EP2094716A2 - Verfahren zur herstellung von (poly)thioalkoxy- und/oder halogensilanen, neue, durch dieses verfahren erhaltene produkte und deren verwendung als kupplungsmittel - Google Patents

Verfahren zur herstellung von (poly)thioalkoxy- und/oder halogensilanen, neue, durch dieses verfahren erhaltene produkte und deren verwendung als kupplungsmittel

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Publication number
EP2094716A2
EP2094716A2 EP07822459A EP07822459A EP2094716A2 EP 2094716 A2 EP2094716 A2 EP 2094716A2 EP 07822459 A EP07822459 A EP 07822459A EP 07822459 A EP07822459 A EP 07822459A EP 2094716 A2 EP2094716 A2 EP 2094716A2
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EP
European Patent Office
Prior art keywords
carbon atoms
radical
branched
linear
iii
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP07822459A
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English (en)
French (fr)
Inventor
Gérard Mignani
Samir Mansouri
Samuel Arthaud
Thierry Vidal
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Rhodia Operations SAS
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Rhodia Operations SAS
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Publication of EP2094716A2 publication Critical patent/EP2094716A2/de
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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 Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the invention relates to a novel route for the synthesis of alkoxy and / or halosilanes
  • alkoxydisilanes in which the two alkoxylated silane units are connected to each other by a (poly) sulphide bridge.
  • These alkoxysilanes may especially be useful as white-elastomer coupling agents in elastomer compositions comprising a white filler, in particular a siliceous material, as a reinforcing filler.
  • the invention also relates to the elastomer compositions containing such a coupling agent and to articles based on one of these compositions.
  • the coupling agents of the invention may be particularly useful in the preparation of elastomer articles subjected to various stresses, for example such as a variation in temperature, a variation of high frequency stress in the dynamic regime, a significant static stress or a significant bending fatigue in dynamic regime.
  • Examples of such articles are shoe soles, tires, conveyor belts, power transmission belts, hoses, expansion joints, appliance joints, role of engine vibration extractors either with metal reinforcements or with a hydraulic fluid inside the elastomer, cables, cable sheaths, rollers for cable cars.
  • Elastomer compositions suitable for the preparation of such articles should preferably have the following properties:
  • the carbon black is a load which may have such abilities, but this is not the case in general for white charges.
  • the use of reinforcing white filler alone, especially of reinforcing silica alone, may be inappropriate because of the low level of certain properties of the elastomer compositions obtained and consequently of certain properties of the articles using these compositions.
  • the white filler particles, in particular silica particles in fact generally tend, in the elastomeric matrix, to agglomerate together.
  • white-elastomeric coupling agent also called a binding agent, whose particular function is to ensure the connection between the surface of the white filler particles and the (the) elastomer (s), while facilitating the dispersion of this white charge in the elastomeric matrix.
  • white-elastomeric coupling agent is meant in known manner an agent capable of establishing a sufficient connection, chemical and / or physical, between the white charge and the elastomer; such a coupling agent, at least bifunctional, has for example as simplified general formula "Y-B-X", in which:
  • Y represents a functional group (Y-function) which is capable of binding physically and / or chemically to the white charge, such a bond possibly being established, for example, between a silicon atom of the coupling agent and the hydroxyl groups (OH) of surface of the white charge (for example surface silanols when it is silica);
  • X represents a functional group (X function) capable of binding physically and / or chemically to the elastomer, for example via a sulfur atom;
  • B represents a hydrocarbon group for connecting Y and X.
  • the coupling agents must not be confused with simple white charge-covering agents, which, in known manner, may comprise the active Y function with respect to the white charge but lack the active X function. vis-à-vis the elastomer.
  • Coupling agents in particular silica-elastomer, have been described in a large number of documents, the best known of which are bifunctional organoxysilanes carrying at least one organoxysilyl function as a Y function and, as function X, at least one function capable of reacting with the elastomer, such as in particular a polysulfide functional group.
  • polysulphurized organoxysilanes polysulphurized alkoxysilanes, especially polysulfides of bis-trialkoxyl (Ci-C 4) silylpropyl as described in numerous patents or patent applications (for example FR-A-2149339). , FR-A-2206330, US-A-3842111, US-A-3873489, US-A-3997581).
  • TESPT bis-triethoxysilylpropyl tetrasulfide
  • TESPT bis-triethoxysilylpropyl tetrasulfide
  • the TESPT can indeed be obtained in three synthesis steps using as basic raw material a hydrogenochlorosilane, a reagent extremely delicate to handle for safety reasons.
  • the reaction involving hydrogenochlorosilane is a precious metal catalyzed hydrosilylation reaction, the selectivity of which remains modest and leads to the formation of a co-product.
  • the preparation of the elastomer compositions (s) comprising reinforcing white filler particles and a polysulfide organoxysilane coupling agent, it can occur, for example during the kneading step in a conventional internal mixer, a chemical reaction involving the organoxy part of the silane and OH surface of the white charge, for example the surface silanols when it is silica.
  • a chemical reaction involving the organoxy part of the silane and OH surface of the white charge for example the surface silanols when it is silica.
  • this chemical reaction is a condensation reaction that is accompanied by a significant release of ethanol; more precisely, this chemical reaction, when using organoxysilanes such as TESPT carrying three silicon-bonded ethoxy functional groups, releases up to three moles of ethanol per mole of silane.
  • This liberated alcohol is generally at the origin of technical problems during the subsequent processing of the elastomer compositions (s), marked for example by the appearance of undesirable porosity especially during the extrusion of said compositions and / or training undesirable bubbles in the elastomer itself.
  • a reduction in the release of alcohol may be desirable for ecological and health reasons.
  • One of the objectives of the present invention is to provide an alternative route to alkoxysilanes and halosilanes, in particular polysulphide monoalkoxysilanes, especially those as defined by formula (F) above.
