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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • 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
  • C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L7/00—Compositions of natural rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

• the field of the present invention is that of the use of a particular combination of silicone compounds as a silica-elastomer coupling agent in compositions of natural or synthetic elastomer (s) comprising a siliceous material with title of reinforcing filler.
• the invention also relates to the elastomer compositions obtained thanks to the use of an effective amount of said combination of silicone compounds, as well as to the processes for preparing these compositions. It also relates to articles made of elastomer (s) having a body comprising the abovementioned 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, either with a hydraulic fluid inside the elastomer, spring parts located between the rigid, articulated metallic elements, of the track of a vehicle in contact with the ground, cables, sheaths cables, shoe soles and rollers for cable cars.
• the field of the invention is that of a high-performance use capable of providing elastomer (s) compositions which have, in particular, to meet the constraints of use which have been mentioned above, an exothermicity in dynamic regime (tangent delta) as low as possible and, if possible, excellent mechanical properties, in particular good values of tear resistance, abrasion resistance and residual compressive deformation (DRC).
• Other properties which can be improved are, for example, the properties of resistance to water and to leached water of vulcanizates derived from certain elastomers.
• silica particles have an unfortunate tendency, in the elastomer matrix, to agglomerate with one another.
• the negative consequence of these silica / silica interactions is to limit the reinforcement properties to a level substantially lower than that which it would theoretically be possible to achieve if all the silica / elastomer interactions capable of being created during the mixing operation, were actually obtained.
• the use of silica raises processing difficulties due to silica / silica interactions which tend in the raw state to increase the consistency of the elastomer compositions, in any case to make processing more difficult than the implementation of carbon black.
• the interactions between the silica and the crosslinking system when it is based on sulfur penalize the speed and the yield of the crosslinking.
• compositions of silica-reinforced elastomers comprising low levels of coupling agents as effective as mercaptosilanes, but while avoiding vulcanizations premature and processing problems associated with too high a viscosity of the compositions.
• ⁇ an effective amount of a particular association of silicone compounds consisting of the combination: - of at least one functionalized polyorganosiloxane (in abbreviation: POS) comprising, per molecule, at least one functional siloxyl unit (in abbreviation: MO1) capable of binding chemically and / or physically with the hydroxyl sites on the surface of the silica particles,
• POS functionalized polyorganosiloxane
• MO1 functional siloxyl unit
• At least one functionalized organosilane comprising, per molecule, at least one functional group (in abbreviation: G1) capable of chemically and / or physically bonding with MO1 units and / or hydroxyl sites silica particles and at least one other functional group (abbreviation: G2) capable of bonding chemically and / or physically to the elastomer chain (s),
• compositions of natural or synthetic elastomer (s) comprising a siliceous material as reinforcing filler, intended for the manufacture of article in elastomer (s).
• the silicone POS compounds are preferably chosen from the compounds (A) and their mixtures, the compounds (B) and their mixtures, the compounds (C) and their mixtures, and mixtures of the abovementioned species, where: * (A) are compounds comprising, per molecule:
• Y is a linear or branched alkoxyl radical chosen from C-pC ⁇ alkoxyls, and in particular C ⁇ Cs, methoxyl, ethoxyl and (iso) propoxyl being more particularly retained, - ⁇ - and other share, at least one functional siloxyl unit of formula:
• * R corresponds to the same definition as that given above for the substituent R of the unit (I) and can be identical or different from the latter
• * W is a monovalent hydrocarbon radical having from 2 to 30 carbon atoms and possibly atoms of S and / or O and constituting a functional residue, connected to silicon by an Si-C bond, this residue being chosen from the following groups:
• R * (C) are hydroxylated or alkoxylated silicone resins having, per molecule, at least 2 different units chosen from those of formula: R ' 3 SiO 0 5 (M), R' 2 SiO (D), R'SiO 1 5 (T) and SiO 2 (Q), at least one of these units being a unit T or Q, the radicals R ', identical or different, being mainly chosen from alkyl radicals, linear or branched at C r C 6 , vinyl, phenyl and trifluoro-3,3,3 propyl, and having a content by weight of hydroxyl or alkoxyl groups (in particular methoxyl and ethoxyl) of between 0.1 and 10%.
• the polyorganosiloxanes (A) are remarkable in that the functional substituent Y is hydrolyzable and allows grafting on silica while the functional substituent W is more difficult to hydrolyze than the functional substituent Y and is capable of expressing various properties depending on its chemical nature.
