EP1250383A1 - Verwendung einer assoziation einer zusammensetzung basierend auf mit einem kupplungsaktivator funktionalisierten organosilanen, als kupplungssystem für weissen füllstoff enthaltende dienelastomerzusammensetzungen - Google Patents

Verwendung einer assoziation einer zusammensetzung basierend auf mit einem kupplungsaktivator funktionalisierten organosilanen, als kupplungssystem für weissen füllstoff enthaltende dienelastomerzusammensetzungen

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Publication number
EP1250383A1
EP1250383A1 EP00993721A EP00993721A EP1250383A1 EP 1250383 A1 EP1250383 A1 EP 1250383A1 EP 00993721 A EP00993721 A EP 00993721A EP 00993721 A EP00993721 A EP 00993721A EP 1250383 A1 EP1250383 A1 EP 1250383A1
Authority
EP
European Patent Office
Prior art keywords
chosen
coupling
vulcanization
elastomer
constituent
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.)
Withdrawn
Application number
EP00993721A
Other languages
English (en)
French (fr)
Inventor
Pierre Barruel
Nathalie Guennouni
Gérard Mignani
Hervé PARISOT
Jean-Claude Tardivat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from FR9916709A external-priority patent/FR2803305B1/fr
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1250383A1 publication Critical patent/EP1250383A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond

Definitions

  • the field of the present invention is that of the use of a combination (i) of a member of a group of coupling agents formed by organosilanes each carrying an activated ethylenic double bond with (2i) a very small amount of a suitable coupling activator, as a white filler-elastomer coupling system in diene rubber (s) compositions comprising a white filler as reinforcing filler.
  • the invention also relates to the diene elastomer (s) compositions obtained by using said combination, as well as to the diene elastomer (s) articles having a body comprising the above-mentioned compositions.
  • elastomeric article where the invention is most useful, are those subject in particular to the following constraints: variations in temperature and / or variations in stress of high frequency in dynamic regime; and / or a significant static stress; and / or significant flexion fatigue in dynamic regime.
  • Types of articles are for example: conveyor belts, power transmission belts, flexible hoses, expansion joints, seals of household appliances, supports acting as engine vibration extractors either with metallic reinforcements, or with a hydraulic fluid inside the elastomer, cables, cable sheaths, shoe soles and rollers for cable cars.
  • the field of the invention is that of a high-performance use capable of providing elastomer compositions which have in particular: for great ease of processing the raw mixtures prepared, in particular at the level of extrusion operations and calendering, rheological properties marked by the lowest possible viscosity values; to achieve excellent productivity of the vulcanization installation, the shortest possible vulcanization times; and to meet the usage constraints mentioned above, excellent reinforcing properties conferred by a load, in particular optimal values of modulus of elasticity in tension, tensile strength and tensile strength abrasion.
  • the particles of white filler in particular of silica, have an unfortunate tendency, in the elastomeric matrix, to agglomerate between them.
  • These filler / filler interactions have the harmful consequence of limiting the reinforcement properties to a level significantly lower than that which it would theoretically be possible to achieve if all the white filler-elastomer bonds capable of being created during the mixing operation. , were actually obtained.
  • the use of white filler raises processing difficulties due to filler / filler interactions which tend in the raw state to increase the viscosity of the elastomer compositions, in any case to make processing more difficult.
  • a coupling agent also called a bonding agent, which has the function of ensuring the connection between the surface of the white filler particles and the elastomer, while facilitating the dispersion of this white charge within the elastomeric matrix.
  • Coupled agent white filler-elastomer
  • Y-B-X an agent capable of establishing a sufficient connection, of chemical and / or physical nature, between the white filler and the diene 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 physically and / or chemically binding to the white charge, such a bond being able to be established, for example, between a silicon atom of the coupling agent and the hydroxyl (OH) groups on the surface of the white filler (for example surface silanols when it is silica);
  • X represents a functional group ("X" function) capable of binding physically and / or chemically to the diene elastomer, for example via a sulfur atom;
  • B represents a hydrocarbon group making it possible to link Y and X.
