Modified conjugated diene-based polymer and method for preparing the same
The present invention provides a modified conjugated diene-based polymer which includes a functional group derived from a substituted styrene-based compound and a functional group derived from an aminosilane-based compound, a method for preparing the same, and a rubber composition including the same. The modified conjugated diene-based polymer includes the functional group derived from an aminosilane-based compound of Formula 1 and a functional group derived from a substituted styrene-based compound of Formula 2 at both terminals of a main chain, and thus, shows a high modification ratio. When applying the polymer in a rubber composition, excellent affinity with a filler may be shown, and as a result, agglomeration of a filler in the rubber composition may be prevented, and the dispersibility of the filler may be increased, thereby improving the processability of the rubber composition.
1. A modified conjugated diene-based polymer comprising a functional group derived from an aminosilane-based compound of the following Formula 1 and a functional group derived from a substituted styrene-based compound of the following Formula 2:
in Formula 1 or Formula 2,
A 1 and A 2 are each independently a substituted or unsubstituted divalent hydrocarbon group of 1 to 20 carbon atoms,
R 1 to R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms,
L 1 to L 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms,
R 5 is a hydrogen atom or a monovalent hydrocarbon group of 1 to 3 carbon atoms,
D is a monovalent hydrocarbon group of 1 to 5 carbon atoms, comprising N or O, and
k is an integer of 0 to 5.
2. The modified conjugated diene-based polymer of claim 1 , wherein in Formula 1, A 1 and A 2 are each independently selected from the group consisting of a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms, an arylene group of 6 to 20 carbon atoms, and —[(X) n —(Y) n ]— (where X and Y are each independently a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms or an arylene group of 6 to 20 carbon atoms, X and Y are not the same, and m and n are each independently an integer of 1 to 3).
3. The modified conjugated diene-based polymer of claim 1 , wherein in Formula 1, R 1 to R 4 are each independently selected from the group consisting of a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, and an alkylaryl group of 7 to 20 carbon atoms.
4. The modified conjugated diene-based polymer of claim 1 , wherein in Formula 1, L 1 to L 4 are each independently selected from the group consisting of a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, and an alkylaryl group of 7 to 20 carbon atoms.
5. The modified conjugated diene-based polymer of claim 1 , wherein in Formula 1,
A 1 and A 2 are each independently an alkylene group of 1 to 3 carbon atoms,
R 1 to R 4 are each independently an alkyl group of 1 to 6 carbon atoms, and
L 1 to L 4 are each independently an alkyl group of 1 to 6 carbon atoms.
6. The modified conjugated diene-based polymer of claim 1 , wherein the aminosilane-based compound is one selected from the group consisting of the following Formulae 1a to 1c, or a mixture of two or more thereof:
7. The modified conjugated diene-based polymer of claim 1 , wherein the substituted styrene-based compound of Formula 2 is a compound of the following Formula 2a:
8. The modified conjugated diene-based polymer of claim 1 , wherein the modified conjugated diene-based polymer is a modified polymer of a conjugated diene-based polymer selected from the group consisting of a homopolymer of a conjugated diene-based monomer; and a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer.
9. The modified conjugated diene-based polymer of claim 1 , wherein the modified conjugated diene-based polymer has a number average molecular weight of 50,000 g/mol to 2,000,000 g/mol, a weight average molecular weight of 100,000 g/mol to 4,000,000 g/mol, and molecular weight distribution of 1.1 to 3.0.
10. The modified conjugated diene-based polymer of claim 1 , wherein the modified conjugated diene-based polymer has a mooney viscosity of 40 to 140 at 100° C.
11. A method for preparing the modified conjugated diene-based polymer of claim 1 , the method comprising:
1) reacting a substituted styrene-based compound of the following Formula 2 and an organo-alkali metal compound in a hydrocarbon solvent to prepare a modification initiator composition;
2) performing polymerization reaction of conjugated diene-based monomers, or a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of the modification initiator composition to prepare an active polymer; and
3) reacting the active polymer and an aminosilane-based compound of the following Formula 1:
in Formula 1 or Formula 2,
A 1 and A 2 are each independently a substituted or unsubstituted divalent hydrocarbon group of 1 to 20 carbon atoms,
R 1 to R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms,
L 1 to L 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms,
R 5 is a hydrogen atom or a monovalent hydrocarbon group of 1 to 3 carbon atoms,
D is a monovalent hydrocarbon group of 1 to 5 carbon atoms, comprising N or O, and
k is an integer of 0 to 5.
12. The method for preparing the modified conjugated diene-based polymer of claim 11 , wherein the substituted styrene-based compound is used from 0.1 mol to 3.0 mol based on 1 mol of the organo-alkali metal compound.
13. The method for preparing the modified conjugated diene-based polymer of claim 11 , wherein the aminosilane-based compound is used from 0.1 mol to 2.0 mol based on 1 mol of the organo-alkali metal compound.
14. A rubber composition comprising the modified conjugated diene-based polymer according to claim 1 .
15. The rubber composition of claim 14 , wherein the rubber composition further comprises a filler of 0.1 parts by weight to 150 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.