  • Another objective of the invention is that this alternative polysulfurized alkoxysilane synthesis route is preferably simple and economical to implement.
  • Another object of the present invention is to provide new alkoxysilanes, in particular polysulfurized monoalkoxysilanes, with specific alkylene (preferably isopropylene) patches, comprising at least two alkoxysilane poles connected to one another by a polysulfide unit and by two specific alkylenes (preferably isopropylenes) on either side of this so-called polysulphide bridge.
  • specific alkylene preferably isopropylene
  • An object of the invention is also to provide new (poly) sulfided alkoxy and / or halosilanes, in particular polysulphide monoalkoxysilanes with a specific alkylene (preferably isopropylene) spindle, which can especially be used as white-elastomer coupling agents in elastomer compositions (s) comprising a white filler, in particular a siliceous material, as a filler reinforcing, these new coupling agents being, advantageously, efficient and economical.
  • the present invention which relates, in its first object, to a process for the preparation of at least one alkoxy and / or halosilane (poly) sulphurized salt characterized in that it consists essentially in reacting, according to an ionic addition mechanism, at least one sulfur-containing reagent (Rs) with at least one alkoxy and / or halosilane of formula (I):
  • R 1 identical or different, each represent:
  • an aryl radical having from 6 to 18 carbon atoms an alkoxy radical -OR 2 , with R 2 corresponding to a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms or an aryl radical having from 6 to 18 carbon atoms;
  • an arylalkyl radical or an alkylaryl radical (C 6 -C 18 aryl, C 1 -C 20 alkyl);
  • a hydroxyl radical (-OH); or a halogen, preferably chlorine; at least one of these radicals R 1 being -OR 2 , -OH or a halogen, and, in addition, these radicals R 1 , when they are neither hydroxyls nor halogens, possibly being carriers of at least one halogen group;
  • Y represents an organic monovalent functional group, preferably chosen from the "sensitive" functional groups R 3 , comprising at least one ethylenic and / or acetylenic unsaturation, in particular selected from:
  • the silane of formula (I) is such that at least one (more preferably only one) of the radicals R 1 is -OR 2 .
  • the invention also relates in its second object to new (poly) sulfided alkoxy and / or halosilanes of formula (III):
  • a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms; an aryl radical having from 6 to 18 carbon atoms;
  • R 2 an alkoxy radical -OR 2 , with R 2 corresponding to a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms or an aryl radical having from 6 to 18 carbon atoms;
  • an arylalkyl radical or an alkylaryl radical C 6 -C 18 aryl, C 1 -C 20 alkyl
  • a hydroxyl radical -OH
  • a halogen preferably chlorine, at least one of these radicals R 1 being -OR 2 , -OH or a halogen, and, furthermore, these radicals R 1 , when they are neither hydroxyls nor halogens, optionally carrying at least one halogen group;
  • R 3 , R 4 which are identical to or different from one another, each represent hydrogen or a monovalent hydrocarbon group chosen from a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms and an alkoxyalkyl radical, linear, branched or cyclic, having from 1 to 20 carbon atoms;
  • R 6 , R 7 and R 8 which are identical to or different from each other, each represent hydrogen or a monovalent hydrocarbon group chosen from a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms and a linear or branched linear alkoxyalkyl radical having from 1 to 20 carbon atoms,
  • n corresponds to an integer greater than or equal to 1, preferably equal to 1 or 2, even more preferably equal to 1 (the formula (III) is then in the latter case called formula (III.I); )
  • x corresponds to an integer or fractional number, generally between 1 and 10, preferably between 1 and 5, and even more preferably between 1.5 and 5, in particular between 2 and 5, and especially between 3 and 5; and 5, even between 3.5 and 4.5 or between 3.8 and 4.2, the limits of these intervals being given within +/- 0.2.
  • novel (poly) sulphidized alkoxy and / or halosilanes of formula (III), in particular of formula (III.1) can be, and preferably, obtained by the process according to the invention.
  • the invention also relates in its third object to the use of at least one polysulfurized alkoxy and / or halosilane of formula (III) (in particular of formula (HL1)), in particular at least one polysulfurized silane of formula (III.1) isopropylene ball joint, as white-elastomeric coupling agent in elastomer compositions, preferably comprising at least one diene elastomer and a white filler (in particular a precipitated silica) as a reinforcing filler, said compositions being for example intended for the manufacture of elastomer (s) diene (s).
  • the present invention relates to a composition of elastomer (s), in particular diene (s), comprising a reinforcing white filler and an effective amount of at least one polysulfurized alkoxy and / or halosilane of formula (III) (In particular of formula (HL1)), in particular a polysulfurized monoorganoxysilane of formula (III.1) with isopropylene ball.
  • the invention relates to a process for the preparation of the abovementioned elastomer compositions.
  • the invention relates to elastomeric articles (s) based on an elastomer composition (s) referred to above.
  • the invention proposes to react a functionalized alkoxy and / or halosilane (I), preferably alkenylated, for example allyl-terminated, with a sulfur-containing reagent (Rs).
  • a functionalized alkoxy and / or halosilane I
  • Rs sulfur-containing reagent
  • the new route according to the invention is based on an ionic addition mechanism that is easy to implement and economical. (Rs) and (I) are reacted according to an ionic addition mechanism.
  • this ionic addition mechanism is (quasi) spontaneous. It does not require activation, in particular actinic activation (photonic: for example, a UV lamp, in particular of the Hg-HP type) and / or thermal and / or ultrasonic activation, and / or by electron bombardment.
  • a thermal activation which generally consists of bringing the reaction medium at a temperature between room temperature and 120 0 C, preferably between 50 and 110 0 C at normal atmospheric pressure.
  • the polysulphurized silanes obtained by the process according to the invention, and especially the novel polysulfide silanes, have particular applications as white-elastomer coupling agents in elastomer (s), in particular diene (s) compositions.
