EP1299451A1 - Utilisation d'un compose organosilicique porteur d'au moins une double liaison ethylenique activee comme agent de couplage dans les compositions de caoutchouc comprenant une charge blanche - Google Patents
Utilisation d'un compose organosilicique porteur d'au moins une double liaison ethylenique activee comme agent de couplage dans les compositions de caoutchouc comprenant une charge blancheInfo
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- EP1299451A1 EP1299451A1 EP01945437A EP01945437A EP1299451A1 EP 1299451 A1 EP1299451 A1 EP 1299451A1 EP 01945437 A EP01945437 A EP 01945437A EP 01945437 A EP01945437 A EP 01945437A EP 1299451 A1 EP1299451 A1 EP 1299451A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- 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
-
- 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
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- 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
-
- 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
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- 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 compound comprising a polyfunctional polyorganosiloxane (abbreviated as POS) carrying at least one activated ethylenic double bond, as coupling agent (white filler-elastomer) in the compositions of rubber comprising a white filler as a reinforcing filler.
- POS polyfunctional polyorganosiloxane
- the invention also relates to the elastomer (s) compositions obtained by using said coupling agent, as well as to the 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 (s) compositions which present 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.
- elastomer (s) compositions which present 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
- carbon black is a filler which exhibits such abilities, but this is not generally the case for white fillers.
- the use of reinforcing white filler alone, in particular of reinforcing silica alone, has been found to be inappropriate because of the low level of certain properties of such compositions and consequently of certain properties of the articles using these compositions.
- the particles of white filler, in particular of silica have an unfortunate tendency, in the elastomer matrix, to agglomerate between them.
- coupling agent white filler-elastomer
- Y represents a functional group (function Y) 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 groups (OH) surface of the white filler (for example surface silanols when it is silica);
- X represents a functional group (function X) capable of binding physically and / or chemically to the elastomer, for example via a sulfur atom; G represents a hydrocarbon group making it possible to link Y and X.
- Coupling agents should 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 white charge but are devoid of the active X function with respect to - screw of the elastomer.
- Coupling agents, in particular silica-elastomer have been described in a large number of documents, the best known being bifunctional alkoxysilanes.
- the present invention taken in its first object, relates to the use: ⁇ of an effective amount of a coupling agent consisting of a compound A carrying at least two functions denoted Y and X, graftable with on the one hand on the white filler by means of the function Y and on the other hand on the elastomer by means of the function X; ⁇ as coupling agent for white filler and elastomer in rubber compositions comprising: - (B) at least one elastomer of rubber type, natural or synthetic;
- the coupling agent is a compound A which comprises a multifunctional POS (compound Apos) comprising, per molecule, and attached to silicon atoms, on the one hand at least one hydroxyl function and / or at least one hydrolyzable function and on the other hand at least one group containing an activated ethylenic double bond;
- POS compound Apos
- the amount of said coupling agent is determined so as to provide in the isoprene rubber composition at least 0.5 phr (part by weight per 100 parts by weight of elastomer (s)) of POS (compound A PO s) -
- the essential characteristic of the coupling agent (compound A PO s) used in the present invention is that it is a POS carrying at least one activated ethylenic double bond (function X) allowing it to be grafted onto the isoprenic elastomer.
- activated bond is meant in a known manner a bond made more capable of reacting (in the present case, with the isoprenic elastomer).
- each ethylenic double bond is preferably activated by the presence of at least one adjacent electron-withdrawing group, that is to say attached to at least 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 functionality Y it is advantageously chosen from at least one hydroxyl radical, at least one alkoxyl radical of formula R 1 O where R 1 represents an alkyl radical, linear or branched, having from 1 to 15 carbon atoms, and a mixture of hydroxyl (s) and alkoxyl (s) radicals.
- the functionality Y is chosen from at least one hydroxyl radical, at least one alkoxyl radical, linear or branched, having from 1 to 6 carbon atoms, and a mixture of hydroxyl (s) and alkoxyl (s) radicals. C-
- the functionality Y is chosen from at least one hydroxyl radical, at least one alkoxyl radical, linear or branched having from 1 to 3 carbon atoms (that is to say methoxyl, ethoxyl, propoxyl and / or isopropoxyl), and a mixture of hydroxyl (s) and alkoxyl (s) C- ⁇ -C 3 .
