Modified conjugated diene-based polymer and method of preparing the same
The present invention relates to a modifier represented by Formula 1, a method of preparing the same, a modified conjugated diene-based polymer having a high modification ratio which includes a modifier-derived functional group, and a method of preparing the polymer.
1. A modifier represented by Formula 1:
wherein, in Formula 1,
R 1 , R 4 , and R 5 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms,
R 2 is a divalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 3 is a connecting group represented by Formula 2 or Formula 3,
wherein, in Formula 2 or Formula 3,
R 6 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms; or a substituent represented by Formula 2-1,
R 7 is a divalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 8 to R 10 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms,
wherein, in Formula 2-1,
R 11 is a divalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, and
R 12 and R 13 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms.
2. The modifier of claim 1 , wherein
in Formula 1,
R 1 , R 4 , and R 5 are each independently an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms,
R 2 is an alkylene group having 1 to 6 carbon atoms, and
R 3 is a connecting group represented by Formula 2 or Formula 3,
wherein, in Formula 2 or Formula 3, R 6 is an alkyl group having 1 to 6 carbon atoms or a substituent represented by Formula 2-1, and R 7 to R 10 are an alkylene group having 1 to 6 carbon atoms,
wherein, in Formula 2-1, R 11 is an alkylene group having 1 to 6 carbon atoms, and R 12 and R 13 are each independently an alkyl group having 1 to 6 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms.
3. The modifier of claim 1 , wherein the modifier represented by Formula 1 comprises compounds represented by Formulae 1-1 to 1-5:
4. The modifier of claim 1 , wherein the modifier is a modifier for a conjugated diene-based polymer.
5. A method of preparing the modifier represented by Formula 1 of claim 1 , the method comprising:
performing a first reaction of a compound represented by Formula 4 and an alkyl ketone compound to prepare a compound represented by Formula 5; and
performing a second reaction of the compound represented by Formula 5 and a compound represented by Formula 6:
H 2 N—R 14 [Formula 4]
wherein, in Formula 1, and Formulae 4 to 6,
R 1 to R 5 are the same as defined in claim 1 ,
R 14 is a substituent represented by Formula 4-1 or Formula 4-2,
R 15 is
wherein R 6 and R 7 are the same as defined in claim 1 , and
A is chlorine (Cl) or bromine (Br),
wherein, in Formula 4-1 or Formula 4-2,
R 7 to R 10 are the same as defined in claim 1 , and
R 16 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms; or —RNH 2 , wherein R is a divalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms.
6. The method of claim 5 , wherein the compound represented by Formula 4 and the alkyl ketone compound are reacted at a molar ratio of 1:1 to 1:2.
7. The method of claim 5 , wherein the compound represented by Formula 5 and the compound represented by Formula 6 are reacted at a molar ratio of 1:1 to 1:2.
8. The method of claim 5 , wherein the first reaction is performed in a temperature range of 110° C. to 160° C.
9. The method of claim 5 , wherein the second reaction is performed in a temperature range of 20° C. to 60° C.