  • elastomer in particular diene (s) compositions.
  • a white filler for example a siliceous filler, as reinforcing filler, these compositions being for example intended for the manufacture of elastomeric articles, in particular diene (s), such as, inter alia, soles of shoes, tires .
  • Such coupling agents preferably impart good mechanical properties to the silica filled elastomers in which they are incorporated. The same is true of their rheological characteristics before vulcanization.
  • the good mechanical properties after vulcanization can result in rather high levels of moduli with high elongations, tensile strength, reinforcement indices and / or hardness (shore or other). They thus offer a good compromise with regard to the rheological properties before vulcanization and the mechanical properties after vulcanization.
  • the (poly) sulphidized alkoxy and / or halosilanes obtained by the process according to the invention advantageously comprise a polyisulfide unit [S] x .
  • Y has the following formula (II):
  • the symbols R 3 , R 4 which are identical to or different from each other, each represent hydrogen or a monovalent hydrocarbon group chosen from an alkyl radical, linear, branched or cyclic, having from 1 to 20 carbon atoms, carbon and a straight or branched linear alkoxyalkyl radical having from 1 to 20 carbon atoms;
  • the symbol R 5 represents -CH 2 or -CR 6 R 7 , the symbols R 6 , R 7 , which are identical to or different from each other, each representing hydrogen or a monovalent hydrocarbon group chosen from an alkyl radical, linear, branched or cyclic, having from 1 to 20 carbon atoms and a linear, branched or cyclic alkoxyalkyl radical having from 1 to 20 carbon atoms, methyl being particularly preferred;
  • the symbol n corresponds to an integer greater than or equal to 1, preferably equal to 1 or 2, even more preferably equal to 1 (the formula
  • Y has the following formula (IL1):
  • the symbols R 3 , R 4 which are identical to or different from each other, each represent hydrogen or a monovalent hydrocarbon group chosen from a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms, carbon and a straight or branched linear alkoxyalkyl radical having from 1 to 20 carbon atoms;
  • the symbol R 5 represents -CH 2 or -CR 6 R 7 , the symbols R 6 , R 7 , identical to or different from each other, each representing hydrogen or a group monovalent hydrocarbon chosen from a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms and a linear, branched or cyclic alkoxyalkyl radical having from 1 to 20 carbon atoms, methyl being particularly preferred.
  • the functional group Y of the alkoxy and / or halosilane (I) forming the starting material of the process according to the invention proves to be a precursor of the ball (s) which connects (s) the silicon to the unit sulfur in the alkoxides and / or halosilanes (poly) sulfides obtained.
  • R 4 corresponds to H
  • R 5 corresponds to -CH 2 , so that the (ionic) addition of (Rs) takes place on the carbon in beta ( ⁇ ) of the alkoxy and / or halosilane (I).
  • R 4 corresponds to an alkyl radical (preferably methyl or ethyl) and R 5 corresponds to -CH 2 , so that the addition of (Rs) is operates on the beta carbon ( ⁇ ) of the alkoxy and / or halosilane (I).
  • Rs alkyl radical
  • R 5 corresponds to -CH 2
  • the addition of the alkoxy and / or halosilane (I) on the beta ( ⁇ ) carbon leads, by the process according to the invention, to new (poly) sulphurized alkoxy and / or halosilanes.
  • R 4 corresponds to H and R 5 corresponds to -CR 6 R 7 , with R 6 and R 7 representing -CH 3 , so that the addition (ionic ) of (Rs) operates on the gamma carbon ( ⁇ ) of the alkoxy and / or halosilane (I).
  • the (ionic) addition according to the invention of the alkenyl-terminated Y of formula (II), preferably of formula (IL1), of the silane (I) benefits from total regioselectivity and from a high isolated yield, for example greater than 90%: this total regioselectivity means that the double bond of the radical Y reacts with the sulfur-containing reagent (Rs) without secondary reaction.
  • the alkoxysilane or the halosilane of formula (I) used in the process according to the invention can be obtained by reacting at least one halogen and / or alkoxysilane with at least one halogenated organic compound, preferably an allyl halide, in the presence of at least one metal selected from the group comprising Mg, Na, Li, Ca, Ba, Cd, Zn, Cu, their mixtures and their alloys (preferably magnesium), in the presence of an ethereal organic solvent and or an acetal-type solvent, according to a mechanism based on the Barbier reaction.
  • at least one halogen and / or alkoxysilane preferably an allyl halide
  • Another route of synthesis of the alkoxy and / or halosilane of formula (I) of departure may be a more traditional route, in particular in which a trialkoisilane and / or trihalosilane functionalized with a halogenated alkyl group is employed, according to a reaction mechanism.
  • Grignard type which involves a halogeno magnesium Grignard reagent, namely MeMgCl. This synthetic route is described in particular in applications JP-A-2002179687 and WO-A-03/027125.
  • the sulfur-containing reagent (Rs) is chosen from the group comprising HS x H, O, O'-dialkyl (preferably ethyl) -dithiophosphonate (HSPS), M ' 2 S X , (M 'being an alkali metal), xS, HS x and mixtures thereof, the symbol x corresponding to an integer or fractional number, preferably a number ranging from 1 to 10, even more preferably from 1 to 5 , in particular from 1.5 to 5, the limits of these intervals being given within +/- 0.2.
  • HSPS sulfur-containing reagent
  • reagents (Rs) are economical and readily available.
  • the reagents (Rs) of the polysulfane type (HS x H) may for example be prepared according to a procedure described in the literature, in particular by W. Post et al., J.Org.Chem.,
  • the Na 2 S x salt can be reacted with dilute HCl at room temperature according to the following general reaction: Na 2 S x + 2H + - ⁇ y H 2 S n + (ly) H 2 S + (x -yn- (ly)) S + 2Na +
  • this metal polysulfide may be prepared, for example, by reaction of an alkali metal sulphide M' 2 S, containing water of crystallization, with elemental sulfur. , operating at a temperature between 60 and 300 0 C, under vacuum and in the absence of organic solvent.