- Coupling agents included in the scope of the present invention are coupling agents or compounds A which comprise multifunctional POSs containing similar or different units of formula:
- the 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; preferably, the symbols R 2 are chosen from the radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, cyclohexyl and phenyl; more preferably, the symbols R 2 are methyl radicals;
- the symbols Y which are identical or different, each represent a hydroxyl or alkoxyl function R 1 O, the definition of which is that given above with regard to the functionality Y;
- the symbols X identical or different, each represent a function carrying an activated ethylenic double bond, chosen: (3.1) from functions carrying an ethylenic double bond activated by at least one activating group having the general or particular definitions mentioned above - before; (3.2) or, advantageously, from the radicals having the formulas (X / a), (X / b), (X / c), and their mixtures
- + B- is O, NH, N-alkyl, N-phenyl, S, CH 2 , CH-alkyl or CH-phenyl; + B 2 is N, CH, C-alkyl or C-phenyl;
- R '" can also represent a monovalent COOH group or a derivative group of ester or amide type
- the divalent radical A is intended to ensure the bond with the polysiloxane chain and consists of a divalent hydrocarbon radical, saturated or unsaturated, which may comprise one or more heteroatoms such as oxygen and nitrogen, comprising from 1 to 18 atoms of carbon; (3.3) or, very advantageously, from the radicals having the following formulas (11/1) to (II / 5), and their mixtures:
- the symbol V represents a divalent radical -O- or -NR 6 -; preferably, the symbol V is a radical -O- or -NR 6 - where R 6 has the preferred definition indicated below; more preferably, the symbol V is a radical -O- or -NR 6 - where R 6 has the more preferred definition indicated below;
- the symbol W represents a monovalent group COOR 7 or a monovalent group CONR 8 R 9 ; preferably, the symbol W is a COOR 7 group or a CONR 8 R 9 group in which the radicals R 7 , R 8 and R 9 have the preferred definitions indicated below; more preferably, the symbol W is a COOR 7 group or a CONR 8 R 9 group in which the radicals R 7 , R 8 and R 9 have the more preferred definitions indicated below;
- R 3 is a divalent alkylene radical, linear or branched, comprising from 1 to 15 carbon atoms whose free valence is carried by a carbon atom and is linked to a silicon atom, said radical R 3 being able to be interrupted within of the alkylene chain by at least one heteroatom (such as oxygen and nitrogen) or at least one divalent group comprising at least one heteroatom (such as oxygen and nitrogen), and in particular by at least one divalent residue of general formula —rest- chosen from: -O-, -CO-, -CO-O-, -COO-cyclohexylene (optionally substituted by an OH radical) -, -O-alkylene (linear or branched C 2 -C 6 , optionally substituted by an OH or COOH radical) -, -O-CO-alkylene (linear or branched in
- R 3 also represents a divalent aromatic radical of general formula —radical— chosen from: -phenylene (ortho, meta or para) -alkylene (linear or branched in C 2 -C 6 ) -, -phenylene (ortho, meta or para) -O-alkylene (linear or branched C 2 -C 6 ) -,
- R 3 represents an alkylene radical 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 radical - (CH 2 ) 2 - or - (CH 2 ) 3 -; with the precision according to which, in the definitions of R 3 which precede, the divalent residues and radicals mentioned when they are not symmetrical, can be positioned with the valence v1 on the left and with the valence v2 on the right or vice versa with the valence v2 on the left and valence v1 on the right; + the symbols R 4 and R 5 , identical or different, each represent a hydrogen atom, a halogen atom, a cyano radical, an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or a radical
- R 6 , R 7 , R 8 , R 9 and R 10 identical or different, each represent a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or a phenyl radical , the symbols R 8 and R 9 being able, in addition, to form together and with the nitrogen atom to which they are linked, a single saturated ring having from 3 to 8 carbon atoms in the ring; preferably, the symbols R 6 ,
- R 7 , R 8 , R 9 and R 10 are chosen from a hydrogen atom, and the methyl, ethyl, n-propyl, n-butyl radicals, the symbols R 8 and R 9 can, in addition, form together and with the nitrogen atom a pyrrolidinyl or piperidyl ring; more preferably, these symbols are chosen from a hydrogen atom and a methyl radical, the symbols R 8 and R 9 being able, in addition, to form together and with the nitrogen atom a piperidyl ring;
- the rate of Y functions, expressed by the number, per molecule, of Y functions per 100 silicon atoms, is at least 0.8%, and preferably lies in the range from 1 to 100%;
- the rate of X functions, expressed by the number, per molecule, of X functions per 100 silicon atoms, is at least 0.4%, and preferably lies in the range from 0, 8 to 100%.
- each multifunctional POS of formula (I) can have either a linear structure or a cyclic structure, or a mixture of these structures, which structures may also have a certain molar amount of ramifications ("T" motifs).
- the coupling agent is a compound "which comprises a multifunctional POS"; this expression should be interpreted as meaning that the coupling agent or compound A forming part of the present invention can be in the form of a multifunctional POS in the pure state or in the form of a mixture of such POS with a quantity variable weight (generally much less than 50% in the mixture) of another (or others) compound (s) which can (can) consist in: (i) one and / or the other of the reactants departure from which the multifunctional POSs are prepared, when the conversion rate of said reagents is not complete; and or
- the scope of the invention includes coupling agents or compounds A which comprise multifunctional POSs, chosen from the family of POSs conforming to formula (I), which are essentially linear and have the following average formula:
- n is in the range from 0 to 100
- * p is in the range from 0 to 100
- n + p + q + r + s + t giving the total number of silicon atoms is in the range from 2 to 250
- n is in the range from 0 to 50
- p is in the range from 0 to 20
- R 6 are chosen as indicated above in point (3.3) concerning formula (I), (we will then speak, for short, in this case, of POS / 2 polymer of ester type), • the symbols R 2 and Y are as defined above in points (1) and (2) relating to formula (I);
- n + p + q + r + s giving the total number of silicon atoms is in the range from more than 2 to 50, - the ratio 100 s / (n + p + q + r + s) giving the rate of reasons "T" is ⁇ 10,
- n ' is in the range from 0 to 9
- the coupling agents or compounds A are prepared comprising the multifunctional POSs in accordance with formulas (I), (III) and (III ′) given above by various methods. These processes involve in particular: organosilane carrying an X function and at least two Y functions, and a linear, ⁇ -dihydroxylated POS, - a redistribution and equilibration reaction between an organosilane carrying an X function and at least two functions Y and / or halogeno, and an organocyclosiloxane which can optionally carry one or more Y functions in the chain,
- a coupling reaction between an organosilane carrying an X function and at least two Y functions, and a polysilazane - a coupling reaction between a precursor POS, linear or cyclic, carrying at least one Y function and functionalized with at least one motif attached to a silicon atom, in particular of the -alkylene type (linear or branched C 2 -C 6 ) -OH, -alkylene (linear or branched C 2 -C 6 ) -NR 6 H or - alkylene (linear or branched C 2 -C 6 ) -COOH, and a reactive compound capable of reacting with the abovementioned motif (s) to give rise to the desired function X,
- the coupling agents or compounds A comprising the multifunctional POSs in accordance with formulas (I), (III) and (Ml ′) are prepared by a process which consists, for example: (a) in hydrolyzing an organosilane of aqueous formula : R 2
- q is either equal to zero [when the silane (IV) is hydrolyzed in the absence of the silane (V)]
- a number different from zero when the silane (IV is hydrolyzed)
- the coupling agents or compounds A which are preferably used in the context of the invention are those comprising the POS / 1 polymers of imide type.