  • the coupling agents must in particular not be confused with simple white charge recovery agents which in known manner may include the active Y function with respect to the charge white but lack the active X function vis-à-vis the diene elastomer.
  • Coupling agents in particular silica-elastomer, have been described in a large number of documents, the best known being bifunctional aikoxysilanes.
  • TESPT bis 3-thethoxysilylpropyl tetrasulphide
  • an association (i) of a member of a group of coupling agents formed by organoxysilanes each carrying a double bond activated with (2i) a very low quantity of an appropriate coupling activator offers coupling performance superior to that linked to the use of polysulphurized aikoxysilanes, in particular TESPT and also avoids the problems of premature roasting as well as the problems of implementation linked to a excessively high viscosity of the diene elastomer (s) compositions in the raw state, specific in particular to mercaptosilanes.
  • the coupling agent which is of interest in the present invention, has the essential characteristic of being the carrier of an activated ethylenic double bond (function "X") allowing it to be grafted onto the diene elastomer.
  • activated bond is meant in a known manner a bond made more capable of reacting (in the present case, with the diene elastomer).
  • coupling agent white filler-diene elastomer
  • Y organoxysilyl function
  • Organoxysilanes such as, for example, aikoxysilanes, carrying an activated ethylenic double bond are known to those skilled in the art, in particular as coupling agents (white filler-diene elastomer) in rubber compositions; cf. documents US-A-4 370 448, US-A-4 603 158, DE-A-4 319 142, the patent application published under the number JP64-29385 which describe in detail such known compounds and / or their processes obtaining.
  • the ethylenic double bond is most often activated by the presence of an adjacent electron-attracting group, that is to say attached to one of the two carbon atoms of the ethylenic double bond.
  • an "electron-attracting” group is a radical or functional group capable of attracting electrons to itself more than a hydrogen atom would if it occupied the same place in the molecule considered.
  • the Applicant has therefore found an association (i) of a member of a group of coupling agents formed by organoxysilanes each carrying a double activated linkage, chosen from agents of this type known in the prior art with (2i) a very small amount of an appropriate coupling activator, which makes it possible to meet the need for being able to have optimized coupling performance which are desired. More specifically, the present invention, taken in its first object, relates to the use:
  • the identical or different symbols R 1 each represent a monovalent hydrocarbon group chosen from: an alkyl radical, linear or branched, having from 1 to 4 carbon atoms; a linear or branched alkoxyalkyl radical having from 2 to 6 carbon atoms; a cycloalkyl radical having from 5 to 8 carbon atoms. and a phenyl radical;
  • the identical or different symbols R 2 each represent a monovalent hydrocarbon group chosen from: an alkyl radical, linear or branched, having from 1 to 6 carbon atoms; a cycloalkyl radical having from 5 to 8 carbon atoms; and a phenyl radical;
  • Z is a function, comprising an activated ethylenic double bond
  • R 3 is a linear or branched divalent alkylene hydrocarbon radical having from 1 to 10 carbon atoms, which can be interrupted by at least one oxygenated heteroatom, the free valence of which is carried by one carbon atom is linked to the atom of Yes ;
  • R 4 , R 5 , R 6 and R 7 which are identical or different from each other, each represent a hydrogen atom or a monovalent hydrocarbon group chosen from: an alkyl radical, linear or branched, having from 1 to 6 atoms carbon; and a phenyl radical; a is a number chosen from 1, 2 and 3; • and (2i) from 0.05 to a value less than 1 part by weight, per 100 parts by weight of diene elastomer (s), of at least one coupling activator consisting of a radical initiator of the type those with thermal ignition;
  • At least one diene elastomer chosen from: homopolymers obtained by polymerization of a diene monomer carrying two ethylenic double bonds, conjugated or not; the copolymers obtained by copolymerization of at least two conjugated or unconjugated dienes or by copolymerization of one or more diene (s) conjugated or not with one or more ethylenically unsaturated monomer (s); natural rubber; the copolymers obtained by copolymerization of isobutene and isoprene, as well as the halogenated versions of these copolymers; and a mixture of the above-mentioned elastomers with each other;
  • the coupling agents or constituents (i) are compounds consisting essentially of a functionalized organosilane of formula (I).