  • (Rs) corresponds to O, O'-dialkyl (preferably ethyl) -dithio-phosphonate (HSPS) or to HSH
  • the product of the reaction is reacted between (I) and (Rs) with a secondary sulfur-containing reagent (Rs2) selected from the group consisting of S x and / or X1S-SX2, with the symbol x as defined above and X1 and X2 representing a halogen, preferably the chlorine, this secondary sulfurization being advantageously carried out in basic medium, for example containing in the base, K3CO3, Na 2 CO 3, K3PO4, EtONa or mixtures thereof.
  • the product of the reaction between (I) and (Rs) is a sulphurized monosilane which can be converted into polysulfurized disilane using the secondary sulfur-containing reagent (Rs2).
  • the process according to the invention also incorporates advantageous quantitative aspects.
  • the molar ratio (I) / (Rs) is in particular between 5 and 0.1, preferably between 3 and 0.5, and more preferably between 2 and 0.7.
  • the (ionic) addition of the process according to the invention can be carried out in the presence of solvent (s), preferably chosen from the group of hydrocarbon solvents. non-reactive, in particular chosen from aromatic hydrocarbons free of carbonyl or hydroxyl functions.
  • solvent preferably chosen from the group of hydrocarbon solvents. non-reactive, in particular chosen from aromatic hydrocarbons free of carbonyl or hydroxyl functions.
  • the process according to the invention can be carried out for example under atmospheric pressure. It is possible to run (Rs) on a foot of (I), for example between 50 and 70 ° C.
  • the reaction medium obtained can be treated by filtration of any residual sulfur, washing with an organic solvent, such as heptane, and then washing the filtrate with an aqueous solution, in particular of pH between 7 and 8, the organic solvent such as that heptane can then be removed under reduced pressure.
  • an organic solvent such as heptane
  • the process according to the invention may comprise at least one hydrolysis step making it possible to convert at least one of the radicals R 1 corresponding to -OR 2 of the alkoxy and / or halosilane (poly) sulphide to hydroxyl (-OH). .
  • the new synthetic route proposed in the first subject of the invention as described above is also very interesting in that it leads to new alkoxy and / or (poly) sulfide halosilanes.
  • the invention therefore aims at new alkoxy and / or halosilanes
  • the invention aims in its second object of new alkoxy and / or halosilanes (poly) sulfides of formula (III.1) below, whether or not obtained by the process according to the first subject of the invention:
  • a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms; an aryl radical having from 6 to 18 carbon atoms;
  • alkoxy radical -OR 2 an alkoxy radical -OR 2 , with R 2 corresponding to a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms or an aryl radical having from 6 to 18 carbon atoms; alkylaryl radical (C 6 cis, C1-C20);
  • a hydroxyl radical (-OH); or a halogen, preferably chlorine; at least one of these radicals R 1 being -OR 2 , -OH or a halogen, and, in addition, these radicals R 1 , when they are neither hydroxyls nor halogens, possibly being carriers of at least one halogen group;
  • R 3 , R 4 which are identical to or different from one another, each represent hydrogen or a monovalent hydrocarbon group chosen from a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms and an alkoxyalkyl radical, linear, branched or cyclic, having from 1 to 20 carbon atoms;
  • the symbols R 6 , R 7 and R 8 which are identical to or different from each other, each represent hydrogen or a monovalent hydrocarbon group chosen from a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms and a linear or branched linear alkoxyalkyl radical having from 1 to 20 carbon atoms,
  • x corresponds to an integer or fractional number, generally between 1 and 10, preferably between 1 and 5, and even more preferably between 1.5 and 5, in particular between 2 and 5, and especially between 3 and 5; and 5, even between 3.5 and 4.5 or between 3.8 and 4.2, the limits of these intervals being given within +/- 0.2.
  • the products (III), in particular (III.1), can be further distinguished by their preferred method of production according to the process according to the invention; they are then advantageously derived from an ionic addition of (Rs) to the ⁇ -carbon of the Y group (formula (II), especially (ILl)) of the silane (I).
  • the (poly) sulphidized alkoxy and / or halosilanes of formula (III), in particular (III.1) are preferably capable of being prepared by the process according to the invention (in particular by the ionic addition of (Rs) to carbon ⁇ of the Y group (formula (II), in particular (IL1)) of the silane (I)).
  • two of the substituents R 1 of at least one of the two terminal silicas are alkyl radicals, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, CH 3 O-CH 2 - and CH 3 O-CH (CH 3 ) CH 2 - (for example methyl, ethyl, n-propyl and isopropyl) or aryl radicals, for example phenyl, these two substituents R 1 being preferably methyl;
  • the third substituent R 1 is preferably an alkoxy-OR 2 , in particular with R 2 corresponding to methyl, ethyl, n-propyl, isopropyl, n-butyl, CH 3 O -CH 2 - or CH 3 O-CH (CH 2) 3 ) CH 2 - (for example methyl, ethyl, n-propyl or isopropyl).
  • the products of formula (III), especially of formula (III.1), which are especially targeted by the present invention are (poly) sulphidized alkoxysilanes, more particularly (poly) sulphidized alkoxysilanes of formula (III.2):
  • R 1'1 , R 1'2 , R 1'3 identical or different from each other, meet one of the definitions given in the above discussion for R 1 ;
  • R 1 1 and R 1'3 corresponding preferably to an alkyl (advantageously methyl or ethyl) and
  • R 1'2 corresponding preferably to an alkoxy (advantageously methoxy or ethoxy),
  • the symbol x corresponding to an integer or fractional, understood in general between 1 and 10, preferably between 1 and 5, and more preferably between 1.5 and 5, in particular between 2 and 5, in particular between 3 and 5, or even between 3.5 and 4.5 or between 3.8 and 4.2, the limits of these intervals being within +/- 0.2.
