Reinforcement materials, elastomeric compositions and tyres for vehicles wheels comprising the same

A derivatised silica (SIL-A-B) made by a process comprising:

• providing silanised silica (SIL-A), wherein the silanised silica (SIL-A) is made by a process comprising:
• providing silica (C),
• providing at least one silanising agent of formula (A),
• (R1)3Si—X (A)
• wherein
• R1, the same or different from each other, are chosen from R2, OR2, OSi(OR2)3, OH, halogen, and group X, provided that at least one R1 is equal to OR2, OSi(OR2)3, OH, or halogen;
• R2, the same or different from each other, are chosen from linear and branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms;
• group X is a reactive alkenyl group chosen from X1, X2, and X3, wherein
• X1 is a group —R3-C(Wa)═C(R4)R4,
• X2 is a group —R3-C(R4)=C(Wa)R4, and
• X3 is a group —R3-Wb-C(R4)=C(R4)R4,
• wherein
• R3 is absent or is chosen from linear and branched alkylene groups with 1 to 10 carbon atoms,
• Wa is H or an electron-attractor group chosen from COOR4, CONR4R4, NO2, CN, COR4, SO3R4, NR4R4, and halogen,
• Wb is a group chosen from —O—CO—, —COO—, —NR4-CO—, —CO—NR4-, —SO—, —SO2—, and —CO—, and
• R4, the same or different from each other, are H or are chosen from the groups R2 defined above;
• placing the silica (C) and the silanising agent (A) in contact in a first reaction medium,
• allowing the silica (C) and the silanising agent (A) to react until the silanised silica (SIL-A) is obtained, and
• separating the silanised silica (SIL-A) from the first reaction medium;
• placing the silanised silica (SIL-A) in contact, in a second reaction medium, with at least one compound of formula (B) chosen from the silsesquioxanes of formula (B1), (B2), the compounds of formula (B3), and mixtures thereof,
• wherein
• n is an even number ranging from 4 to 24,
• x is an integer ranging from 3 to 23, y is an integer ranging from 1 to 6, and x+y≤24, and
• groups R, the same or different from each other, are chosen from R2 and X,
• provided that at least one of groups R is a group X,
• wherein R2, R4 and X are as defined above;
• adding at least one radical initiator (D) to the second reaction medium;
• and
• allowing the silanised silica (SIL-A), the at least one compound of (B), and the at least one radical initiator (D) to react until a derivatised silica (SIL-A-B) is obtained.

An elastomeric composition comprising:

• at least 100 phr of at least one solid diene elastomeric polymer (E), and
• at least 3 phr of a derivatised silica (SIL-A-B) made by a process comprising:
• providing silanised silica (SIL-A), the silanised silica made by a process comprising:
• providing silica (C),
• providing at least one silanising agent of formula (A),
• (R1)3Si—X (A)
• wherein
• R1, the same or different from each other, are chosen from R2, OR2, OSi(OR2)3, OH, halogen, and group X, provided that at least one R1 is equal to OR2, OSi(OR2)3, OH, or halogen;
• R2, the same or different from each other, are chosen from linear and branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms;
• group X is a reactive alkenyl group chosen from X1, X2, and X3, wherein
• X1 is a group —R3-C(Wa)═C(R4)R4,
• X2 is a group —R3-C(R4)=C(Wa)R4, and
• X3 is a group —R3-Wb-C(R4)=C(R4)R4,
• wherein
• R3 is absent or is chosen from linear and branched alkylene groups with 1 to 10 carbon atoms,
• Wa is H or an electron-attractor group chosen from COOR4, CONR4R4, NO2, CN, COR4, 303R4, NR4R4, and halogen,
• Wb is a group chosen from —O—CO—, —COO—, —NR4-CO—, —CO—NR4-, —SO—, —SO2—, and —CO—, and
• R4, the same or different from each other, are H or are chosen from the groups R2 defined above;
• placing the silica (C) and the silanising agent (A) in contact in a first reaction medium,
• allowing the silica (C) and the silanising agent (A) to react until the silanised silica (SIL-A) is obtained, and
• separating the silanised silica (SIL-A) from the first reaction medium;
• placing the silanised silica (SIL-A) in contact, in a second reaction medium, with at least one compound of formula (B) chosen from the silsesquioxanes of formula (B1), (B2), the compounds of formula (B3), and mixtures thereof,
• wherein
• n is an even number ranging from 4 to 24,
• x is an integer ranging from 3 to 23, y is an integer ranging from 1 to 6, and x+y≤24, and
• groups R, the same or different from each other, are chosen from R2 and X,
• provided that at least one of groups R is a group X,
• wherein R2, R4 and X are as defined above;
• adding at least one radical initiator (D) to the second reaction medium;
• and
• allowing the silanised silica (SIL-A), the at least one compound of (B), and the at least one radical initiator (D) to react until a derivatised silica (SIL-A-B) is obtained.