• the substituent W of the unit of formula II is chosen from the following radicals:
• alkyl radical (i) comprising from 8 to 30 carbon atoms and preferably chosen from the following alkyl radicals: octyl, dodecyl, undecyl, tridecyl;
• radical (2i) comprising a double bond, and optionally another conjugate to the first, said radical advantageously being hexenyl or dodecenyl;
• the polyorganosiloxanes (A) may have a linear and / or branched structure and / or cyclical.
• the preferred radicals R are: methyl, ethyl, n-propyl, isopropyl or n-butyl, preferably methyl. Even more preferably, at least 80% by number of the radicals R are methyls.
• the preferred alkoxy radicals Y are ethoxyls.
• Z is a monovalent radical chosen from the radicals formed by hydrogen and from those meeting the definitions of R, Y and W,
• linear functionalized polyorganosiloxanes (A) mention may be made of the compounds corresponding to the following formulas:
• radicals W can be of identical or different nature when n> 1 and s> 1.
• polyorganosiloxanes are obtained according to a process consisting in: - firstly, reacting a starting polyorganosiloxane comprising units of formula (II) as defined above, in which W represents hydrogen with at least one alcohol from which the functionality Y of the unit (I), and useful both as a reagent and as a reaction solvent, in the presence of a catalyst of which at least one of the active elements is chosen from transition metals, according to a dehydrogenocondensation mechanism (1st phase), - and on the other hand, to implement the addition of the polyorganosiloxane transformed by dehydrogenocondensation on at least one olefinic compound from which the functionality W of the unit (II) is derived according to a hydrosilylation mechanism (2nd phase), presence of a catalyst and preferably at a temperature between 5 and 100 ° C and more preferably still between 20 and 90 ° C.
• the alcohols used are linear or branched monohydroxylated alkanols (primary, secondary, or tertiary, preferably primary), preferably chosen from the following list: methanol, ethanol, (iso) propanol, (n) butanol , ethanol being preferred.
• the catalyst it is advantageously chosen from those containing at least one of the following elements: Pt, Rh, Ru, Pd, Ni and their associations, this catalyst being optionally coupled to an inert support or not.
• the catalyst is taken from the family of platinum catalysts traditionally used for carrying out hydrosilylation reactions. These platinum catalysts are widely described in the literature. Mention may in particular be made of the complexes of platinum and of an organic product described in American patents US-A-3 159601, US-A-3 159 602, US-A-3 220 972, and European patents EP-A -57,459, EP-188,978 and EP-A-190,530 as well as the platinum and organopolysiloxane vinyl complexes described in American patents US-A-3,419,593, US-A-3,715,334, US-A -3,377,432 and US-A-3,814,730.
• the Karstedt catalyst is an example of a platinum catalyst suitable for the process used here (US-A-3,775,452 Karstedt).
• Nickel-based catalysts such as Raney nickel, for example, are a possible alternative to platinum catalysts.
• the dehydrogenocondensation can be carried out over a wide temperature range ranging, for example, from 0 to 200 ° C., but it is clear that it is preferred that it takes place at a temperature between 20 and 80 ° C preferably between 40 and 70 ⁇ C.
• the second phase of the process consists of an addition reaction of the hydrogenated intermediate polyorganosiloxane produced by dehydrogenocondensation, on at least one olefinic compound carrying at least one ⁇ bond.
• hydrosilylation is initiated by adding the olefinic compound from which the radical W as defined above is derived, to the intermediate alkoxylated polyorganosiloxane once the dehydrogenocondensation is complete.
• this addition can be made when the evolution of hydrogen has ceased.
• the reactive acene can be formed by a mixture of products comprising one or more precursor species of radicals W, which determine the multifunctionality of the final polyorganosiloxane. In the case where several species W are provided, it is preferable first to react the acene corresponding to the second functionality, then once the latter has fully reacted, the aicene corresponding to the second is incorporated. third feature and so on.
• the olefinic compound precursor of W can be used before this first phase of the process begins, or even during it.
• the olefinic compounds used can be easily deduced from the definition of W given above.
• the choice as to this radical is determined by the targeted applications (one or more different functionalities).