  • the present invention relates, for example, to the compounds of the following formulas: ## STR2 ## wherein CH 2 CH 2 (CH 3 ) -S x - (CH 3 ) -CH-CH 2 -SiCl 3 (C 2 H 5 O) 3 Si-CH 2 -CH- (CH 3 ) ) -S x - (CH 3) -CH-CH 2 -Si (OC 2 H 5 ) 3 in which the symbol x corresponds to an integer or fractional number between 1.5 and 5, in particular between 2 and 5, in particular between 3 and 5, for example between 3.5 and 4.5 or between 3.8 and 4.2, the limits of these ranges being given within +/- 0.2.
  • Particularly preferred compounds according to the invention have the formula (C 2 H 5 O) (CH 3 ) 2 Si-CH 2 -CH- (CH 3 ) -S x - (CH 3 ) -CH-CH 2 -Si ( CH 3 ) 2 (OC 2 H 5 ), in which the symbol x corresponds to an integer or fractional number between 1.5 and 5, preferably between 2 and 5, in particular between 3 and 5, for example between 3.5 and 4.5 or 3.8 to 4.2, the limits of these ranges being within +/- 0.2; mention may in particular be made of bis-monoethoxydimethylsilylisopropyl tetrasulfide (MESiPrT abbreviated).
  • the symbol x of the formulas (III), (III.1), (III.2) and formulas above is an integer or fractional number which represents the number of sulfur atoms present in a molecule of these formulas. This number may be an exact number of sulfur atoms in the case where the synthetic route of the compound in question can give rise to only one kind of polysulfide product.
  • this number is rather the average of the number of sulfur atoms per molecule of compound under consideration, insofar as the synthesis route chosen gives rise rather to a mixture of polysulfur products each having a different number of sulfur atoms.
  • the polysulfurized compounds synthesized consist in fact of a distribution of polysulfides, ranging from monosulphide or disulfide S 2 to heavier polysulfides (for example S ⁇ s) centered on a mean value in moles (value of the symbol x) falling within the general areas mentioned above.
  • the polysulfurized monoorganoxysilanes synthesized consist of a polysulfide distribution comprising a molar ratio of (S 3 + S 4 ) equal to or greater than 40% and, preferably, equal to or greater than 50%; and (S 2 + S ⁇ s) equal to or less than 60% and, preferably, equal to or less than 50%.
  • the molar level of S 2 is advantageously equal to or less than 30% and, preferably, equal to or less than 20%. All limit values are given to the measurement accuracy (by NMR), with an absolute error of approximately ⁇ 1.5 (eg 20 ⁇ 1.5% for the last indicated rate).
  • these novel products may find a particularly advantageous application as coupling agents between a white filler (such as a siliceous material, for example a precipitated silica) and an elastomer in elastomer compositions (s). ), especially diene (s), which comprise such a white filler as a reinforcing filler.
  • a white filler such as a siliceous material, for example a precipitated silica
  • diene (s) which comprise such a white filler as a reinforcing filler.
  • These novel compounds (III), in particular (III.1), in particular (III.2) preferably offer a very satisfactory compromise with regard to the rheological properties before vulcanization and the mechanical and / or dynamic properties after vulcanization.
  • the invention relates to the use of at least one polysulfurized silane of formula (III), preferably of formula (III.1), in particular of formula (III.2), as a white filler-elastomer coupling in elastomer (s) compositions, for example diene (s), especially comprising at least one diene elastomer and a white filler (in particular precipitated silica) as a reinforcing filler, said compositions being example intended for the manufacture of elastomeric articles, in particular diene (s).
  • elastomer for example diene (s), especially comprising at least one diene elastomer and a white filler (in particular precipitated silica) as a reinforcing filler, said compositions being example intended for the manufacture of elastomeric articles, in particular diene (s).
  • the present invention resides in elastomer (s) compositions, in particular diene (s), comprising a reinforcing white filler and, as a coupling agent, (an effective amount of) at least one a polysulfurized silane of formula (III), preferably of formula (III.1), in particular of formula (III.2). More particularly, these compositions may comprise (the parts being given by weight), per 100 parts of diene elastomer (s):
  • the amount of coupling agent (s), chosen especially in the abovementioned ranges, is determined so that it represents from 0.5 to 20%, preferably from 1 to 15%, and more preferably, from 1 to 10%, relative to the weight of the reinforcing white filler.
  • a compound of formula (III), preferably of formula (III.1), in particular of formula (III.2) may also make it possible to completely get rid of or almost totally the presence of zinc or a zinc derivative (such as ZnO), usually employed as a vulcanization activator, in the elastomer (s) composition (s), in particular diene (s), comprising such a compound (III), preferably (III.1), especially (III.2), and a reinforcing white filler, intended for example for the manufacture of elastomeric articles (s), in particular diene (s).
  • Said elastomer compositions according to the invention may, for example, comprise less than 0.75 part, in particular less than 0.5 part, of zinc (per 100 parts of elastomer (s) (diene (s)) .
  • the coupling agent may be grafted onto the reinforcing white filler (via in particular its alkoxysilyl function, for example ethoxysilyl), the white filler thus "precoupled” can then be bonded to the elastomer by the intermediate of the polysulfide free function.
  • the term "reinforcing white filler” is intended to mean, in particular, a white filler capable of reinforcing on its own, with no other means than that of a coupling agent, an elastomer composition (s) of the type rubber, natural (s) and / or synthetic (s).
  • the physical state under which the reinforcing white filler is present is indifferent, that is to say that said filler may be for example in the form of powder, microbeads or granules.
  • the reinforcing white filler consists of silica, alumina or a mixture of these two species.
  • the reinforcing white filler is formed by silica.
  • silica capable of being used in the invention are suitable in particular all precipitated or pyrogenic silicas, in particular those having a BET specific surface area less than or equal to 450 m 2 / g.