- An advantageous procedure, for preparing the coupling agents or compounds A comprising the POS / 1 polymers of imide type corresponds to a process (d) which makes it possible to prepare compounds comprising POS / 1 polymers of the imide type in the formula ( III) of which the symbol q is equal to zero and consists in carrying out the following steps (d1) and (d2): (d1) we react:
- this reaction being carried out in the presence of a catalyst, supported or not supported on an inorganic material (such as for example a siliceous material), based on at least one Lewis acid, by operating at atmospheric pressure and at a temperature lying in the range from room temperature (23 ° C) to 150 ° C, and preferably from 60 ° C to 120 ° C;
- a catalyst supported or not supported on an inorganic material (such as for example a siliceous material)
- an inorganic material such as for example a siliceous material
- reaction medium obtained is stabilized by treatment of the latter with at least one halosilane of formula (R 2 ) 3 Si-halogeno where the halo residue is preferably chosen from a chlorine or bromine atom, by operating in the presence of at least one non-nucleophilic organic base which is not reactive with respect to the imide function formed in situ during step (d1).
- the disilazane is used in an amount at least equal to 0.5 mole per 1 mole of starting organosilane and preferably ranging from 1 to 5 moles per 1 mole of organosilane.
- the preferred Lewis acid is ZnCI 2 and / or ZnBr 2 and / or Znl 2 . It is used in an amount at least equal to 0.5 moles per 1 mole of organosilane and, preferably, ranging from 1 to 2 moles per 1 mole of organosilane.
- the reaction is carried out in a heterogeneous medium, preferably in the presence of a solvent or of a mixture of solvents common to the organosilicon reagents.
- the preferred solvents are of the aprotic polar type such as for example chlorobenzene, toluene, xylene, hexane, octane, decane.
- the most preferred solvents are toluene and xylene.
- This method (d) can be implemented by following any operating method known per se.
- a procedure which is very suitable is as follows: firstly, the reactor is supplied with Lewis acid, then a solution of the organosilane is gradually poured into all or part of the solvent (s); in a second step, the reaction mixture is brought to the chosen temperature, then the disilazane is poured which can optionally be used in the form of a solution in part of the solvent (s); then in a third step, the reaction mixture obtained is treated with at least one halosilane in the presence of one or more organic base (s) with a view to its stabilization; and finally in a fourth step, the stabilized reaction medium is filtered to remove the Lewis acid and the salt formed in situ during stabilization, then it is subjected to devolatilization under reduced pressure to remove the solvent (s) ( s).
- the halosilane (s) is (are) used in an amount at least equal to 0.5 mole per 1 mole of starting organosilane and, from preferably ranging from 0.5 to 1.5 moles per 1 mole of organosilane.
- organic bases those which are preferred are in particular tertiary aliphatic amines (such as for example N-methylmorpholine, triethylamine, triisopropylamine) and hindered cyclic amines (such as for example 2,2,6-tetraalkyl , 6 piperidines).
- the organic base (s) is (are) used in an amount at least equal to 0.5 mole per 1 mole of starting organosilane and preferably ranging from 0.5 to 1 , 5 moles per 1 mole of organosilane.
- a second advantageous procedure, usable for preparing the coupling agents or compounds A comprising the POS / 1 polymers of imide type corresponds to a process (e) which makes it possible to prepare compounds comprising POS / 1 polymers of the imide type in the formula (III) of which the symbol q is different from zero and consists in carrying out the only step (d1) defined as indicated above, but in which the disilazane of formula (XI) has been replaced by a cyclic polysilazane of formula:
- This method (e) can be implemented using the procedure which is suitable, presented above with regard to the implementation of method (d), and based on the realization of only the first beats, second beats and fourth beats of which we spoke above.
- the polysilazane is used in an amount at least equal to 0.5 / h mole for 1 mole of starting organosilane and preferably ranging from 1 / h to 5 / h moles for 1 mole of organosilane ( h being the number of silazane units in the polysilazane of formula (XII)).
- A which can be in the form of a multifunctional POS in the pure state (or compound A PO s) or in the form of a mixture of a multifunctional POS (or compound A PO s) with a variable quantity by weight (generally much less than 50% in the mixture) of another (or other) compound (s) which can (can) consist for example in: (i) a small amount of the starting organosilane of formula ( X) unreacted; and / or (ii) a small amount of the organosilane of formula:
- n "and q" are whole or fractional numbers satisfying the following cumulative conditions: • n "is in the range from 1 to 9,
- the coupling agents or compounds A which are still preferably used in the context of the invention are those comprising POS / 2 polymers of acid type or of ester type.