• the hydrosilylation phase can take place advantageously at room temperature and in bulk or in solution, for example in alcohol which served as solvent and reagent for the dehydrogenocondensation reaction.
• the crude polyorganosiloxanes which are obtained can be purified in particular by passing over a column filled with an ion exchange resin and / or by simple devolatiization of the reactants introduced in excess and optionally of the solvent used, with a heating operated between 100 and 180 ° C under reduced pressure.
• the starting polyorganosiloxane is selected from those corresponding to the following formula:
• the starting polyorganosiloxanes used, for example, in the preparation of cyclic functionalized products are those selected from those corresponding to the following average formula:
• silanols such as the following commercial products manufactured by Hûls America Inc. appearing in the 1994 catalog of the company ABCR - Roth-Sochiel SARL under the references:
• the compounds (C) are silicone resins consisting of small macromolecular networks of one or more cycle (s) by virtue of their presence in the molecule of at least 2 different units chosen from the units M, D, T and Q, l at least one of these units being a T or Q unit, and comprising reactive functions.
• resins are chosen in which structure the radicals R ′ of the units M, D, T, Q are the methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.
• R ′ the radicals R ′ of the units M, D, T, Q are the methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.
• MQ resins MQ resins, MDQ resins, DT resins and MDT resins comprising the radicals R ′ mentioned in the preceding paragraph and having a content by weight of hydroxyl or alkoxyl groups of between 1 and 6%.
• Resins having a molecular mass of less than 25,000 can be used more particularly.
• ORGANOSILANES As organosilane compounds which can be used in the context of the invention, one or more compounds corresponding to at least one of the four general formulas (IX) to (XII) are suitable. following:
• R 1 represents an alkyl group containing 1 to 10 carbon atoms, or the phenyl radical
• X represents a hydrolyzable group chosen from: - halogens, preferably chlorine,
• alkoxy radicals themselves optionally substituted by alkoxy radicals
• X may optionally represent a hydroxyl group (OH),
• Alk represents a divalent hydrocarbon group, chosen from linear or branched alkylene, having from 1 to 10 atom (s) and advantageously from 1 to 6, optionally substituted by an aryl radical at CQ - C-
• 2, > m 'represents 0 or 1,
• (Ar) represents a hydrocarbon group, chosen from aryls, having from 6 to 12 atoms, and preferably 6 to 8,
• D represents a group capable of forming a bond with at least one of the elastomers of the composition.
• group D can also include other groups capable of reacting with the elastomers of the composition, for example: D represents:
• the mixed disulphide of dibenzyl thiocarbamate and ⁇ -propyltrimethoxysilane and the mixed disulfide of dibenzyl thiocarbamate and ⁇ -propyltriethoxysilane are suitable.
• the solution prepared during the second step is slowly added. Once the addition is complete, it is left to react for 24 hours at room temperature.
• the recovered solution is then filtered to remove the sodium chloride formed.
• the solvents are evaporated.
• a viscous yellow liquid is recovered; it is purified by successive solubilizations in toluene.
• R represents a linear or branched C 1 -C 4 alkyl or alkenyl group, a C 3 -C 30 cycloalkyl or cycloalkenyl group or a C 6 -C 20 carbocyclic or heterocyclic aryl group.
• (R ⁇ ) represents a divalent hydrocarbon group, chosen from linear or branched alkylene and alkylenoxy, having from 1 to 10 carbon atom (s) and advantageously from 1 to 6,
• Alkenyl represents a hydrocarbon group, linear or branched, cyclic or not, comprising one or more double bonds, having from 2 to 20 carbon atoms and preferably from 2 to 6.
• the double bonds are preferably conjugated and / or associated at least to an activating group located in ⁇ .
• This family of linking agent corresponding to the formula (XI) is preferably used in rubber compositions with at least one radical initiator, preferably consisting of at least one peroxide.
• OS compounds which are very suitable are the mercaptosilanes of formula (IX); use is preferably a mercapto-3-propyl-tri (alkoxy C r C 6) silane and more preferably the 3-mercapto propyltrimethoxy (or triethoxy) silane.
• Other compounds of this type which are very suitable are the bis (C r C 4 silylpropyl trialkoxy) -tetrasulfides of formula (IX); preferably bis (triethoxysiiylpropyl) -tetrasulfide is used.