  • a precipitation silica is used, which can be conventional or, preferably, highly dispersible.
  • highly dispersible silica in particular any silica having an ability to deagglomeration and dispersion in a very large polymeric matrix, particularly observable by electron or optical microscopy, thin sections.
  • dispersible silicas mention may be made of silica Perkasil
  • KS 430 from Akzo
  • silicas BV3380 and Ultrasil 7000 from Degussa
  • silicas Zeosil 1165 MP and 1115 MP from Rhodia
  • silica Hi-SiI 2000 from PPG silicas Zeopol 8741 or 8745 from the Huber company.
  • Treated precipitated silicas such as, for example, the silicas containing aluminum described in patent applications EP-A-0735088, 0762992 and
  • precipitation silicas possessing: a CTAB specific surface area of between 100 and 240 m 2 / g, for example between 110 and 180 m 2 / g, a BET specific surface area of between 100 and 250 m 2 are particularly suitable; / g, for example between 110 and 190 m 2 / g, optionally, a DOP oil uptake of less than 300 ml / 100 g, for example between 200 and 295 ml / 100 g, and optionally, a surface area BET / surface area ratio specific CTAB between 1.0 and 1.6.
  • Silica also refers to blends of different silicas.
  • the CTAB specific surface area is the external surface, which can be determined according to the NF T 45007 method (November 1987).
  • the BET surface area can be measured according to the method of BRININER - EMMETT - TELLER described in "The Journal of the
  • the DOP oil intake can be determined according to the standard
  • a dispersible alumina having:
  • a BET specific surface area of between 30 and 400 m 2 / g, for example between 60 and 250 m 2 / g,
  • reinforcing aluminas there may be mentioned Alumina A125, CR125, D65CR from the company Baikowski.
  • Diene elastomers that can be used in the compositions according to the fourth subject of the invention more specifically mean:
  • Homopolymers obtained by polymerization of a conjugated diene monomer having from 4 to 22 carbon atoms for example: 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl 1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-methyl-3-isopropyl butadiene, 1,3, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene;
  • vinyl aromatic monomers having 8 to 20 carbon atoms for example: styrene, ortho-, meta- or para-methylstyrene, the commercial "vinyl-toluene" mixture, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene;
  • vinyl nitrile monomers having from 3 to 12 carbon atoms, for example acrylonitrile or methacrylonitrile;
  • acrylic ester monomers derived from acrylic acid or methacrylic acid with alkanols having from 1 to 12 carbon atoms, for example methyl acrylate, ethyl acrylate or propyl acrylate; n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; copolymers which may contain between 99 and 20% by weight of diene units and between 1 and 80% by weight of vinyl aromatic units, vinyl nitriles and / or acrylic esters;
  • ternary copolymers obtained by copolymerization of ethylene, an ⁇ -olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type, such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene (EPDM elastomer);
  • one or more elastomer chosen from (1) polybutadiene, polychloroprene, polyisoprene [or poly (2-methyl-1,3-butadiene)]; (2) poly (isoprene-butadiene), poly (isoprene-styrene), poly (isoprene-butadiene-styrene), poly (butadiene-styrene), poly (butadiene-acrylonitrile); (4) natural rubber; (5) butyl rubber; (6) a mixture of the abovementioned elastomers (1), (2), (4),
  • compositions according to the invention also contain all or part of the other constituents and auxiliary additives usually used in the field of elastomer (s) and rubber (s) compositions.
  • vulcanizing agents chosen from sulfur or sulfur-donor compounds, for example thiuram derivatives
  • vulcanization accelerators such as, for example, guanidine derivatives or thiazole derivatives
  • vulcanization activators such as, for example, zinc oxide, stearic acid and zinc stearate;
  • additive for other additive (s), there may be mentioned for example: a conventional reinforcing filler consisting of carbon black; carbon blacks are suitable for all carbon blacks, especially those of the type HAF, ISAF, SAF; by way of nonlimiting examples, mention may be made of Nl 15, N134, N234, N339, N347 and N375 carbon blacks; in general, the amount of carbon black is determined so that, on the one hand, the reinforcing white filler used represents more than 50% of the weight of the white filler + carbon black, and, d on the other hand, the amount of total reinforcing filler (white filler + carbon black) remains within the indicated ranges of values previously for the reinforcing white filler, about the weight constitution of the compositions;
  • a conventional white filler with little or no strength such as clays, bentonite, talc, chalk, kaolin, titanium dioxide or a mixture of these species;
  • antioxidants or antiozonants such as, for example, N-phenyl-N'- (1,3-dimethylbutyl) -p-phenylenediamine;
  • the compositions in accordance with the invention may contain reinforcing filler recovery agents, comprising, for example, the only function Y, capable in a known manner, thanks to an improvement in the dispersion of the filler in the elastomer matrix (s) and a lowering of the viscosity of the compositions, to improve the ability to implement the compositions in the green state.
  • reinforcing filler recovery agents consist, for example, of alkylakoxysilanes (in particular alkyltriethoxysilanes), polyols, polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkanol amines), and ⁇ , û-poly-dimethylsiloxanes. dihydroxylated.
  • Such an assisting agent when one is used, is employed at 1 to 10 parts by weight, and preferably 2 to 8 parts, per 100 parts of reinforcing white filler.
  • the process for preparing the diene (s) elastomer compositions comprising a reinforcing white filler and at least one coupling agent can be carried out according to a conventional procedure in one or two stages.
  • vulcanizing agent (s) and optionally: the product are introduced and kneaded in a conventional internal mixer, for example of the Banbury or Brabender type. (or) vulcanization accelerators and / or vulcanization activator (s).
  • the result of this first mixing step is then resumed on an external mixer, generally a roller mixer, and the (or) vulcanizing agent (s) and optionally: the accelerator (s) are then added thereto vulcanization and / or vulcanization activator (s). It may be advantageous for the preparation of certain articles to implement a two-step process both conducted in an internal mixer.
