2012-05-22 | Continental Ag | Tire composition with improved vulcanizing agent |
US9447262B2 (en) | 2011-03-02 | 2016-09-20 | Momentive Performance Materials Inc. | Rubber composition containing blocked mercaptosilanes and articles made therefrom |
TWI432470B (en) * | 2011-12-30 | 2014-04-01 | Chi Mei Corp | Modified high cis conjugated diene copolymer and manufacturing method of the same |
JP2015172018A (en) * | 2014-03-12 | 2015-10-01 | ダイソー株式会社 | Sulfur-containing organic silicon product, production method thereof, and rubber composition |
JP6377476B2 (en) * | 2014-09-25 | 2018-08-22 | 東洋ゴム工業株式会社 | Organosilane and rubber composition using the same |
US9856359B2 (en) | 2015-04-08 | 2018-01-02 | The Boeing Company | Core-shell particles, compositions incorporating the core-shell particles and methods of making the same |
CN112313315A (en) | 2018-05-25 | 2021-02-02 | 雪佛龙奥伦耐有限责任公司 | Method for preventing or reducing low speed pre-ignition in a direct injection spark ignition engine using a silane containing lubricant |
CA3101046C (en) | 2018-05-25 | 2024-04-09 | Chevron U.S.A. Inc. | Method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines with manganese-containing lubricant |
US11440878B2 (en) | 2019-11-01 | 2022-09-13 | The Goodyear Tire & Rubber Company | Functional disulfide vegetable oils, method of making and use in rubber compositions and tires |
US11440877B2 (en) | 2019-11-01 | 2022-09-13 | The Goodyear Tire & Rubber Company | Silane disulfide vegetable oils, method of making and use in rubber compositions and tires |
US11667775B2 (en) | 2021-01-28 | 2023-06-06 | The Goodyear Tire & Rubber Company | Resin-modified vegetable oils in rubber compositions and tires |
CN116102889B (en) * | 2022-12-27 | 2024-04-12 | 双安电力科技有限公司 | Mixed silicon rubber for high-strength composite insulator and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0819694A2 (en) * | 1996-07-18 | 1998-01-21 | Degussa Aktiengesellschaft | Mixtures of organo-polysulfanes and process for the preparation of rubber mixtures containing them |
CA2231302A1 (en) * | 1997-03-11 | 1998-09-11 | Bayer Aktiengesellschaft | Rubber mixtures containing polysulphide polyether silanes |
Family Cites Families (68)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3476826A (en) * | 1966-05-23 | 1969-11-04 | Thiokol Chemical Corp | Organo-silane modified polysulfide polymers as adhesive additives or primers for high rank polysulfide based adhesive compositions |
BE787691A (en) | 1971-08-17 | 1973-02-19 | Degussa | ORGANOSILICIC COMPOUNDS CONTAINING SULFUR |
US4076550A (en) | 1971-08-17 | 1978-02-28 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Reinforcing additive |
US3978103A (en) | 1971-08-17 | 1976-08-31 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Sulfur containing organosilicon compounds |
US3997356A (en) | 1971-08-17 | 1976-12-14 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Reinforcing additive |
DE2141160C3 (en) | 1971-08-17 | 1982-01-21 | Degussa Ag, 6000 Frankfurt | Organosilicon compounds containing sulfur |
US3873489A (en) | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
DE2360471A1 (en) | 1973-12-05 | 1975-06-12 | Dynamit Nobel Ag | PROCESS FOR THE PRODUCTION OF ALKYLALCOXISILANES CONTAINING POLYSULPHIDE BRIDGES |
AR207457A1 (en) | 1974-01-10 | 1976-10-08 | Degussa | ADHESIVE RUBBER MIXTURE TO IMPROVE ADHESIVENESS OF VULCANIZABLE MIXTURES OF TEXTILES OR METALLIC FABRICS AFTER VULCANIZING |