• OS compounds are the tri (C 1-6 alkoxy) alkyisilanes of formula (XI), each alkoxy radical possibly being itself able to be substituted by a C- alkoxy radical
• a second subject of the present invention consists of the elastomer compositions comprising a siliceous filler obtained by virtue of the use of an effective amount of the particular combination of silicone compounds, which has been mentioned above. , consisting in the combination of at least one POS compound with at least one OS compound. More specifically, these compositions include (the parts are given by weight):
• siliceous filler 10 to 100 parts of siliceous filler, and preferably 20 to 80,
• SILICON LOAD SILICON LOAD
• highly dispersible silica means 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.
• the dispersibility of the silica is also assessed by means of an ultrasound deagglomeration aptitude test followed by a measurement, by diffraction on a granulometer, of the size of the silica particles to determine the median diameter (D50) of the particles and the desagglomeration factor (Fd) after desagglomeration as described in US-A-5,403,570, the content of which is incorporated herein.
• silicas having a CTAB specific surface of 450 m 2 / g or less and in particular those described in US-A-5,403,570 and patent applications WO-A -95/09127 and WO-A-95/09128, the content of which is incorporated here, or the Zeosil 1165 MP silica from the company Rhône-Poulenc.
• DOP oil intake of less than 300 ml / 100 g, preferably between 200 and 295 ml / 100 g,
• Fd ultrasound deagglomeration factor
• the physical state under which the silica is present that is to say that it is in the form of powder, microbeads, granules, beads is indifferent as is the specific surface of the silica.
• silica also means blends of different silicas.
• Silica can be used alone or in the presence of other white fillers.
• CTAB specific surface is determined according to the NFT 45007 method of November 1987.
• BET specific surface area 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 oil intake DOP is determined according to standard NFT 30-022 (March 1953) using dioctylphthalate.
• elastomers capable of being used for the compositions in accordance with the second object of the invention, is meant: (1) homopolymers obtained by polymerization of a conjugated diene monomer having from 4 to 22 carbon atoms, such as for example : 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl butadiene-1,3, 2-methyl-3-ethyl butadiene -1, 3, 2-chloro-butadiene-1, 3, 2-methyl-isopropyl-3 butadiene-1,3, phenyl-1 butadiene-1,3, pentadiene-1,3, hexadiene-2 , 4; (2) the copolymers obtained by copolymerization of one or more of the above-mentioned conjugated dienes together or with one or more ethylenically unsaturated monomers chosen from:
• vinyl aromatic monomers having from 8 to 20 carbon atoms, such as for example: styrene, ortho-, meta- or paramethylstyrene, chlorostyrenes, vinyl mesitylene, divinyl benzene, vinyl naphthalene;
• - vinyl nitrile monomers having from 3 to 12 carbon atoms, such as, for example, acrylonitrile, methacrylonitrile;
• acrylic ester monomers derived from acrylic acid or methacrylic acid with alkanols having from 1 to 12 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate , n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacryate, ethyl methacrylate, n-butyl methacryate, isobutyl methacryiate;
• ternary copolymers obtained by copolymerization of ethylene, of an ⁇ -olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having of 6 to 12 carbon atoms, such as for example the elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type such as in particular hexadiene-1, 4, ethylidene norbornene, dicyclopentadiene (elastomer EPDM);
• elastomer chosen from: polybutadiene, polychloroprene, polyisoprene, poly (styrene-butadiene), poly (acrylonitrile-butadiene) in hydrogenated form or not , poly (styrene-butadiene-isoprene), a terpolymer (ethylene-propyiene-diene unconjugated monomer), butyl rubber.
• elastomer chosen from: polybutadiene, polychloroprene, polyisoprene, poly (styrene-butadiene), poly (acrylonitrile-butadiene) in hydrogenated form or not , poly (styrene-butadiene-isoprene), a terpolymer (ethylene-propyiene-diene unconjugated monomer), butyl rubber.
• compositions in accordance with the invention also contain all or part of the other constituents and auxiliary additives usually used in the field of elastomer (s) and rubber compositions.