- Amino POS is represented for short, in the following, by the simplified formula:
- the amino POS of formula (XV) can be prepared, in a manner known per se, by carrying out for example a redistribution and equilibration reaction between on the one hand a
- Coupling agents or compounds A comprising POS / 2 polymers of the ester type which constitute another category of coupling agents which are also preferably targeted within the framework of the present invention, can be prepared by applying the advantageous procedures below. -after defined.
- the coupling agents or compounds A comprising the POS / 2 polymers of the ester type can be prepared by esterification of an intermediate maleamic acid POS by carrying out the following steps: (g1) coupling reaction, as explained above with regard to process (f), between the amino POS (XV) and maleic anhydride (XVI), then (g2) esterification reaction of the medium comprising the POS / 2 of the acid type formed, to lead to the compound comprising the desired ester type POS / 2, by applying the following synthesis scheme:
- R 4 C CR 5 ⁇ Si-R 3 -NR 6 -CCr V COOH
- step (g2) With regard to the practical way of implementing step (g2), reference will be made for more details to the contents of the following documents which describe, possibly starting from other reagents, procedures applicable to the conduct of this step:
- the coupling agents or compounds A comprising the POS / 2 polymers of ester type can be prepared by forming an amide function by adding the amino POS (XV) to an ester derivative (XIX) obtained from a mono-ester of maleic acid (XVIII), by carrying out the steps the following steps : (h1) alcoholysis of maleic anhydride (XVI) with alcohol R 7 -OH, (h2) activation of the carboxylic acid function of the mono-ester of maleic acid (XVIII) obtained, using the various methods of activation described in the field of peptide synthesis, to lead to the activated ester derivative (XIX), then (h3) addition of the amino POS (XV) to said activated ester derivative (XIX) to lead to the compound comprising POS / 2 ester type desired, applying the following synthesis scheme:
- step (h1) cf. in particular J. Med. Chem., 1983, 26, pages 174-181; - for stages (h2) and (h3): cf. John JONES, Amino Acid and Peptide-Synthesis, pages 25-41, Oxford University Press, 1994.
- DCCI dicyclohexylcarbodiimide
- HO-SN N-hydroxysuccinimide
- T-COOH " .
- Activation methods (j) and (2j) are especially preferred.
- they can advantageously be carried out starting, for example, from an organosilane of formula:
- organosilanes are products which can be prepared by applying either of the methods (g1) and (g2) described above, in the conduct of which the amino POS (XV) will be replaced by the amino alkoxysilane of formula (XVII).
- POSs described above could be grafted beforehand on the reinforcing white fillers, in particular on silica, by means of their function (s) Y, the reinforcing white fillers thus precoupled then being able to be linked to the isoprenic elastomer via their free function (s) X with activated ethylenic double bond.
- a second object of the present invention relates to the compositions comprising: (B) at least one isoprenic elastomer (hereinafter denoted compound B), (C) a reinforcing white filler (hereinafter denoted compound C) , and (A) an adequate amount of coupling agent consisting of compound A comprising the multifunctional POS which has been defined above, carrying on the one hand at least one hydroxyl radical and / or at least one hydrolysable radical and on the other hand at least one activated ethylenic double bond (or compound A PO s) -
- compositions include (the parts are given by weight):
- the amount of coupling agent is determined so that it represents from 1% to 20%, preferably from 2 to 15%, more preferably from 3 at 8%, relative to the weight of the reinforcing white filler.
- isoprene elastomers which are used for the compositions in accordance with the second subject of the invention, is understood more specifically: (1) synthetic polyisoprenes obtained by homopolymerization of isoprene or 2-methyl-butadiene-1, 3;
- vinyl aromatic monomers having 8 to 20 carbon atoms, such as for example: styrene, ortho-, meta- or paramethylstyrene, the commercial "vinyl-toluene" mixture, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinyl mesitylene, divinylbenzene, vinylnaphthalene;
- vinyl nitrile monomers having from 3 to 12 carbon atoms, such as for example acrylonitrile, methacrylonitrile;
- the acrylic ester monomers derived from acrylic acid or from 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 methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylate d 'isobutyl;
- copolymer polyisoprenes containing between 99% and 20% by weight of isoprenic units and between 1% and 80% by weight of diene units, aromatic vinyls, vinyl nitriles and / or acrylic esters, and consisting for example in poly (isoprene -butadiene), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene);
- (6) a mixture containing a majority quantity (ranging from 51% to 99.5% and preferably from 70% to 99% by weight) of the abovementioned elastomer (1) or (3) and a minority quantity (ranging from 49% to 0.5% and preferably from 30% to 1% by weight) of one or more diene elastomers other than isoprene.
- diene elastomer other than isoprene is meant in a manner known per se: the homopolymers obtained by polymerization of one of the diene monomers conjugates defined above in point (2.1), such as for example polybutadiene and polychloroprene; the copolymers obtained by copolymerization of at least two of the above-mentioned conjugated dienes (2.1) together or by copolymerization of one or more of the above-mentioned conjugated dienes (2J) with one or more of the above-mentioned unsaturated monomers (2.2), (2.3) and / or (2.4), such as for example poly (butadiene-styrene) and poly (butadiene-acrylonitrile).
- the homopolymers obtained by polymerization of one of the diene monomers conjugates defined above in point (2.1), such as for example polybutadiene and polychloroprene the copolymers obtained by copolymerization of at least two of the
- isoprenic elastomers chosen from: (1) synthetic homopolymer polyisoprenes; (2) synthetic polyisoprenes copolymers consisting of poly (isoprene-butadiene), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene); (3) natural rubber; (4) butyl rubber; (5) a mixture of the above-mentioned elastomers (1) to (4) with one another; (6) a mixture containing a majority quantity of the abovementioned elastomer (1) or (3) and a minority quantity of dienic elastomer other than isoprene consisting of polybutadiene, polychloroprene, poly (butadiene-styrene) and poly (butadiene-acrylonitrile).