SU580840A3 (en) | 1974-02-07 | 1977-11-15 | Дегусса (Фирма) | Method of preparing sulfur-containing silicones |
DE2536674C3 (en) | 1975-08-18 | 1979-09-27 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Crosslinkable mixtures based on rubber, organosilanes and silicate fillers |
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 |
US4125552A (en) | 1975-12-29 | 1978-11-14 | Dow Corning Corporation | Preparation of alkyl polysulfides |
DE2712866C3 (en) | 1977-03-24 | 1980-04-30 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the preparation of organosilicon compounds containing sulfur |
DE2747277C2 (en) | 1977-10-21 | 1982-06-09 | Degussa Ag, 6000 Frankfurt | Granular organosilane preparation, its manufacture and use |
DE2819638C3 (en) | 1978-05-05 | 1986-11-13 | Degussa Ag, 6000 Frankfurt | Vulcanizable halogen rubber compounds |
DE2848559C2 (en) | 1978-11-09 | 1982-01-21 | Degussa Ag, 6000 Frankfurt | Rubber mixtures resulting in reversion-free vulcanizates and their use |
DE2856229A1 (en) | 1978-12-27 | 1980-07-03 | Degussa | BIS- (SILYLAETHYL) -OLIGOSULFIDES AND METHOD FOR THE PRODUCTION THEREOF |
DE3028365A1 (en) | 1980-07-26 | 1982-02-18 | Degussa Ag, 6000 Frankfurt | BITUMINOESIC BINDING AGENT, METHOD FOR THE PRODUCTION AND USE THEREOF |
DE3305373C2 (en) | 1983-02-17 | 1985-07-11 | Degussa Ag, 6000 Frankfurt | Elastic molding compound, method of manufacturing and deforming and use of the same |
DE3311340A1 (en) | 1983-03-29 | 1984-10-11 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING SULFURIZED ORGANOSILICIUM COMPOUNDS |
DE3314742A1 (en) | 1983-04-23 | 1984-10-25 | Degussa Ag, 6000 Frankfurt | NATURAL OXIDIC OR SILICATIC FILLERS MODIFIED ON THE SURFACE, A METHOD FOR THE PRODUCTION AND THEIR USE |
DE3437473A1 (en) | 1984-10-12 | 1986-04-17 | Degussa Ag, 6000 Frankfurt | SYNTHETIC, SILICATIC FILLERS MODIFIED ON THE SURFACE, A METHOD FOR THE PRODUCTION AND THE USE THEREOF |
DE3610811A1 (en) | 1986-04-01 | 1987-10-08 | Degussa | USE OF SUBSTITUTED N-TRICHLORMETHYLTHIODICARBOXIMIDES IN COMBINATION WITH N; N'-SUBSTITUTED BIS- (2,4-DIAMINO-S-TRIAZINE-6-YL) -OLIGOSULFIDES IN VULCANIZABLE RUBBER RUBBERS |
JPH068366B2 (en) | 1987-04-23 | 1994-02-02 | 株式会社ブリヂストン | Rubber composition for tires |
DE3736583C1 (en) | 1987-10-29 | 1988-11-24 | Degussa | Use of shiny precious metal preparations for microwave-resistant decorations on dishes |
DE4004781A1 (en) | 1990-02-16 | 1991-08-22 | Degussa | Modifying surface of natural or synthetic oxidic or silicate fillers - using organo:silicon cpds. useful in vulcanisable natural rubber mixts. to improve rubber properties |
DE4023537A1 (en) | 1990-07-25 | 1992-01-30 | Degussa | CHEMICALLY MODIFIED ROUGS WITH ORGANOSILICIUM COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
DE4119959A1 (en) | 1991-06-18 | 1992-12-24 | Degussa | METHOD FOR PRODUCING VULCANIZABLE, RUSSELED PLASTIC AND RUBBER MIXTURES |
DE4128203C1 (en) | 1991-08-26 | 1993-05-13 | Degussa Ag, 6000 Frankfurt, De | |
DE4236218C2 (en) | 1991-12-19 | 2001-08-16 | Degussa | Vulcanizable EPDM rubber compounds |
US5466767A (en) | 1992-08-06 | 1995-11-14 | Degussa Aktiengesellschaft | Shaped organosiloxane polycondensates, process for their preparation and use |
JP2932693B2 (en) | 1992-10-05 | 1999-08-09 | 宇部興産株式会社 | Pyrimidine compounds |
DE4308311C2 (en) | 1993-03-16 | 1995-04-06 | Degussa | Use of precipitated silicas with high spec. Surface for improving the transparency and brightness properties of vulcanizable, light rubber mixtures, rubber mixtures containing the precipitated silicas and their production |