An elastomeric composition comprising:

• at least 100 phr of at least one solid diene elastomeric polymer (E);
• at least 5 phr of silica (C);
• at least 0.3 phr of a silanising agent of formula (A),
• (R1)3Si—X (A)
• wherein
• R1, the same or different from each other, are chosen from R2, OR2, OSi(OR2)3, OH, halogen, and group X, provided that at least one R1 is equal to OR2, OSi(OR2)3, OH, or halogen;
• R2, the same or different from each other, are chosen from linear and branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms;
• group X is a reactive alkenyl group chosen from X1, X2, and X3, wherein
• X1 is a group —R3-C(Wa)═C(R4)R4,
• X2 is a group —R3-C(R4)=C(Wa)R4, and
• X3 is a group —R3-Wb-C(R4)=C(R4)R4,
• wherein
• R3 is absent or is chosen from linear and branched alkylene groups with 1 to 10 carbon atoms,
• Wa is H or an electron-attractor group chosen from COOR4, CONR4R4, NO2, CN, COR4, SO3R4, NR4R4, and halogen,
• Wb is a group chosen from —O—CO—, —COO—, —NR4-CO—, —CO—NR4-, —SO—, —SO2—, and —CO—, and
• R4, the same or different from each other, are H or are chosen from the groups R2 defined above;
• and
• at least 0.5 phr of a compound of formula (B), wherein formula (B) is chosen from the silsesquioxanes of formula (B1), (B2), the compounds of formula (B3), and mixtures thereof,
• wherein
• n is an even number ranging from 4 to 24,
• x is an integer ranging from 3 to 23, y is an integer ranging from 1 to 6, and x+y≤24, and
• groups R, the same or different from each other, are chosen from R2 and X,
• provided that at least one of groups R is a group X,
• wherein R2, R4 and X are as defined above.

A vulcanisable elastomeric composition for a tyre for vehicle wheels, comprising:

• at least 0.1 phr of at least one vulcanising agent (F);
• and
• an elastomeric composition comprising at least 100 phr of at least one solid diene elastomeric polymer (E) and at least 3 phr of a derivatised silica (SIL-A-B) made by a process comprising:
• providing silanised silica (SIL-A), the silanised silica made by a process comprising:
• providing silica (C),
• providing at least one silanising agent of formula (A),
• (R1)3Si—X (A)
• wherein
• R1, the same or different from each other, are chosen from R2, OR2, OSi(OR2)3, OH, halogen, and group X, provided that at least one R1 is equal to OR2, OSi(OR2)3, OH, or halogen;
• R2, the same or different from each other, are chosen from linear and branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms;
• group X is a reactive alkenyl group chosen from X1, X2, and X3, wherein
• X1 is a group —R3-C(Wa)═C(R4)R4,
• X2 is a group —R3-C(R4)=C(Wa)R4, and
• X3 is a group —R3-Wb-C(R4)=C(R4)R4,
• wherein
• R3 is absent or is chosen from linear and branched alkylene groups with 1 to 10 carbon atoms,
• Wa is H or an electron-attractor group chosen from COOR4, CONR4R4, NO2, CN, COR4, SO3R4, NR4R4, and halogen,
• Wb is a group chosen from —O—CO—, —COO—, —NR4-CO—, —CO—NR4-, —SO—, —SO2—, and —CO—, and
• R4, the same or different from each other, are H or are chosen from the groups R2 defined above;
• placing the silica (C) and the silanising agent (A) in contact in a first reaction medium,
• allowing the silica (C) and the silanising agent (A) to react until the silanised silica (SIL-A) is obtained, and
• separating the silanised silica (SIL-A) from the first reaction medium;
• placing the silanised silica (SIL-A) in contact, in a second reaction medium, with at least one compound of formula (B) chosen from the silsesquioxanes of formula (B1), (B2), the compounds of formula (B3), and mixtures thereof,
• wherein
• n is an even number ranging from 4 to 24,
• x is an integer ranging from 3 to 23, y is an integer ranging from 1 to 6, and x+y≤24,
• groups R, the same or different from each other, are chosen from R2 and X,
• provided that at least one of groups R is a group X,
• wherein R2, R4 and X are as defined above;
• adding at least one radical initiator (D) to the second reaction medium;
• and
• allowing the silanised silica (SIL-A), the at least one compound (B), and the at least one radical initiator (D) to react until a derivatised silica (SIL-A-B) is obtained.