- isoprene elastomers chosen from: (1) synthetic polyisoprenes homopolymers; (3) natural rubber; (5) a mixture of the above-mentioned elastomers (1) and (3); (6) a mixture containing a majority quantity of the abovementioned elastomer (1) or (3) and a minority quantity of dienic elastomer other than isoprene consisting of polybutadiene and poly (butadiene-styrene).
- the expression "reinforcing white charge” is understood to define a “white” charge (that is to say inorganic or mineral), sometimes called “clear” charge, capable of reinforcing on its own, without other means than that of a coupling agent, an elastomer composition (s) of rubber type, natural (s) or synthetic (s).
- the reinforcing white filler is present is immaterial, that is to say that said filler can be in the form of powder, micro pearls, granules or beads.
- the reinforcing white filler or compound C 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 is meant 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. More preferably, 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 area ranging from 100 to 250 m 2 / g, preferably from 100 to 190 m 2 / g, - a DOP oil intake of less than 300 ml / 100 g, preferably ranging from 200 to 295 ml / 100 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) by using dioctylphthalate.
- a highly dispersible alumina is advantageously used having:
- BET specific surface area ranging from 30 to 400 m 2 / g, preferably from 80 to 250 m 2 / g,
- aluminas A125, CR125, D65CR from the company BAIKOWSKI.
- compositions in accordance with the second subject of the invention contain as coupling agent a compound A comprising a multifunctional POS carrying function (s) X chosen from the radicals of formulas (II / 2), (II / 3), (H / 4) and / or (H / 5), such as for example a compound A comprising an acid type POS / 2 polymer or a polymer POS / 2 of ester type, it may be advantageous, if necessary depending on the particular conditions of implementation of the invention and the final destination of the rubber compositions, to add to the composition, at least one coupling activator or compound D.
- a compound A comprising a multifunctional POS carrying function (s) X chosen from the radicals of formulas (II / 2), (II / 3), (H / 4) and / or (H / 5), such as for example a compound A comprising an acid type POS / 2 polymer or a polymer POS / 2 of ester type
- compositions in accordance with the invention may therefore also contain at least one coupling activator, capable of activating, that is to say of increasing the coupling function of the coupling agent described above;
- this coupling activator used in very small proportion (at most equal to 1 part per 100 parts by weight of elastomer (s)), is a radical initiator (also called radical initiator) of the thermal initiation type.
- 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 which can be introduced into the compositions of 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 the form thermal. It is believed that the generation of these free radicals can promote, during the manufacture (thermomechanical kneading) of the rubber compositions, a better interaction between the coupling agent and the isoprenic elastomer.
- a radical initiator is chosen whose decomposition temperature is less than 180 ° C, more preferably less than 160 ° C, such temperature ranges making it possible to fully benefit from the coupling activation effect, during manufacture. compositions according to the invention.
- the coupling activator when one is used, is preferably chosen from the group consisting of peroxides, hydroperoxides, azido compounds, bis (azo) compounds, peracids, peresters and a mixture of two or more more than two of these compounds.
- the coupling activator when one is used, 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 or a mixture of two or more of these compounds.
- benzoyl peroxide acetyl peroxide, lauryl peroxide, cumyl peroxide, t-butyl peroxide, butyl peracetate, butyl hydroperoxide, cumene hydroperoxide, f-butyl cumyl peroxide, 2,5-dimethyl-2,5-bis (.- butyl) 3-hexyne peroxide, 1,3-bis (f-butyl- peroxide) isopropyl) benzene, 2,4-dichlorobenzoyl peroxide, t-butyl perbenzoate, 1 J bis (t-butyl) -3,3,5-trimethylcyclohexane per
- Trigonox 29-40 50% by weight of peroxide on a solid support of calcium carbonate.
- the radical initiator when one is used, is 1,1'-azobis (isobutyronitrile).
- the radical initiator when one is used, is used in very small proportion in the compositions in accordance with the invention, namely at a rate ranging from 0.05 to 1 part, preferably from 0.05 to 0.5 parts, and even more preferably from 0.1 to 0.3 parts, per 100 parts of elastomer (s).
- 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 (s) compositions.
- vulcanization agents chosen from sulfur or sulfur-donor 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;
- a conventional reinforcing filler such as carbon black (in this case, the reinforcing white filler used constitutes more than 50% of the weight of the '' white reinforcing 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; antioxidants; antiozonants, such as for example N-phenyl-N '- (1,3-dimethyl butyl) -p-phenylene-diamine; plasticizers and implementation assistants.
- additives capable, for example, of limiting and / or standardizing the heating of the compositions and / or of avoiding the occurrence of the roasting phenomenon.
- Such additives can be lubricants, agents for covering the white charge (agent comprising the only Y function capable of physically and / or chemically binding to the white charge), inhibitors of prevulcanization, and they can make it possible to improve appreciably. , if necessary, the ease of processing the compositions in the raw state.
- processing aids consist, for example, of: polyols; polyethers (e.g.
- polyethylene glycols polyethylene glycols
- primary, secondary or tertiary amines for example trialcanol-amines
- ⁇ , ⁇ -dihydroxylated polydimethylsiloxanes Such a processing aid, when one is used, is used in an amount of 0.05 to 10 parts by weight, and preferably 0.08 to 8 parts, per 100 parts by weight of elastomer (s).