US5723529A (en) | 1994-12-21 | 1998-03-03 | The Goodyear Tire & Rubber Company | Silica based aggregates, elastomers reinforced therewith and tire tread thereof |
CA2105719A1 (en) | 1993-06-28 | 1994-12-29 | Rene Jean Zimmer | Silica based aggregates, elastomers reinforced therewith and tire with tread thereof |
US5399739A (en) | 1994-04-18 | 1995-03-21 | Wright Chemical Corporation | Method of making sulfur-containing organosilanes |
DE4415658A1 (en) | 1994-05-04 | 1995-11-09 | Bayer Ag | Rubber compounds containing sulfur-containing organosilicon compounds |
US5405985A (en) | 1994-07-08 | 1995-04-11 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
US5468893A (en) | 1994-07-08 | 1995-11-21 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
JP2788212B2 (en) | 1994-11-11 | 1998-08-20 | 横浜ゴム株式会社 | Surface-treated carbon black and rubber composition using the same |
US5674932A (en) | 1995-03-14 | 1997-10-07 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
US5580919A (en) | 1995-03-14 | 1996-12-03 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
FR2732364A1 (en) | 1995-03-29 | 1996-10-04 | Michelin & Cie | PROCESS FOR TREATING A STAINLESS STEEL BODY SO AS TO PROMOTE ITS ADHESION TO A RUBBER COMPOSITION |
US5616655A (en) | 1995-09-11 | 1997-04-01 | The Goodyear Tire & Rubber Company | Sulfur vulcanizable rubber containing sodium thiosulfate pentahydrate |
MX9603304A (en) | 1995-09-23 | 1997-03-29 | Degussa | Process for the production of vulcanizable rubber mixtures. |
DE19541404A1 (en) | 1995-11-07 | 1997-05-15 | Degussa | Process for the selective synthesis of silylalkyl disulfides |
FR2743564A1 (en) | 1996-01-11 | 1997-07-18 | Michelin & Cie | RUBBER COMPOSITIONS FOR SILICA-BASED TIRE CASINGS CONTAINING A REINFORCING ADDITIVE BASED ON A FUNCTIONALIZED POLYORGANOSILOXANE AND AN ORGANOSILANE COMPOUND. |
US5663358A (en) | 1996-01-22 | 1997-09-02 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon disulfide compounds |
US5675014A (en) | 1996-01-22 | 1997-10-07 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon disulfide compounds |
US5605951A (en) | 1996-02-20 | 1997-02-25 | The Goodyear Tire & Rubber Company | Silica reinforced rubber compostition and tire with tread thereof |
US5733963A (en) | 1996-02-20 | 1998-03-31 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread thereof |
US5780538A (en) | 1996-03-11 | 1998-07-14 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5914364A (en) | 1996-03-11 | 1999-06-22 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5672639A (en) | 1996-03-12 | 1997-09-30 | The Goodyear Tire & Rubber Company | Starch composite reinforced rubber composition and tire with at least one component thereof |
DE19610281A1 (en) | 1996-03-15 | 1997-09-18 | Bayer Ag | Process for the preparation of polysulfidic silyl ethers |
US5719207A (en) | 1996-03-18 | 1998-02-17 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5698619A (en) | 1996-06-24 | 1997-12-16 | The Goodyear Tire & Rubber Company | Aminosilane compounds in silica-filled rubber compositions |
DE19702046A1 (en) | 1996-07-18 | 1998-01-22 | Degussa | Mixtures of organosilane polysulfanes and a process for the preparation of rubber blends containing these blends |
US5663396A (en) | 1996-10-31 | 1997-09-02 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
JP3388531B2 (en) | 1996-11-29 | 2003-03-24 | 信越化学工業株式会社 | Method for desulfurizing polysulfide silane |