• vulcanizing agents such as for example organic peroxides and / or hardening agents chosen from sulfur or sulfur-donating compounds, such as for example thiuram derivatives and other compound (s) used ( s) in this context such as for example zinc oxide, stearic acid and zinc stearate;
• - sulfur hardening accelerators such as, for example, guanidine derivatives, thiazole derivatives or sulfenamide derivatives; • in the case of other additive (s), mention may be made, for example:
• - fillers such as, for example, carbon black, titanium dioxide and / or kaolin;
• Antiozonants such as for example N-phenyl-N '- (1,3-dimethyl butyl) -p-phenylene-diamine;
• the elastomer compositions according to the invention and comprising a coupling agent consisting of at least one polyorganosiloxane POS and at least one organosilane compound OS exerting a siiice-elastomer bond allow: * to use significant levels of organosilane agents OS belonging to the mercaptosilane family, without causing a penalty in terms of "safety in roasting", and without disturbing the use of the compositions of elastomer (s),
• a third subject of the present invention relates to the processes for the preparation of elastomer compositions (s) comprising a siliceous filler, described above in part II of this thesis.
• the combination of at least one POS compound with at least one OS compound, playing the role of siiice-elastomer coupling agent can be prepared beforehand and be added as it is after its preparation, immediately or at another time, in the mixture of elastomer (s) comprising the siliceous filler
• a variant of said one-phase process consists in adding directly at the time of use, simultaneously or one after the other, at least one silicone POS compound and at least one silicone OS compound in the mixture of elastomer (s) comprising the siliceous filler at any time during the preparation of this mixture.
• phase 1 to first prepare a first mixture comprising the elastomer (s), a siliceous filler and at least one silicone compound POS and optionally part of the usual auxiliary constituent (s)
• phase 2 then immediately or at another time, then to prepare a second mixture comprising the first mixture, at least one silicone compound OS and all or part of the usual auxiliary component (s).
• a usual external mixer such as for example a cylinder mixer.
• POS with the siliceous filler for example by coating the silica with the POS silicone compound (s).
• phase 1 of the so-called two-phase process in which the silicone compound (s) POS is reacted in situ with the silica in the presence of the elastomer (s) ), the mixture obtained, known as the first mixture, which comprises the siliceous filler coated with (or) silicone compound (s) POS and the (or) elastomer (s), is also, to the knowledge of the Applicant , a new product, and this is a fifth object of the present invention.
• This first mixture can be used, in the state it is in after it has been obtained, to add to it, immediately or at another time, at least one silicone compound OS and all or part of the auxiliary constituent (s) (s) usual (s), so as to prepare te second mixture which we spoke above about phase 2 of the process known as in two phases.
• this first mixture can already constitute in itself, in the state it is in after it has been obtained, or in the state corresponding to the addition, if necessary, of other auxiliary constituent (s).
• auxiliary constituent s
• usual (s) a new composition of elastomer (s) loaded with a siliceous material (but not containing this time of silicone compound OS), capable of leading to vuicanisats and articles which can be already interesting as regards improvements sought in matters of, for example, the rheology of the compositions, certain mechanical properties and properties of resistance to water and leached water.
• This coated product can be used, for example, in the state in which it is found after it has been obtained, to be incorporated, immediately or at another time, into the elastomer (s), so as to prepare the first mixture. which was mentioned above in connection with ia phase 1 of the so-called two-phase process.
• a seventh object of the present invention relates to elastomeric articles having a body comprising either the compositions described above within the framework of the second object of the invention (cf. part II), or the compositions described below. before in the context of the fifth subject of the invention (cf. part IV).
• the present invention is particularly useful for preparing articles consisting of engine mounts, vehicle track parts, shoe soles, cable car rollers, seals for household appliances and cable sheaths. The following examples illustrate the present invention.
• Example 1 illustrate two identical elastomer compositions, representative of formulations for engine supports, with the exception of the coupling agent which, in Example 1, is the silicone POS compound corresponding to the formula (V-1) and, in Example 2, is the combination of said POS with the silicone compound OS consisting of 3-mercapto propyltrimethoxysilane.
• vulcanizing agent (4) anti-zone protector based on N-phenyl-N '- (1,3-dimethyl butyl) -p- phenylenediamine, sold by the company AKZO Chemicals; (5) antioxidant protector based on 2,2,4-trimethyl 1,2-dihydro-1,2-quinoline polymer, sold by the company AKZO Chemicals;
• phase 2 is introduced into a cylinder mixer maintained at 30 ° C to be calendered there.
• DTMT and sulfur are introduced into this mixer.
• the final mixture is calendered in the form of sheets 2.5 to 3 mm thick.
• Test tube used cylinder with a diameter of 19 mm and a height of 25 mm (see method ASTM D623-67).