- a third object of the present invention relates to the process for the preparation of elastomeric compositions (s) comprising a reinforcing white filler and an effective amount of coupling agent.
- This process can be done according to a conventional procedure in one or two stages.
- all the necessary constituents are introduced and kneaded into a conventional internal mixer, for example of the BANBURY type or of the BRABENDER type, generally with the exception of the vulcanization agent (s) and optionally: vulcanization accelerator (s) and / 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).
- a fourth object of the present invention relates to articles made of isoprene elastomer (s) having a body comprising the compositions described above in the context of the second object of the invention.
- the present invention is particularly useful for preparing articles consisting for example of engine mounts, shoe soles, cable car rollers, seals for household appliances and cable sheaths.
- This example illustrates the preparation of a coupling agent or compound A according to the invention, comprising a POS / 1 polymer of imide type.
- This compound A is prepared by implementing process (d) which has been explained above in the present specification, with N- [ ⁇ -propyl (methy! Diethoxy) as the starting organosilane ) silane] maleamic.
- 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 (244.82 g, or 1.28 moles) is gradually poured at the temperature of 20 ° C (temperature of the reaction maintained at this value by means of an ice-water bath placed under the reactor), on a solution of maleic anhydride (128.2 g, or 1.307 moles) in toluene as solvent (442, 5 g), over a period of 105 minutes.
- the reaction medium is then left at 23 ° C for 15 hours.
- reaction medium is filtered through a sintered glass of porosity 3 and a solution of the desired maleamic acid silane in toluene is thus recovered, a solution which is used in the form in which it is found, for use. of the following process (d).
- This solution contains 0.157 moles of maleamic acid silane per 100 g of solution.
- the reaction mixture is brought to the temperature of 54 ° C., then the gradual pouring of the hexamethyldisilazane (65.12 g, or 0.403 mole) is carried out over a period of one hour; at the end of pouring, the temperature of the reaction medium is 82 ° C., and it is maintained at this value for another 1 hour 30 minutes;
- the reaction medium obtained is filtered on a fritted glass of porosity 3 and containing 2 cm of silica, and then the resulting filtrate was devolatilized at 30 ° C by establishing a reduced pressure of 10.10 2 Pa to give a brown oil comprising the POS / 1 oligomer of the desired imide type.
- Said brown oil was subjected to proton NMR and silicon NMR ( 29 Si) analyzes. The results of these analyzes reveal that the reaction product obtained at the end of process (d) contains:
- EXAMPLE 2 This example illustrates the preparation of a coupling agent or compound A according to the invention, comprising another POS / 1 polymer of imide type.
- This other compound A is prepared by implementing process (e) which has been explained above in the present specification, with N- [ ⁇ -propyl (methyldiethoxy) acid as the starting organosilane. silane] maleamic.
- the reaction medium is filtered through a sintered glass of porosity 3 and a solution of the desired maleamic acid silane in toluene is thus recovered, a solution which is used in the form in which it is found for the implementation of the following process.
- This solution contains 0.157 moles of maleamic acid silane per 100 g of solution.
- - 1st stage in a 3 liter glass reactor, equipped with a stirring system and a dropping funnel, ZnCI 2 (168.2 g, or 1.2342 moles) is introduced, then the solid is heated at 80 ° C for 1 hour 30 minutes under a reduced pressure of 4.10 2 Pa; the reactor is then returned to atmospheric pressure, operating under an argon atmosphere, and 365 cm 3 of toluene are then poured in, then gradually 704.8 g of the malane acid silane solution (320 g, ie 1.107 moles) into toluene which was obtained previously in point 1;
- the dropping funnel is charged by the cyclic hexaméthyltrisilazane (88.7 g, 0.404 mole) and 208 cm 3 of toluene; the temperature of the reaction medium is 72 ° C., then the cyclic hexamethyltrisilazane is poured in gradually over a period of 2 hours 25 minutes; at the end of pouring, the orange-colored organic solution obtained is heated to a temperature of
- reaction medium is filtered through a "cardboard filter", then the toluene is removed after devolatilization under reduced pressure.
- This example illustrates the preparation of a coupling agent or compound A according to the invention, comprising a POS / 2 polymer of acid type.
- This compound A is prepared by implementing method (f) which has been explained above in the present specification, consisting in reacting an amine POS of formula (XV) with maleamic anhydride.
- the reaction medium is heated at 95 ° C for 6 hours. At the end of this time, the reaction medium is left for 15 hours at room temperature (23 ° C.), then it is neutralized using 0.241 g of a mixture based on phosphoric acid and polydimethylsiloxane oligomers, operating at 90 ° C for 1 hour.
- the reaction medium obtained is then devolatilized by operating at 180 ° C and under a reduced pressure of 3J0 2 Pa, for 30 minutes.
- the amino POS was subjected to proton and silicon NMR analyzes. The results of these analyzes reveal a mixture of linear (85% molar) and cyclic (15% molar) structures having the following average formulas:
- the amino POS thus obtained contains 0.5 mole of amino functions per 100 g of product.
- a solution of maleic anhydride (30.67 g, or 0.3128 mole) in CH 2 CI is introduced into a 1 I glass reactor, fitted with a stirring system and a dropping funnel. 2 as solvent (400 cm 3 ), then the temperature of the reaction medium is lowered to 8 ° C., and the amine POS (62.11 g) is then poured gradually over a period of 1 hour 15 minutes while maintaining the temperature reaction medium at 8 ° C during casting. At the end of casting, the reaction medium is left for 15 hours at room temperature (23 ° C). The solvent is then removed under reduced pressure, operating at a temperature which does not exceed 30 ° C.