  • the expression "essentially” should be interpreted as meaning that the functionalized organosilane falling within the scope of the present invention may be in the form of a functionalized organosilane of formula (I) in the pure state or in the form of a mixture of such an organosilane with a variable molar quantity, generally equal to or less than 35 mol% in the mixture, of other organosilicon compound (s) comprising at least one linear, cyclic and / or networked siloxane oligomer formed of patterns corresponding to the following formulas: (R 8 ) 2 ZSiO 1 2 (VI-1), R 8 ZSi ⁇ 2/2 (VI-2) and / or ZSiO 32 (VI-3), in which: the symbols R 8 identical or different each represent a monovalent radical chosen from the hydroxy
  • the amount molar of which we speak above is expressed in number of atoms of Si (or of organosilicon units) belonging to (the) other (s) compound (s) organosilicon (s) per 100 atoms of Si present in the total mixture.
  • siloxane oligomers are new products which will constitute another aspect of the present invention taken in its first object.
  • the amount of the other organosilicon compound (s) will vary essentially depending on the operating conditions used to carry out the processes which can be used for the preparation of the functionalized organosilane of formula (I).
  • the preferred radicals R 1 are chosen from the radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, CH 3 OCH 2 -, CH 3 OCH 2 CH 2 -, CH 3 OCH (CH 3 ) CH 2 -; more preferably, the radicals R 1 are chosen from the radicals: methyl, ethyl, n-propyl and isopropyl.
  • the preferred radicals R 2 are chosen from the radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, cyclohexyl and phenyl; more preferably, the radicals R 2 are methyls.
  • R 3 represents an alkylene residue which corresponds to the following formulas: - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, -CH 2 -CH (CH 3 ) -, - (CH 2 ) 2 -CH (CH 3 ) - (CH 2 ) -,
  • R 3 is a residue - (CH 2 ) 2 - or - (CH 2 ) 3 -;
  • R 4 , R 5 , R 6 and R 7 are chosen from: a hydrogen atom, and the methyl, ethyl, n-propyl and n-butyl radicals; more preferably, these symbols are chosen from a hydrogen atom and a methyl radical.
  • Typical functionalized organosilanes corresponding to formula (I) are those of formula:
  • R 1 are chosen from the methyl and ethyl radicals
  • R 2 is a methyl radical
  • - a is a number equal to 2 or 3
  • coupling activators or constituents (2i) the use of which is essential for the coupling of white filler and diene elastomer
  • one or more compounds capable of activating, that is to say of increasing, are suitable, the coupling function of the coupling agent described above;
  • such coupling activator, used in very small proportions, is a radical initiator (also called radical initiator) of the type of those with thermal initiation.
  • a radical initiator is an organic compound capable, following an energetic activation, of generating free radicals in situ, in its surrounding medium.
  • the radical initiator used in the invention is an initiator of the thermal initiation type, that is to say that the energy supply, for the creation of free radicals, must be in thermal form. It is believed that the generation of these free radicals promotes, during the manufacture (thermomechanical kneading) of the rubber compositions, a better interaction between the coupling agent and the diene elastomer.
  • a radical initiator is preferably chosen, the decomposition temperature of which is less than 180 ° C., more preferably less than 160 ° C., of such temperature ranges making it possible to fully benefit from the coupling activation effect, during the manufacture of the rubber compositions.
  • the coupling activator is preferably chosen from the group consisting of peroxides, hydroperoxides, azido compounds, bis (azo) compounds, peracids, peresters or a mixture of two or more of these compounds.
  • the coupling activator is chosen from the group consisting of peroxides, bis (azo) compounds, peresters or a mixture of two or more of these compounds.
  • peroxides bis (azo) compounds
  • peresters peresters or a mixture of two or more of these compounds.
  • benzoyl peroxide acetyl peroxide
  • lauryl peroxide cumyl peroxide
  • t-butyl peroxide t-butyl peroxide
  • .-Butyl peracetate Hydroperoxide.
  • the radical initiator used is the peroxide of 1, 1 bis (t-butyl) -3,3,5-trimethylcyclohexane.