DE19651849A1 (en) | 1996-12-13 | 1998-06-18 | Degussa | Process for the preparation of bis (silylorganyl) polysulfanes |
US5684172A (en) | 1997-02-11 | 1997-11-04 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon polysulfide compounds |
US5753732A (en) | 1997-03-06 | 1998-05-19 | The Goodyear Tire & Rubber Company | Unsaturated amine-functional silane compounds and their use in rubber compositions |
CA2205789A1 (en) | 1997-05-22 | 1998-11-22 | Bayer Inc. | Process for hydrophobicizing particles, and their use as fillers in polymer masterbatches |
JP3498559B2 (en) | 1997-12-01 | 2004-02-16 | 信越化学工業株式会社 | Method for producing short-chain polysulfide silane mixture |
DE19819373A1 (en) | 1998-04-30 | 1999-11-04 | Degussa | Process for the preparation of mixtures of organosilicon oligosulfanes with a high proportion of organanosilicon disulfanes |
CN1256374C (en) | 1998-07-22 | 2006-05-17 | 米凯林技术公司 | Coupling system (white filler/diene elastomer) based on polysulphide alkoxysilane, enamine and guanidine derivative |
-
2000
- 2000-09-08 US US09/657,934 patent/US6359046B1/en not_active Expired - Lifetime
-
2001
- 2001-09-04 JP JP2002525155A patent/JP4200002B2/en not_active Expired - Fee Related
- 2001-09-04 PL PL36099701A patent/PL360997A1/en unknown
- 2001-09-04 WO PCT/US2001/028079 patent/WO2002020534A1/en active IP Right Grant
- 2001-09-04 CA CA2419986A patent/CA2419986C/en not_active Expired - Fee Related
- 2001-09-04 KR KR1020037003411A patent/KR100850110B1/en active IP Right Grant
- 2001-09-04 CN CNB018153135A patent/CN1222530C/en not_active Expired - Fee Related
- 2001-09-04 AT AT01966637T patent/ATE270299T1/en not_active IP Right Cessation
- 2001-09-04 ES ES01966637T patent/ES2223003T3/en not_active Expired - Lifetime
- 2001-09-04 DE DE60104131T patent/DE60104131T2/en not_active Expired - Lifetime
- 2001-09-04 BR BR0113741-7A patent/BR0113741A/en not_active IP Right Cessation
- 2001-09-04 EP EP01966637A patent/EP1315734B1/en not_active Expired - Lifetime
- 2001-09-04 PT PT01966637T patent/PT1315734E/en unknown
- 2001-09-04 TR TR2004/01890T patent/TR200401890T4/en unknown
- 2001-09-04 CZ CZ2003641A patent/CZ2003641A3/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0819694A2 (en) * | 1996-07-18 | 1998-01-21 | Degussa Aktiengesellschaft | Mixtures of organo-polysulfanes and process for the preparation of rubber mixtures containing them |
CA2231302A1 (en) * | 1997-03-11 | 1998-09-11 | Bayer Aktiengesellschaft | Rubber mixtures containing polysulphide polyether silanes |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1247812A1 (en) * | 2001-04-06 | 2002-10-09 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compounds and preparation processes |
US6759545B2 (en) | 2001-04-06 | 2004-07-06 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compounds and preparation processes |
WO2008085453A1 (en) * | 2006-12-28 | 2008-07-17 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
WO2008085450A2 (en) * | 2006-12-28 | 2008-07-17 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
WO2008085454A1 (en) * | 2006-12-28 | 2008-07-17 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
WO2008085455A1 (en) | 2006-12-28 | 2008-07-17 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compostions |
WO2008085450A3 (en) * | 2006-12-28 | 2008-09-04 | Momentive Performance Mat Inc | Free-flowing filler composition and rubber composition containing same |
CN101616924B (en) * | 2006-12-28 | 2014-12-10 | 莫门蒂夫性能材料股份有限公司 | Silated cyclic core polysulfides, their preparation and use in filled elastomer compostions |
