Rubber composition for tire comprising an organosiloxane coupling agent

Abstract

A subject-matter of the present invention is a rubber composition intended for the manufacture of tyres or of tyre semi-finished products, based on at least one isoprene elastomer, an inorganic filler as reinforcing filler and a polyfunctional organosiloxane coupling agent capable of providing the bonding between the reinforcing inorganic filler and the isoprene elastomer, comprising per molecule, grafted to its silicon atoms, on the one hand at least one hydroxyl or hydrolysable functional group allowing it to be grafted to the reinforcing inorganic filler and, on the other hand, at least one group bearing at least one azodicarbonyl functional group —CO—N═N—CO— allowing it to be grafted to the isoprene elastomer.

1 . A tire comprising a rubber composition based on at least one isoprene elastomer, an inorganic filler as reinforcing filler and a polyfunctional organosiloxane coupling agent which provides the bonding between the said reinforcing inorganic filler and the isoprene elastomer, wherein the said organosiloxane comprises per molecule, grafted to its silicon atoms, on the one hand at least one hydroxyl or hydrolysable functional group allowing it to be grafted to the reinforcing inorganic filler and, on the other hand, at least one group bearing at least one azodicarbonyl functional group —CO—N═N—CO— allowing it to be grafted to the isoprene elastomer. 
   
   
       2 . The tire according to  claim 1 , the organosiloxane being composed of identical or different siloxyl units of average formula:
   G 3   c G 2   b G 1   a SiO (4-a-b-c)/2   (I)   
     in which:
 a, b and c are each whole or fractional numbers from 0 to 3; 
 the G 1  radicals, which are identical or different if several are present, represent a monovalent hydrocarbon radical; 
 the G 2  radicals, which are identical or different if several are present, represent a hydroxyl or hydrolysable group; 
 the G 3  radicals, which are identical or different if several are present, represent a group bearing the azodicarbonyl functional group (—CO—N═N—CO—), 
 
     with the proviso that:
 0<(a+b+c)≦3; 
 at least one G 2  radical (i.e., b≧1) and at least one G 3  radical (i.e., c≧1) are present in the siloxane molecule. 
 
   
   
       3 . The tire according to  claim 2 , the organosiloxane being composed of identical or different siloxyl units of average formula (III):
   (A-CO—N═N—CO-Z) C G 2   b G 1   a SiO (4-a-b-c)/2      
     in which:
 Z is a divalent bonding group connecting the azodicarbonyl functional group to a silicon atom of the organosiloxane; 
 A represents a monovalent hydrocarbon radical or the group of formula Z′ in which Z′, which is identical to or different from Z, is a divalent bonding group which makes it possible to connect the azodicarbonyl functional group to a silicon atom (identical to or different from the Si atom connected to Z) of the organosiloxane; 
 A, Z and if applicable Z′, independently, may comprise one or more heteroatoms. 
 
   
   
       4 . The tire according to  claim 3 , the organosiloxane being composed of identical or different siloxyl units of average formula (V):
   G 2   b G 1   a (A-CO—N═N—CO-Z)SiO (3-a-b)/2      
     in which:
 a is a whole or fractional number from 0 to 2; 
 b is a whole or fractional number from 1 to 2; 
 (a+b)≦2. 
 
   
   
       5 . The tire according to  claim 4 , the organosiloxane corresponding to the formula (VII):
   [(G 0 ) 3 SiO 1/2 ] m [(G 0 ) 2 SiO 2/2 ] n [G 0 SiO 3/2 ] o [SiO 4/2 ] p [(G 2 ) b′ (G 1 ) a′ (A-CO—N═N—CO-Z)SiO (3-a′-b′)/2 ] q      
     in which:
 a′represents an integer chosen from 0, 1 and 2; 
 b′represents an integer chosen from 0, 1 and 2; 
 the sum a′+b′lies within the range extending from 0 to 2, with the condition according to which, when b′=0, then at least one of the G 0  symbols corresponds to the definition of G 2 ; and
 either at least one of the symbols m, n, o or p is a whole or fractional number other than 0 (zero) and q represents a whole or fractional number equal to or greater than 1; 
 or q is greater than 1 and then each of the symbols m, n, o or p has any value; 
 
 the G 0  symbols, which are identical or different, each represent one of the groups corresponding to G 2  or G 1 . 
 
   
   
       6 . The tire according to  claim 5 , in which the sum a′+b′ is equal to 1 or 2; m lies within the range from 1 to 2; n=o=p=0 (zero) and q=1. 
   
   
       7 . The tire according to  claim 6 , the organosiloxane corresponding to at least one of the formulae (XI) and (XII) (Et=ethyl):
   [Me 3 SiO 1/2 ][(EtO) 2 (A-CO—N═N—CO-Z)SiO 1/2 ]  (XI)     [Me 3 SiO 1/2 ] 2 [(EtO)(A-CO—N═N—CO-Z)SiO 2/2 ]  (XII).   
   
   
       8 . The tire according to  claim 7 , the organosiloxane being a siloxane oligomer comprising from 2 to 12, silicon atoms. 
   
   
       9 . The tire according to  claim 7 , the A symbol representing the monovalent radical Et-O— and the Z symbol representing the divalent radical —NH—(CH 2 ) 3 —. 
   
   
       10 . The tire according to  claim 1 , in which:
 the G 1  radicals, which are identical to or different from one another, are chosen from the group consisting of C 1 -C 6  alkyl groups, the cyclohexyl group and the phenyl group;   the G 2  radicals, which are identical to or different from one another, are chosen from the group consisting of the hydroxyl group, C 1 -C 8  alkoxyl groups and C 5 -C 8  cycloalkoxyl groups.   
   
   
       11 . The tire according to  claim 10 , in which:
 the radicals G 1  are chosen from methyl and ethyl;   the radicals G 2  are chosen from hydroxyl, methoxyl and ethoxyl.   
   
   
       12 . The tire according to  claim 1 , the organosiloxane being composed of identical or different siloxyl units of average formula (VIII):
   G 2   b G 1   a (R—O—CO—N═N—CO-Z)SiO (3-a-b)/2      
     in which:
 a, b, Z, G 1  and G 2  have the definitions given above; 
 R represents a C 1 -C 4  alkyl. 
 
   
   
       13 . The tire according to  claim 1 , the organosiloxane being composed of identical or different siloxyl units of average formula (IX):
   G 2   b G 1   a (Z′-CO—N═N—CO-Z)SiO (3-a-b)/2 .   
   
   
       14 . The tire according to  claim 3 , Z and, if applicable, Z′ representing a divalent hydrocarbon radical comprising from 1 to 18 carbon atoms. 
   
   
       15 . The tire according to  claim 2 , in which:
 G 1  is the methyl or ethyl radical;   G 2  is the hydroxyl, methoxyl or ethoxyl radical;   Z (and, if applicable, Z′) represents a divalent hydrocarbon radical comprising from 1 to 18 carbon atoms.   
   
   
       16 . The tire according to  claim 15 , in which:
 G 1  is the methyl radical;   G 2  is the hydroxyl or ethoxyl radical;   Z (and, if applicable, Z′) is a C 1 -C 10  alkylene comprising a heteroatom chosen from O, S and N.   
   
   
       17 . The tire according to  claim 16 , in which Z (and, if applicable, Z′) is a divalent radical chosen from the group consisting of —(CH 2 ) y —, —NH—(CH 2 ) y — and —O—(CH 2 ) y —, y being an integer from 1 to 6. 
   
   
       18 . The tire according to  claim 1 , wherein the rubber composition is present in the tread of the tire. 
   
   
       19 - 21 . (canceled)