  • a compound is sold, for example, by the company Flexsys under the name Trigonox 29-40 (40% by weight of peroxide on a solid support of calcium carbonate).
  • the radical initiator used is 1, 1 '-azobis (isobutyronitrile).
  • Vazo 64 is marketed for example by the company Du Pont de Nemours under the name Vazo 64.
  • the radical initiator is used in very small proportion, namely at a rate ranging from 0.05 to a value less than 1 part by weight per 100 parts by weight of diene elastomer (s).
  • a particularly low level preferably ranging from 0.05 to 0.5 part per 100 parts of elastomer (s)
  • a free radical initiator rate will be chosen ranging from 0.1 to 0.3 part per 100 parts of elastomer (s).
  • the optimal content of coupling activator or constituent (2i) will be adjusted, within the ranges indicated above, according to the particular conditions for carrying out the invention, namely the type of diene elastomer (s) ( s) or constituent (3i), of the nature of the reinforcing white filler or constituent (4i), and of the nature and the quantity of (or) coupling agent (s) or constituent (i) used.
  • the amount of the coupling activator represents between 1% and 10%, more preferably between 2% and 6% by weight relative to the amount of the coupling agent (s).
  • a second subject of the present invention consists in the diene elastomer (s) compositions comprising a reinforcing white filler, obtained by using the combination (i) of at least one coupling agent chosen from the group of coupling agents, each member of which is a compound consisting essentially of a functionalized organosilane of formula (I) which has been mentioned above, with (2i) the very small amount of coupling activator (s) which also spoke above.
  • compositions comprise (the parts are given by weight): • per 100 parts of elastomer (s) or constituent (3i),
  • the expression "reinforcing white filler” is intended to define, a white filler capable of reinforcing on its own, without other means than that of a coupling agent, an elastomer composition (s) of the type rubber, natural (s) or synthetic (s).
  • the white reinforcing white filler consists of silica, alumina or a mixture of these two species.
  • the reinforcing white filler consists of silica, taken alone or as a mixture with alumina.
  • silica capable of being used in the invention, all precipitated or pyrogenic silicas known to those skilled in the art having a BET specific surface area ⁇ 450 m 2 / g are suitable. Precipitation silicas are preferred, these can be conventional or highly dispersible.
  • highly dispersible silica any silica having an ability to disaggregate and to disperse in a very large polymer matrix observable by electron or optical microscopy, on fine sections.
  • highly dispersible silicas mention may be made of those having a specific CTAB surface of 450 m 2 / g or less and particularly those described in patent US-A-5,403,570 and patent applications WO-A-95 / 09127 and WO-A-95/09128 the content of which is incorporated here.
  • treated precipitated silicas such as for example silicas "doped" with aluminum described in patent application EP-A-0 735 088, the content of which is also incorporated here.
  • precipitation silicas having:
  • CTAB specific surface ranging from 100 to 240 m 2 / g, preferably from 100 to 180 m 2 / g, a BET specific surface ranging from 100 to 250 m 2 / g, preferably from 100 to 190 m 2 / g ,
  • silica also means blends of different silicas.
  • CTAB specific surface is determined according to the NFT 45007 method of November 1987.
  • BET specific surface is determined according to the method of BRUNAUER, EMMET, TELLER described in "The Journal of the American Chemical Society, vol. 80, page 309 (1938) "corresponding to standard NFT 45007 of November 1987.
  • the DOP oil intake is determined according to standard NFT 30-022 (March 1953) using dioctylphthalate.
  • a highly dispersible alumina is advantageously used having:
  • a BET specific surface area ranging from 30 to 400 m 2 / g, preferably from 80 to 250 m 2 / g, an average particle size at most equal to 500 nm, preferably at most equal to 200 nm, and
  • aluminas A125, CR125, D65CR from the company BAIKOWSKI.
  • the coupling agent previously described could be grafted beforehand (via the "Y” function) onto the reinforcing white filler, the filler thus “precoupled” being able to be subsequently linked to the elastomer, via the free function "X" ".