- This example illustrates the preparation of a coupling agent or compound A according to the invention, comprising a POS / 2 polymer of ester type.
- This compound A is prepared by implementing method (h) [with activation method (2d)] which has been explained above in this memo.
- maleic anhydride In a 2 liter tetracol reactor, maleic anhydride is introduced (698.1 g, or 7.12 moles), then it is melted by heating the reactor using '' an oil bath brought to 70 ° C. Once all of the anhydride has melted, methanol (221.4 g, or 6.92 moles) is introduced, with stirring, via a dropping funnel. The medium is then left under stirring for 20 hours at 23 ° C, then it is devolatilized by establishing a reduced pressure of 10.10 2 Pa for 1 hour, and finally it is filtered on filter paper. 786.9 g of monomethyl ester of maleic acid of formula (86% yield) are thus recovered:
- the N-hydroxysuccinimide (39) is introduced into a 2-liter glass reactor, equipped with mechanical stirring and a dropping funnel. , 20 g, i.e. 0.3406 mol), tetrahydrofuran as solvent (200 cm 3 ) and the monomethyl ester of the acid maleic (40.1 g, or 0.3085 mole).
- the reaction medium is stirred, and the dicyclohexylcarbodiimide (69.3 g, or 0.3363 mole) is poured in gradually, at room temperature (23 ° C.), over a period of 10 minutes. The medium becomes heterogeneous due to the precipitation of dicyclohexylurea. After a reaction period of 50 minutes, the reaction medium is filtered through
- ⁇ -aminopropylsilane of formula (C 2 H 5 O) 2 CH 3 Si (CH 2 ) 3 NH 2 (1700, 3 g, i.e. 8.9 moles).
- the pouring of water (1442.5 g, or 80.13 moles) is done using a pouring pump having a flow rate of 10 cm 3 / hour.
- the reaction is exothermic throughout the casting and the temperature is not controlled.
- a water-ethanol mixture is removed under reduced pressure of 10.10 1 Pa, first at 40 ° C, then at 70 ° C to completely remove the ethanol and thus lead to an amino oil intermediate.
- a polydimethylsiloxane oil ⁇ , ⁇ are introduced into another 1 liter reactor, also provided with mechanical stirring and with a condenser.
- -dihydroxylated (230.92 g) having a viscosity of 50 mPa.s at 25 ° C and titrating 12% by weight of OH, as well as catalyst based on potassium siliconate (0.0416 g).
- the reaction medium is heated at 90 ° C for 6 hours.
- the reaction medium is left for 15 hours at room temperature (23 ° C), then it is neutralized using 0.0974 g of a mixture based on phosphoric acid and polydimethylsiloxane oligomers , operating at 90 ° C for 1 hour.
- the reaction medium obtained is filtered through a microporous filter of 0.5 ⁇ m.
- the POS thus obtained contains 0.51 amino function per 100 g of product.
- EXAMPLES 5 TO 8 The purpose of these examples is to demonstrate the coupling performance (white charge-isoprenic elastomer) of a compound A comprising a multifunctional POS (compound A P os) which has been defined above, carrying on the one hand at least one hydroxyl radical and / or at least one alkoxyl radical and on the other hand at least one activated ethylenic double bond. These performances are compared with those of a conventional coupling agent based on a TESPT silane.
- composition No. 1 (control 1): absence of coupling agent;
- composition No. 2 (control 2): coupling agent based on TESPT silane (4 pce);
- composition No. 3 (Example 5): coupling agent or compound A, providing in composition 1, 86 phr of POS / 1 polymer of imide type, prepared in Example 1;
- Example 6 coupling agent or compound A, providing in the composition 2.65 phr of POS / 1 polymer of imide type, prepared in Example 2;
- - Composition No. 5 (Example 7): coupling agent or compound A, providing in the composition 4.66 phr of the POS / 2 polymer of the acid type, prepared in Example 3;
- composition No. 6 (Example 8): coupling agent or compound A, providing 5.02 phr of the POS / 2 polymer of the ester type, prepared in Example 4, in the composition.
- the contents of the mixer are drained or dropped after 5 minutes.
- the temperature reached is around 145 ° 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 composition to be tested is placed in the test chamber 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 measurement is measured. test chamber, the composition completely filling the chamber in question.
- 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 toasting time TS-2 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 the raw mixtures at this temperature without having initiation of vulcanization.
- the measurements are carried out on the uniformly vulcanized compositions for 20 minutes at 160 ° C.
- the tensile tests are carried out in accordance with the indications of standard NF T 46-002 with H2 type test pieces. The 10%, 100%, 300% modules and the breaking strength are expressed in MPa; the elongation at break is expressed in%.
- the measurement is carried out according to the indications in standard ASTM D 3240. The given value is measured at 15 seconds.
- the measurement is carried out according to the indications in standard NF T 46-012 using method 2 with a rotating test tube holder. The measured value is the loss of substance (in mm 3 ) on abrasion; the lower it is, the better the abrasion resistance.
- compositions of Examples 5 to 8 have higher modulus values (M 300%) and higher reinforcement indices than the control mixture without coupling agent and which can be higher than those obtained with the TESPT silane (control 2).