KR101475397B1 (en) * | 2006-12-28 | 2014-12-23 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Free-flowing filler composition and rubber composition containing same |
KR101484678B1 (en) | 2006-12-28 | 2015-01-21 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Free-flowing filler composition and rubber composition containing same |
KR101484684B1 (en) | 2006-12-28 | 2015-01-21 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
EP2829543A1 (en) * | 2006-12-28 | 2015-01-28 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
EP2829544A1 (en) * | 2006-12-28 | 2015-01-28 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
KR101520959B1 (en) | 2006-12-28 | 2015-05-15 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Silated core polysulfides their preparation and use in filled elastomer compositions |
Also Published As
Publication number | Publication date |
---|---|
US6359046B1 (en) | 2002-03-19 |
CA2419986C (en) | 2011-08-02 |
TR200401890T4 (en) | 2004-09-21 |
CN1222530C (en) | 2005-10-12 |
EP1315734B1 (en) | 2004-06-30 |
CA2419986A1 (en) | 2002-03-14 |
KR20030029946A (en) | 2003-04-16 |
CZ2003641A3 (en) | 2003-06-18 |
JP4200002B2 (en) | 2008-12-24 |
ATE270299T1 (en) | 2004-07-15 |
BR0113741A (en) | 2004-01-13 |
JP2004514657A (en) | 2004-05-20 |
DE60104131D1 (en) | 2004-08-05 |
DE60104131T2 (en) | 2005-08-25 |
PL360997A1 (en) | 2004-09-20 |
KR100850110B1 (en) | 2008-08-04 |
CN1452625A (en) | 2003-10-29 |
ES2223003T3 (en) | 2005-02-16 |
PT1315734E (en) | 2004-09-30 |
EP1315734A1 (en) | 2003-06-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1315734B1 (en) | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions | |
US7629430B2 (en) | Hybrid silicon-containing coupling agents for filled elastomer compositions | |
JP5450093B2 (en) | Tire compositions and parts containing silylated core polysulfides | |
JP4607098B2 (en) | Coupling agent for mineral-filled elastomer compositions | |
KR101510227B1 (en) | Mercapto-functional silane | |
KR101490417B1 (en) | Mercaptofunctional silane and process for its preparation | |
US7550540B2 (en) | Rubber composition and articles therefrom both comprising mercapto-functional silane | |
US8372906B2 (en) | Halo-functional silane, process for its preparation, rubber composition containing same and articles manufactured therefrom | |
EP2121349A1 (en) | Rubber composition, process of preparing same and articles made therefrom | |
KR101430688B1 (en) | Elastomer composition containing mercaptofunctional silane and process for making same | |
WO2008021298A1 (en) | Process for making mercapto-functional silane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): BR CA CN CZ JP KR PL SG |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2419986 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: PV2003-641 Country of ref document: CZ |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2001966637 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2002525155 Country of ref document: JP Ref document number: 1020037003411 Country of ref document: KR Ref document number: 018153135 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 1020037003411 Country of ref document: KR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 2001966637 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: PV2003-641 Country of ref document: CZ |
|
WWG | Wipo information: grant in national office |
Ref document number: 2001966637 Country of ref document: EP |