  • lastomers or constituents (3i) capable of being used for the compositions in accordance with the second subject of the invention means more specifically: (1) homopolymers obtained by polymerization of a conjugated diene monomer having from 4 to 22 carbon atoms, for example: butadiene-1, 3, 2-methyl butadiene-1, 3, 2,3-dimethyl butadiene-1, 3, 2,3-diethyl butadiene-1, 3, 2-methyl-3-butadiene-1, 3, 2-chloro-butadiene-1, 3, 2-methyl-isopropyl-3 butadiene-1, 3, phenyl-1 butadiene-1, 3, pentadiene-1, 3, 2,4-hexadiene;
  • elastomer chosen from: (1) polyisoprene [or poly (2-methyl-butadiene-1, 3)]; (2) poly (isoprene-butadiene), poly (isoprene-styrene), poly (isoprene-butadiene-styrene); (3) natural rubber;
  • butyl rubber (5) a mixture of the aforementioned elastomers (1), (2), (3), (4) with one another; (5 ′) a mixture containing a majority amount (ranging from 51% to 99.5% and preferably from 70% to 99% by weight) of polyisoprene (1) and / or natural rubber (3) and a minority amount (ranging from 49% to 0.5% and preferably from 30% to 1% by weight) of polybutadiene, polychloroprene, poly (butadiene-styrene) and / or poly (butadiene-acrylonitrile).
  • 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-donating compounds, such as, for example, thiuram derivatives
  • - vulcanization accelerators such as, for example, guanidine derivatives, thiazole derivatives or sulfenamide derivatives
  • - vulcanization activators such as, for example, zinc oxide, steraric acid and zinc stearate; • in the case of other additive (s), for example:
  • the reinforcing white filler used constitutes more than 50% of the weight of the whole reinforcing white filler + carbon black
  • - a conventional white filler with little or no reinforcing, such as, for example, clays, bentonite, talc, chalk, kaolin, titanium dioxide or a mixture of these species; - antioxidant agents;
  • antiozonants such as for example N-phenyl-N '- (1,3-dimethyl butyl) -p-phenylene-diamine;
  • the compositions in accordance with the invention may contain agents for recovering the reinforcing filler, comprising for example the only function Y, capable in known manner, thanks to an improvement in the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve the ability to process the compositions in the raw state.
  • agents for recovering the reinforcing filler comprising for example the only function Y, capable in known manner, thanks to an improvement in the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve the ability to process the compositions in the raw state.
  • agents consist, for example, of polyols, polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialcanol-amines), and ⁇ , ⁇ -dihydroxylated polydimethylsiloxanes.
  • Such an aid to implementation when one is used, is used at a rate of 1 to 10 parts by weight
  • diene elastomer (s) compositions comprising a white reinforcing filler or constituent (4i), at least one coupling agent or constituent (i) and at least one coupling activator or constituent (2i) can be done according to a standard operating procedure in one or two stages.
  • all the necessary constituents are added and kneaded into a usual internal mixer, for example of the BANBURY or BRABENDER type, with the exception of the vulcanization agent (s) and optionally (or) vulcanization accelerators and / or (or) vulcanization activator (s).
  • the result of this first mixing step is then taken up on an external mixer, generally a roller mixer, and then the vulcanizing agent (s) is added thereto and optionally: the accelerator (s) vulcanization agent and / or the vulcanization activator (s).
  • an external mixer generally a roller mixer
  • the vulcanizing agent (s) is added thereto and optionally: the accelerator (s) vulcanization agent and / or the vulcanization activator (s).
  • the preparation of certain articles may be advantageous for the preparation of certain articles to implement a two-step process both carried out 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: the vulcanization accelerator (s) and / or (or) the vulcanization activators.
  • the purpose of the second step which follows is essentially to subject the mixture to an additional heat treatment.
  • the result of this second step is also then taken up on an external mixer to add the vulcanizing agent (s) to it and optionally: the vulcanization accelerator (s), and / or the vulcanization activator (s).
  • the working phase in an internal mixer is generally carried out at a temperature ranging from 80 ° C to 200 ° C, preferably from 80 ° C to 180 ° C.