• Test tube used cylinder with a diameter of 19 mm and a height of 25 mm (cf. method ASTM D623-67).
• Equipment used instron 1342 viscoelasticimeter, Instron 3411 hydraulic compressor and data acquisition and processing computer system.
• Test temperature 25 ° C.
• test piece is statically subjected to a prestress of 10% (deformation compared to its initial height). A sinusoidal stress is then applied to it: - frequency: 155 Hz,
• the delta tangent at 155 Hz is defined by the ratio: viscous module 155 Hz / elastic module 155 Hz.
• Test tube used cylinder with a diameter of 19 mm and a height of 25 mm (cf. method ASTM D623-67).
• Equipment used Instron 1342 viscoelasticimeter, Instron 3411 hydraulic compressor and data acquisition and processing computer system.
• Test temperature 25 ° C.
• test piece is statically subjected to a 10% prestress
• the stiffness (N / mm) is then measured for each frequency. This is defined by the ratio of the force exerted on the specimen and the deformation that the specimen then presents (mm) (compared to its initial height).
• the frequency stiffening 15 - 155 Hz is then defined by the ratio: stiffness at 155 Hz / stiffness at 15 Hz. (5)
• the measurements are carried out according to the indications in standard ASTM D 624 73 with ISO R type test pieces. 34 with 1.5mm notch.
• Example 3 illustrate two identical elastomer compositions, representative of washing machine seal formulations, with the exception of the coupling agent which, in Example 3, is the POS silicone compound corresponding to the formula (V- 1) and, in Example 4, is the combination of said POS with the silicone compound OS consisting of 3-mercapto propyltrimethoxysiiane.
• composition is prepared as follows: In an internal mixer (BANBURY type) rotating at 80 rpm, the following operations are carried out:
• the final mixture is calendered in the form of sheets 2.5 to 3 mm thick.
• the OMO detergent used is the reinforced formula intended for machine or hand washes, put on sale in supermarkets in the Lyon region.
• the detergent used ARIEL is that intended for handwashing, sold for sale in supermarkets in the Lyon region.
• Ethylene-propylene-diene monomer elastomer sold by the company ESSO CHIMIE under the name VISTALON 2504; (2) Vulcanizing agent;
• Each composition is prepared as follows:
• the final mixture is calendered in the form of sheets 2.5 to 3 mm thick.
• the detergent is that used in Examples 3 and 4.
• the detergent is that used in Examples 3 and 4.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silicon Polymers (AREA)
• Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Toys (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=9488148

Family Applications (1)

Country Status (16)

Families Citing this family (26)

Family Cites Families (7)

• 1996
  • 1996-01-11 FR FR9600440A patent/FR2743565B1/fr not_active Expired - Fee Related
• 1997
  • 1997-01-07 MA MA24449A patent/MA24050A1/fr unknown
  • 1997-01-08 AR ARP970100071A patent/AR005393A1/es unknown
  • 1997-01-08 AR ARP970100070A patent/AR005392A1/es unknown
  • 1997-01-09 CA CA002239103A patent/CA2239103A1/fr not_active Abandoned
  • 1997-01-09 PL PL97327689A patent/PL327689A1/xx unknown
  • 1997-01-09 JP JP52492297A patent/JP3228756B2/ja not_active Expired - Fee Related
  • 1997-01-09 KR KR1019980705332A patent/KR19990077191A/ko not_active Application Discontinuation
  • 1997-01-09 US US09/101,320 patent/US6245834B1/en not_active Expired - Fee Related
  • 1997-01-09 EP EP97900252A patent/EP0873375A1/de not_active Withdrawn
  • 1997-01-09 AU AU13838/97A patent/AU1383897A/en not_active Abandoned
  • 1997-01-09 BR BR9707139A patent/BR9707139A/pt unknown
  • 1997-01-09 RU RU98114995/04A patent/RU2177011C2/ru active
  • 1997-01-09 WO PCT/FR1997/000037 patent/WO1997025374A1/fr not_active Application Discontinuation
  • 1997-01-10 ID IDP970063A patent/ID19800A/id unknown
  • 1997-01-10 ZA ZA9700213A patent/ZA97213B/xx unknown
  • 1997-01-16 TW TW086100438A patent/TW380150B/zh not_active IP Right Cessation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events