  • the first step all the necessary constituents are introduced and kneaded, with the exception of the vulcanization agent (s) and optionally: vulcanization accelerator (s) and / or vulcanization activators, or a part of the constituents necessary by applying the same exception law.
  • the purpose of second step that follows is essentially to subject the mixture of the first step, optionally supplemented by the addition of the (or) constituent (s) necessary (s) missing with application of the same exception law, a complementary heat treatment .
  • the result of this second step is then also taken up again on an external mixer to add the vulcanization agent (s) and optionally: the vulcanization accelerator (s), and / or the ) vulcanization activators.
  • the working phase in an internal mixer is generally carried out at a temperature ranging from 80 to 200 ° C., preferably from 80 to 180 ° C.
  • This first working phase is followed by the second phase of working in an external mixer while operating at a temperature of lower temperature, generally less than 120 0 C and preferably ranging from 20 to 80 0 C.
  • the final composition obtained is then calendered, for example in the form of a sheet, a plate or a profile usable for the manufacture of elastomeric articles.
  • the vulcanization (or cooking) is conducted in a known manner at a temperature generally ranging from 130 to 200 ° C., optionally under pressure, for a sufficient time which may vary, for example, between 5 and 90 minutes depending in particular on the cooking temperature, of the vulcanization system adopted and the kinetics of vulcanization of the composition under consideration.
  • the present invention taken in its fourth subject, relates to the elastomer compositions (s) previously described both in the raw state (that is to say before cooking) and the cooked state (ie after crosslinking or vulcanization).
  • the elastomer compositions according to the invention can be used for preparing finished or semi-finished articles made of elastomer (s) having a body comprising said compositions.
  • These compositions are for example useful for preparing articles consisting of shoe soles, tires (particularly tire treads), conveyor belts, power transmission belts, hoses, expansion joints. , appliance seals, engine mounts, cables, cable sheaths, ropeway rollers.
  • the one-dimensional silicon-29 NMR analyzes are performed with a Bruker AMX 300 spectrometer and a selective 10 mm 29 Si probe operating at a silicon observation frequency at 59 MHz.
  • the chemical shifts ( ⁇ ) are expressed in ppm; tetramethylsilane is used as an external reference for 1 H and 29 Si chemical shifts.
  • the temperature is controlled by a variable temperature unit ( ⁇ 0.1 0 K).
  • the NMR spectra are carried out at 300 ° C.
  • a "gated reverse" decoupling accumulation sequence of the proton (Waltz 16) is used.
  • the angle of the silicon-29 pulse is equal to 45 ° and the duration between two silicon pulses is fixed at 4.5 seconds.
  • the free precession signal (FID) is obtained after 4096 accumulations.
  • the spectral width is 10870 Hz and the number of points defining the free precession signal is equal to 32768.
  • a simple acquisition sequence with a pulse angle of 30 °, a pulse duration of 4.6 seconds and 256 accumulations is used.
  • the spectral width is 4500 Hz and no mathematical treatment is practiced.
  • the observation frequency is 300 MHz.
  • a proton decoupling accumulation sequence (Waltz 16) is used, with a pulse angle of 30 °, a duration between pulses of 3 seconds and 8192 accumulations.
  • the spectral width is 20000 Hz and the signal is processed by an exponential function before the Fourier transform.
  • the observation frequency is 75 MHz.
  • the deuterated solvent (CDCl3) serves to compensate for possible derivatives of the magnetic field and makes it possible to calibrate the spectra in chemical displacement.
  • Example 1 is a polysulfane synthesis.
  • Examples 2 to 9 are syntheses of polysulfurized bis-monoethoxydimethylsilane.
  • Example 10 is an illustration of the addition of a thiophosphorus compound to
  • Example 11 is an addition of polysulfane to a methally dimethyl ethoxysilane.
  • Example 12 illustrates a ⁇ addition to obtain a polysulfurized bistrichlorosilane.
  • Example 13 illustrates a ⁇ addition to obtain a polysulfide bistriethoxysilane.
  • Example 14 illustrates the route of addition of a polysulfane to the ⁇ -position carbon of the Y allyl radical of the starting allyldimethylethoxysilane (I).
  • Examples 15 and 16 illustrate the optional step of hydrolysis of polysulfurized alkoxysilanes obtained according to the process according to the invention.
  • Example 17 illustrates the coupling agent application in an elastomer composition.
  • Example 4 In a 40 ml stainless steel autoclave 1.03 g are introduced under argon
  • Example 2 (7.26 mmol) of allyldimethylethoxysilane and 0.90 g (6.98 mmol) of polysulfane prepared in Example 1.
  • the reactor was heated to 100 0 C for 16 hours. Let cool.
  • the sulfur formed is filtered off and 683 mg of a light yellow liquid are recovered which has a structure identical to that of the product obtained at the end of Example 2.
  • the reactor is irradiated with a lamp (Hg-HP) for 150 minutes.
  • Example 2 In a stainless steel autoclave of 40 ml are introduced under argon 20 g (0.134 mol) of allyldimethylethoxysilane and 19.6 g (0.137 mol) of polysulfane prepared in Example 1. The reactor was heated to 150 0 C for 16 hours. Let cool. The sulfur formed is filtered off and 27.5 g of a light yellow liquid are recovered which has a structure identical to that of the product obtained at the end of Example 2. The yield is 95%.
  • Example 9 Into a 40 ml autoclave in hastelloy under autogenous pressure, with an oil bath and magnetic stirring, 20.01 g of allyldimethylethoxysilane (129.2 mmol, 1 eq.) And 18.16 g of prepared polysulfane are introduced. in Example 1 (132.2 mmol, 1.02 eq.) Both reagents are immiscible. The reactor is closed, then stirred and heated at 150 0 C for 16 hours. It is allowed to cool and 25.65 g of a yellow oil are obtained which analyzes confirm the unique structure below. The isolated yield is about 90% and the purity greater than 98%.