  • This first working phase is followed by the second working phase in an external mixer by operating at a lower temperature, generally below 120 ° C and preferably ranging from 25 ° C to 70 ° C.
  • the final composition obtained is then calendered, for example in the form of a sheet, a plate or even a profile which can be used for the manufacture of articles made of elastomer (s).
  • Vulcanization (or baking) is carried out in a known manner at a temperature generally ranging from 130 ° C to 200 ° C, for a sufficient time which can vary for example between 5 and 90 minutes depending in particular on the baking temperature, the system of vulcanization adopted and of the vulcanization kinetics of the composition considered.
  • the present invention taken in its second object, relates to the elastomer compositions previously described both in the raw state (ie, before baking) and in the baked state (ie, after crosslinking). or vulcanization).
  • the elastomer (s) compositions will be used to prepare elastomer (s) articles having a body comprising said compositions. These compositions are particularly useful for preparing articles consisting of engine mounts, shoe soles, cable car rollers, seals for household appliances and cable sheaths.
  • the purpose of this example is to demonstrate the improved coupling performance of a compound essentially consisting of an activated double bond alkoxysilane of formula (I) when it is combined with a peroxide as a radical initiator with thermal initiation.
  • These performances are compared on the one hand to those of a conventional coupling agent TESPT, and on the other hand to those of a compound essentially consisting of an alkoxysilane with activated double bond of formula (I), itself, when the latter is used alone, that is to say without being associated with a radical initiator.
  • TESPT coupling agent (4 pce or parts by weight per hundred parts of elastomers) used alone;
  • composition No. 2 (control 2): TESPT (4 phr) with which 0.12 phr of peroxide is associated;
  • composition No. 3 (control 3): compounds essentially consisting of an alkoxysilane with activated double bond of formula (I) consisting of N- [ ⁇ -propyl (methyl-diethoxy) silane] maleamic acid (4.3 pce ), used alone;
  • composition No. 4 compound essentially consisting of N- [ ⁇ -propyl (methyldiethoxy) silane] maleamic acid (4.3 phr), with which 0.12 phr of peroxide is associated.
  • the operation is carried out in a 2 liter glass reactor, equipped with a stirring system and a dropping funnel.
  • the ⁇ -aminopropylsilane of formula (C 2 H 5 O) 2 CH 3 Si (CH 2 ) 3 NH 2 (404, 41 g, ie 2.113 moles) is gradually poured at the temperature of 10 ° C (reaction temperature) , on a solution of maleic anhydride (215.6 g, or 2.20 moles) in dichloromethane CH 2 CI 2 as solvent (773.7 g), over a period of 1 hour 25 minutes.
  • the reaction medium is then left at 17 ° C for 72 hours. At the end of this time, the solvent is removed by evaporation and white crystals based on the desired compound are thus recovered.
  • ⁇ HC CH (C 2 H 5 O) 2 CH 3 Si (CH 2 ) 3 -NH - CO COOH 4 molar units of coded units D (OC 2 H 5 ) of formula CH 3 Z 2 (OC 2 H5) SiO ⁇ 2 belonging to the disiloxane of formula (present at 3.4% by weight):
  • the contents of the mixer are drained or dropped after 5 minutes.
  • the temperature reached is in the range from 135 to 140 ° C.
  • the mixture obtained is then introduced on a roller mixer, maintained at 30 ° C, and TBBS, DPG and sulfur are introduced. After homogenization, the final mixture is calendered in the form of sheets 2.5 to 3 mm thick.
  • the measurements are carried out on the compositions in the raw state.
  • the results relating to the rheology test which is carried out at 160 ° C. for 30 minutes using a MONSANTO 100 S rheometer, are shown in table II below.
  • the composition to be tested is placed in the chamber d
  • the test is regulated at a temperature of 160 ° C., and the resistive torque, opposed by the composition, to a low amplitude oscillation of a biconical rotor included in the test chamber is measured, the composition completely filling the chamber considered.