A tyre component for vehicle wheels, either green or at least partially vulcanised, comprising a vulcanisable elastomeric composition comprising:

• at least 0.1 phr of at least one vulcanising agent (F);
• and
• an elastomeric composition comprising at least 100 phr of at least one solid diene elastomeric polymer (E), and at least 3 phr of a derivatised silica (SIL-A-B) made by a process comprising:
• providing silanised silica (SIL-A), the silanised silica made by a process comprising:
• providing silica (C),
• providing at least one silanising agent of formula (A),
• (R1)3Si—X (A)
• wherein
• R1, the same or different from each other, are chosen from R2, OR2, OSi(OR2)3, OH, halogen, and group X, provided that at least one R1 is equal to OR2, OSi(OR2)3, OH, or halogen;
• R2, the same or different from each other, are chosen from linear and branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms;
• group X is a reactive alkenyl group chosen from X1, X2, and X3, wherein
• X1 is a group —R3-C(Wa)═C(R4)R4,
• X2 is a group —R3-C(R4)=C(Wa)R4, and
• X3 is a group —R3-Wb-C(R4)=C(R4)R4,
• wherein
• R3 is absent or is chosen from linear and branched alkylene groups with 1 to 10 carbon atoms,
• Wa is H or an electron-attractor group chosen from COOR4, CONR4R4, NO2, CN, COR4, SO3R4, NR4R4, and halogen,
• Wb is a group chosen from —O—CO—, —COO—, —NR4-CO—, —CO—NR4-, —SO—, —SO2—, and —CO—, and
• R4, the same or different from each other, are H or are chosen from the groups R2 defined above;
• placing the silica (C) and the silanising agent (A) in contact in a first reaction medium,
• allowing the silica (C) and the silanising agent (A) to react until the silanised silica (SIL-A) is obtained, and
• separating the silanised silica (SIL-A) from the first reaction medium;
• placing the silanised silica (SIL-A) in contact, in a second reaction medium, with at least one compound of formula (B) chosen from the silsesquioxanes of formula (B1), (B2), the compounds of formula (B3), and mixtures thereof,
• (RSiO1,5)n (RSiO1,5)x[RSi(OR4)O]y [RSi(OH)O]3—4
• (B1) (B2) (B3)
• wherein
• n is an even number ranging from 4 to 24,
• x is an integer ranging from 3 to 23, y is an integer ranging from 1 to 6, and x+y≤24,
• groups R, the same or different from each other, are chosen from R2 and X,
• provided that at least one of groups R is a group X,
• wherein R2, R4 and X are as defined above;
• adding at least one radical initiator (D) to the second reaction medium;
• and
• allowing the silanised silica (SIL-A), the at least one compound of (B), and the at least one radical initiator (D) to react until a derivatised silica (SIL-A-B) is obtained.

A tyre for vehicle wheels comprising at least one tyre component, either green or at least partially vulcanized, chosen from tread, carcass structure, belt structure, under-layer, bead protection layers, sidewall, sidewall insert, mini-sidewall, under-liner, rubber layers, bead filler, and sheet, wherein the tyre component comprises a vulcanisable elastomeric composition comprising:

• at least 0.1 phr of at least one vulcanising agent (F);
• and
• an elastomeric composition comprising at least 100 phr of at least one solid diene elastomeric polymer (E), and at least 3 phr of a derivatised silica (SIL-A-B) made by a process comprising:
• providing silanised silica (SIL-A), the silanised silica being obtainable according to a process which preferably comprises:
• providing silica (C),
• providing at least one silanising agent of formula (A),
• (R1)3Si—X (A)
• wherein
• R1, the same or different from each other, are chosen from R2, OR2, OSi(OR2)3, OH, halogen, and group X, provided that at least one R1 is equal to OR2, OSi(OR2)3, OH, or halogen;
• R2, the same or different from each other, are chosen from linear and branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms;
• group X is a reactive alkenyl group chosen from X1, X2, and X3, wherein
• X1 is a group —R3-C(Wa)═C(R4)R4,
• X2 is a group —R3-C(R4)=C(Wa)R4, and
• X3 is a group —R3-Wb-C(R4)=C(R4)R4,
• wherein
• R3 is absent or is chosen from linear and branched alkylene groups with 1 to 10 carbon atoms,
• Wa is H or an electron-attractor group chosen from COOR4, CONR4R4, NO2, CN, COR4, SO3R4, NR4R4, and halogen,
• Wb is a group chosen from —O—CO—, —COO—, —NR4-CO—, —CO—NR4-, —SO—, —SO2—, and —CO—, and
• R4, the same or different from each other, are H or are chosen from the groups R2 defined above;
• placing the silica (C) and the silanising agent (A) in contact in a first reaction medium,
• allowing the silica (C) and the silanising agent (A) to react until the silanised silica (SIL-A) is obtained, and
• separating the silanised silica (SIL-A) from the first reaction medium;
• placing the silanised silica (SIL-A) in contact, in a second reaction medium, with at least one compound of formula (B) chosen from the silsesquioxanes of formula (B1), (B2), the compounds of formula (B3), and mixtures thereof,
• wherein
• n is an even number ranging from 4 to 24,
• x is an integer ranging from 3 to 23, y is an integer ranging from 1 to 6, and x+y≤24,
• groups R, the same or different from each other, are chosen from R2 and X,
• provided that at least one of groups R is a group X,
• wherein R2, R4 and X are as defined above;
• adding at least one radical initiator (D) to the second reaction medium;
• and
• allowing the silanised silica (SIL-A), the at least one compound of (B), and the at least one radical initiator (D) to react until a derivatised silica (SIL-A-B) is obtained.