  • the polysulfurized bis-monoethoxydimethylsilane product obtained in Examples 2 to 9 has the following formula:
  • the reaction mass is then distilled under reduced pressure (minimum pressure: 350 mbar), using a packed column of 60 cm, with retrogradation and a reflux ratio of 1/10. After distillation, the isolated yield of allyldimethylethoxysilane is 79%, without formation of bisallydimethylsilane.
  • This example illustrates the use and the behavior of a polysulfurized alkoxysilane according to the invention, in this case polysulfurized bis-monoethoxydimethylsilane obtained in Example 9 (or bis-monoethoxydimethylsilylisopropyl tetrasulfide (MESiPrT)), as the coupling agent in an industrial rubber composition containing silica as a reinforcing filler.
  • a polysulfurized alkoxysilane according to the invention in this case polysulfurized bis-monoethoxydimethylsilane obtained in Example 9 (or bis-monoethoxydimethylsilylisopropyl tetrasulfide (MESiPrT)), as the coupling agent in an industrial rubber composition containing silica as a reinforcing filler.
  • a first phase allows by thermomechanical work at high temperature (up to a maximum temperature between 130 and 160 0 C). It is followed by a second phase, called productive, mechanical work at temperatures below 110 0 C, this phase allowing the introduction of the vulcanization system.
  • the first phase is carried out by means of a mixing apparatus, in this case a Brabender brand internal mixer (70 ml capacity).
  • the fill factor is 0.75.
  • the initial temperature and the speed of the rotors are fixed each time so as to reach mixing fall temperatures of 130 - 160 ° C. It is decomposed here in two passes.
  • the elastomer and then the reinforcing filler constituted by silica (fractional introduction) with the coupling agent and stearic acid.
  • the duration is between 2 and 10 minutes.
  • a second pass makes it possible to incorporate the zinc oxide and the antioxidant 6-PPD.
  • the duration is between 2 and 5 minutes.
  • the second phase allows the introduction of the vulcanization system (sulfur, DPG, CBS and TBzTD). It is carried out on a roll mill, preheated to 50 ° C. The duration of this phase is between 5 and 10 minutes.
  • the final compositions are then calendered in the form of plates 2 to 3 mm thick.
  • the rheological properties are measured on these compositions in the green state, which notably makes it possible to optimize the duration and the vulcanization temperature.
  • the measurements are performed on the compositions in the green state.
  • the composition to be tested is placed in the controlled test chamber at a temperature of 160 ° C. for 30 minutes, and the resistive torque opposed by the composition is measured at a low amplitude oscillation (3 °).
  • a biconical rotor included in the test chamber the composition completely filling said chamber.
  • the minimum torque (Cm) which reflects the viscosity of the composition at the considered temperature
  • the toasting time Ts2 corresponding to the time required to have a rise of 2 points above the minimum torque at the temperature considered (160 0 C) and which reflects the time during which it is possible to use the raw mixtures at this temperature without having initiation of vulcanization.
  • the coupling agent according to the present invention makes it possible to improve the vulcanization kinetics (Vret max or T90-Ts2) of the corresponding composition with respect to the reference composition, without penalizing the viscosity of the raw mixture (the couple). mini is identical)
  • the use of the coupling agent according to the invention, without penalizing the implementation, allows a gain on the final cooking time.
  • the modules x% correspond to the stress measured at x% of tensile strain. It is possible to determine an energy at break which represents the area under the curve, expressed in Joules.
  • the Shore A hardness measurement of the vulcanizates is carried out according to the indications of ASTM D 2240. The value given (in points) is measured at 15 seconds.
  • composition I containing a coupling agent according to the present invention has a good compromise of mechanical properties, without degradation of the ultimate properties and with a very satisfactory hardness.
  • the dynamic properties are measured on a Metravib VA3000 viscoanalyzer, according to ASTM D 5992.
  • composition I containing a coupling agent according to the invention has a compromise of very satisfactory dynamic properties.
  • the value of the loss factor (tan ⁇ ), which is the reflection of the energy absorbed or restored by the vulcanizate during a deformation under the test conditions mentioned, of the composition I containing a coupling agent according to the invention is close to that of the reference composition R, independently of the dynamic loading mode.
  • composition I containing a coupling agent according to the invention.
  • the composition I consequently has non-degraded hysteretic properties with respect to the reference composition R.

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EP07822459A 2006-11-10 2007-11-09 Verfahren zur herstellung von (poly)thioalkoxy- und/oder halogensilanen, neue, durch dieses verfahren erhaltene produkte und deren verwendung als kupplungsmittel Withdrawn EP2094716A2 (de)

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FR0609838A FR2908411B1 (fr) 2006-11-10 2006-11-10 Procede de preparation d'alcoxy et/ou halogenosilanes (poly)sulfures, nouveaux produits susceptibles d'etre obtenus par ce procede et application comme agents de couplage
PCT/EP2007/062171 WO2008055989A2 (fr) 2006-11-10 2007-11-09 Procede de preparation d'alcoxy et/ou halogenosilanes (poly)sulfures, nouveaux produits susceptibles d'etre obtenus par ce procede et application comme agents de couplage

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CN111234315A (zh) * 2020-02-25 2020-06-05 南京曙光精细化工有限公司 在使用中释放低量voc的含硫硅烷偶联剂及其制备方法

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US5580919A (en) * 1995-03-14 1996-12-03 The Goodyear Tire & Rubber Company Silica reinforced rubber composition and use in tires
US5663358A (en) * 1996-01-22 1997-09-02 The Goodyear Tire & Rubber Company Process for the preparation of organosilicon disulfide compounds
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US20100144959A1 (en) 2010-06-10
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