  • the minimum torque which reflects the viscosity of the composition at the temperature considered the maximum torque and the delta-torque which reflect the rate of crosslinking caused by the action of the vulcanization system
  • the time T-90 necessary to obtain a vulcanization state corresponding to 90% of the complete vulcanization this time is taken as the optimum vulcanization
  • the TS-2 roasting time corresponding to the time necessary to have a rise of 2 points above the minimum torque at the temperature considered (160 ° C) and which reflects the time during which it is possible to use raw mixtures at this temperature without having initiation of vulcanization.
  • the measurements are carried out on the vulcanized compositions at the optimum (temperature: 160 ° C; durations for each composition: time T-90 indicated in Table II).
  • the tensile tests are carried out in accordance with the indications of standard NF T 46-002 with H2 type test pieces.
  • the modules 10%, 100%, 300%, 400%, and the breaking strength are expressed in MPa; the elongation at break is expressed in%.

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EP00993721A 1999-12-30 2000-12-22 Verwendung einer assoziation einer zusammensetzung basierend auf mit einem kupplungsaktivator funktionalisierten organosilanen, als kupplungssystem für weissen füllstoff enthaltende dienelastomerzusammensetzungen Withdrawn EP1250383A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR9916709 1999-12-30
FR9916709A FR2803305B1 (fr) 1999-12-30 1999-12-30 Utilisation d'une association d'un compose a base d'organosilane fonctionnalise avec un activateur de couplage, comme systeme de couplage dans les compositions d'elastomeres dieniques comprenant une charge blanche
FR0007702 2000-06-16
FR0007702A FR2803306B1 (fr) 1999-12-30 2000-06-16 Utilisation d'une association d'un compose a base d'organosilane fonctionnalise avec un activateur de couplage , comme systeme de couplage dans les compositions d4elastomeres dieniques comprenant une charge blanche
PCT/FR2000/003667 WO2001049783A1 (fr) 1999-12-30 2000-12-22 Utilisation d'une association d'un compose a base d'organosilane fonctionnalise avec un activateur de couplage, comme systeme de couplage dans les compositions d'elastomeres dieniques comprenant une charge blanche

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EP1250383A1 true EP1250383A1 (de) 2002-10-23

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EP00993721A Withdrawn EP1250383A1 (de) 1999-12-30 2000-12-22 Verwendung einer assoziation einer zusammensetzung basierend auf mit einem kupplungsaktivator funktionalisierten organosilanen, als kupplungssystem für weissen füllstoff enthaltende dienelastomerzusammensetzungen

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US (1) US20030144403A1 (de)
EP (1) EP1250383A1 (de)
JP (1) JP2003519272A (de)
AR (1) AR027110A1 (de)
AU (1) AU2858101A (de)
FR (1) FR2803306B1 (de)
WO (1) WO2001049783A1 (de)

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KR20020063283A (ko) * 1999-12-30 2002-08-01 소시에떼 드 테크놀로지 미쉐린 에스테르 관능성 그룹을 갖는 커플링제(화이트충전재/탄성중합체)를 포함하는 타이어용 고무 조성물
CN1414993A (zh) * 1999-12-30 2003-04-30 米其林技术公司 用于轮胎的含有通过热制动游离基引发剂而活化的偶联剂(白色填料/二烯弹性体)的橡胶组合物
GB0812185D0 (en) 2008-07-03 2008-08-13 Dow Corning Polymers modified by silanes
GB0812187D0 (en) * 2008-07-03 2008-08-13 Dow Corning Modified polyethylene
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WO2010125123A1 (en) 2009-04-30 2010-11-04 Dow Corning Corporation Elastomer compositions modified by silanes
GB201000121D0 (en) 2010-01-06 2010-02-17 Dow Corning Modified polyolefins
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JP5800285B2 (ja) * 2011-11-18 2015-10-28 ダイソー株式会社 ゴム組成物及び架橋してなる架橋物

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Also Published As

Publication number Publication date
AR027110A1 (es) 2003-03-12
FR2803306A1 (fr) 2001-07-06
WO2001049783A1 (fr) 2001-07-12
FR2803306B1 (fr) 2006-09-22
AU2858101A (en) 2001-07-16
US20030144403A1 (en) 2003-07-31
JP2003519272A (ja) 2003-06-17

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