Functionalized polymer, rubber composition and pneumatic tire
The present invention is directed to a functionalized elastomer comprising the reaction product of a living anionic elastomeric polymer and a polymerization terminator of formula I where X is Cl, Br, or I; m is an integer from 0 to 2, n is an integer from 1 to 3, with the proviso that n+m=3; R 1 , R 2 are independently C1 to C18 alkyl, aryl, or a combination thereof, or R 1 , R 2 are independently —SiR 3 where R is independently alkyl, aryl, alkoxy, or disubstituted amino, or R 1 and R 2 taken together with their common nitrogen atom and optionally a sulfur or oxygen heteroatom to form a five to eight membered ring; R 3 is hydrogen, or C1 to C18 alkyl, aryl, or a combination thereof, or R 3 is —SiR 3 where R is independently alkyl, aryl, alkoxy, or disubstituted amino, or R 3 is —R 6 —R 7 , where R 6 is C1 to C3 alkanediyl and R 7 is selected from the following structures —S—Z, —N(R 8 )(R 9 ), —O(Y), or Si(OR 10 ) 3 , where R 8 and R 9 are independently C1 to C18 alkyl, aryl, or a combination thereof, Y and Z are independently selected from the group consisting of methoxymethyl, tetrahydropyranyl, tetrahydrothiopyranyl, tetrahydrofuranyl, tert-butyl, allyl, 1-ethoxyethyl, benzyl, triphenylmethyl, triethylsilyl, triisopropylsilyl, trimethylsilyl, tert-butyl dimethyl silyl, tert-butyl diphenyl silyl, and isopropyldimethylsilyl, and R 10 are independently C1 to C4 alkyl; or when m=1, the polymerization terminator may have the formula II where R 4 , R 5 are independently C1 to C18 alkyl, aryl, or a combination thereof, or R 4 , R 5 are independently —SiR 3 where R is independently alkyl, aryl, alkoxy, or disubstituted amino, X and R 3 are as defined previously, and k is an integer from 0 to 10.
1. A method of making a functionalized elastomer comprising the steps of:
terminating the reaction product of a living anionic elastomeric polymer with a polymerization terminator of formula I
where X is Cl, Br, or I;
m is an integer from 0 to 1, n is an integer from 2 to 3, with the proviso that n+m=3;
R 1 , R 2 are independently C1 to C18 alkyl, aryl, or a combination thereof, or R 1 , R 2 are independently —SiR 3 where R is independently alkyl, aryl, alkoxy, or disubstituted amino, or R 1 and R 2 taken together with their common nitrogen atom and optionally a sulfur or oxygen heteroatom to form a five to eight membered ring;
R 3 is hydrogen, or C1 to C18 alkyl, aryl, or a combination thereof, or R 3 is —SiR 3 where R is independently alkyl, aryl, alkoxy, or disubstituted amino, or R 3 is —R 6 —R 7 , where R 6 is C1 to C3 alkanediyl and R 7 is selected from the following structures —S—Z, —N(R 8 )(R 9 ), —O(Y), or Si(OR 10 ) 3 , where R 8 and R 9 are independently C1 to C18 alkyl, aryl, or a combination thereof,
Y and Z are independently selected from the group consisting of methoxymethyl, tetrahydropyranyl, tetrahydrothiopyranyl, tetrahydrofuranyl, tert-butyl, allyl, 1-ethoxyethyl, benzyl, triphenylmethyl, triethylsilyl, triisopropylsilyl, trimethylsilyl, tert-butyl dimethyl silyl, tert-butyl diphenyl silyl, and isopropyldimethylsilyl, and
R 10 are independently C1 to C4 alkyl;
or when m=1, the polymerization terminator may have the formula II
where R 4 , R 5 are independently C1 to C18 alkyl, aryl, or a combination thereof, or R 4 , R 5 are independently —SiR 3 where R is independently alkyl, aryl, alkoxy, or disubstituted amino, X and R 3 are as defined previously, and k is an integer from 0 to 10.
2. The method of claim 1 , wherein the living anionic elastomeric polymer is produced in the presence of an organolithium initiator.
3. The method of claim 2 , wherein the polymerization terminator is used in an amount ranging from 0.05 to 5 molar equivalents based on the lithium in the organolithium initiator.
4. The method of claim 1 , wherein the polymerization terminator is selected from one of the following structures:
5. A method of making a functionalized elastomer comprising the steps of:
terminating the reaction product of a living anionic elastomeric polymer with a polymerization terminator of formula I
where X is Cl, Br, or I;
m is 0, n is 3, with the proviso that n+m=3;
R 1 , R 2 are methyl groups;
R 3 is hydrogen, or C1 to C18 alkyl, aryl, or a combination thereof, or R 3 is —SiR 3 where R is independently alkyl, aryl, alkoxy, or disubstituted amino, or R 3 is —R 6 —R 7 , where R 6 is C1 to C3 alkanediyl and R 7 is selected from the following structures —S—Z, —N(R 8 )(R 9 ), —O(Y), or Si(OR 10 ) 3 , where R 8 and R 9 are independently C1 to C18 alkyl, aryl, or a combination thereof,
Y and Z are independently selected from the group consisting of methoxymethyl, tetrahydropyranyl, tetrahydrothiopyranyl, tetrahydrofuranyl, tert-butyl, allyl, 1-ethoxyethyl, benzyl, triphenylmethyl, triethylsilyl, triisopropylsilyl, trimethylsilyl, tert-butyl dimethyl silyl, tert-butyl diphenyl silyl, and isopropyldimethylsilyl, and
R 10 are independently C1 to C4 alkyl;
or when m=1, the polymerization terminator may have the formula II
where R 4 , R 5 are independently C1 to C18 alkyl, aryl, or a combination thereof, or R 4 , R 5 are independently —SiR 3 where R is independently alkyl, aryl, alkoxy, or disubstituted amino, X and R 3 are as defined previously, and k is an integer from 0 to 10.
6. The method of claim 5 , wherein the living anionic elastomeric polymer is produced in the presence of an organolithium initiator.
7. The method of claim 6 , wherein the polymerization terminator is used in an amount ranging from 0.05 to 5 molar equivalents based on the lithium in the organolithium initiator.