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0007696A FR2810329B1 (fr) | 2000-06-16 | 2000-06-16 | Utilisation d'un compose organosilique porteur d'au moins une double liaison ethylenique activee comme agent de couplage dans les compositions de caoutchouc comprenant une charge blanche |
FR0007696 | 2000-06-16 | ||
PCT/FR2001/001856 WO2001096443A1 (fr) | 2000-06-16 | 2001-06-14 | Utilisation d'un compose organosilicique porteur d'au moins une double liaison ethylenique activee comme agent de couplage dans les compositions de caoutchouc comprenant une charge blanche |
Publications (1)
Publication Number | Publication Date |
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EP1299451A1 true EP1299451A1 (fr) | 2003-04-09 |
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ID=8851329
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01945437A Withdrawn EP1299451A1 (fr) | 2000-06-16 | 2001-06-14 | Utilisation d'un compose organosilicique porteur d'au moins une double liaison ethylenique activee comme agent de couplage dans les compositions de caoutchouc comprenant une charge blanche |
Country Status (11)
Country | Link |
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US (1) | US20040059049A1 (fr) |
EP (1) | EP1299451A1 (fr) |
JP (1) | JP2004503635A (fr) |
KR (1) | KR20030010734A (fr) |
CN (1) | CN1443212A (fr) |
AU (1) | AU2001267659A1 (fr) |
BR (1) | BR0111844A (fr) |
CA (1) | CA2412786A1 (fr) |
FR (1) | FR2810329B1 (fr) |
MX (1) | MXPA02012507A (fr) |
WO (1) | WO2001096443A1 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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AU2843901A (en) * | 1999-12-30 | 2001-07-16 | Michelin Recherche Et Technique S.A. | Rubber composition for a tyre, comprising a coupling agent (white filler/dienic elastomer) activated by heat-initiated radical starter |
AU2001285946A1 (en) * | 2000-09-15 | 2002-03-26 | Michelin Recherche Et Technique S.A. | Rubber composition for tyre comprising a citraconimido-alkoxysilane as coupling agent |
FR2886303B1 (fr) * | 2005-05-26 | 2007-07-20 | Rhodia Chimie Sa | Utilisation d'une combinaison particuliere d'un agent de couplage et d'un agent de recouvrement, comme systeme de couplage(charge blanche-elastomere) dans les compositions de caoutchouc comprenant une charge inorganique |
US8257632B2 (en) * | 2007-10-09 | 2012-09-04 | Nan Ya Plastics Corporation | Heat-insulating transparent PVC sheet |
TWI386451B (zh) * | 2009-05-12 | 2013-02-21 | Nanya Plastics Corp | 一種pvc樹脂組成物及其製品 |
FR2946050B1 (fr) * | 2009-06-02 | 2016-10-28 | Rhodia Operations | Utilisation comme agent de couplage,dans une composition d'elastomere(s)comprenant une charge inorganique renforcante d'un compose organosilicique fonctionnalise particulier |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US4565873A (en) * | 1978-08-30 | 1986-01-21 | Ciba-Geigy Corporation | Silanes containing imide groups |
US4806608A (en) * | 1987-03-16 | 1989-02-21 | Loctite Corporation | Curable siloxane maleimide composition |
JP2551902B2 (ja) * | 1992-08-10 | 1996-11-06 | 株式会社巴川製紙所 | 新規なビスナジックイミド化合物およびその製造方法 |
FR2743564A1 (fr) * | 1996-01-11 | 1997-07-18 | Michelin & Cie | Compositions de caoutchouc pour enveloppes de pneumatiques a base de silices contenant un additif de renforcement a base d'un polyorganosiloxane fonctionnalise et d'un compose organosilane . |
JP4025385B2 (ja) * | 1996-12-06 | 2007-12-19 | 東レ・ダウコーニング株式会社 | オルガノペンタシロキサンの製造方法 |
JPH10168089A (ja) * | 1996-12-04 | 1998-06-23 | Toray Dow Corning Silicone Co Ltd | 1−アシルオキシ−オルガノテトラシロキサンおよびその製造方法 |
US6140445A (en) * | 1998-04-17 | 2000-10-31 | Crompton Corporation | Silane functional oligomer |
-
2000
- 2000-06-16 FR FR0007696A patent/FR2810329B1/fr not_active Expired - Fee Related
-
2001
- 2001-06-14 JP JP2002510575A patent/JP2004503635A/ja not_active Withdrawn
- 2001-06-14 CN CN01813056A patent/CN1443212A/zh active Pending
- 2001-06-14 WO PCT/FR2001/001856 patent/WO2001096443A1/fr not_active Application Discontinuation
- 2001-06-14 CA CA002412786A patent/CA2412786A1/fr not_active Abandoned
- 2001-06-14 AU AU2001267659A patent/AU2001267659A1/en not_active Abandoned
- 2001-06-14 MX MXPA02012507A patent/MXPA02012507A/es unknown
- 2001-06-14 EP EP01945437A patent/EP1299451A1/fr not_active Withdrawn
- 2001-06-14 US US10/311,542 patent/US20040059049A1/en not_active Abandoned
- 2001-06-14 KR KR1020027017190A patent/KR20030010734A/ko not_active Application Discontinuation
- 2001-06-14 BR BR0111844-7A patent/BR0111844A/pt not_active IP Right Cessation
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See references of WO0196443A1 * |
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CN1443212A (zh) | 2003-09-17 |
US20040059049A1 (en) | 2004-03-25 |
BR0111844A (pt) | 2003-09-23 |
KR20030010734A (ko) | 2003-02-05 |
MXPA02012507A (es) | 2004-09-10 |
CA2412786A1 (fr) | 2001-12-20 |
AU2001267659A1 (en) | 2001-12-24 |
FR2810329B1 (fr) | 2002-12-06 |
WO2001096443A1 (fr) | 2001-12-20 |
JP2004503635A (ja) | 2004-02-05 |
FR2810329A1 (fr) | 2001-12-21 |
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