Modified polymerization initiator and modified conjugated diene- based polymer including functional group derived therefrom
The present invention relates to a modified polymerization initiator for a conjugated diene-based polymer, and a modified conjugated diene-based polymer including a functional group derived from the modified polymerization initiator.
1. A modified polymerization initiator comprising: one or more units derived from a compound represented by the following Formula 1, and a unit derived from a compound represented by the following Formula 2:
in Formula 1,
X is —NR a R b , —OR c , or —SR d , and
R a to R d are each independently an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkynyl group of 2 to 30 carbon atoms, a cycloalkyl group of 3 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, a heteroalkyl group of 1 to 30 carbon atoms, a heteroalkenyl group of 2 to 30 carbon atoms, a heteroalkynyl group of 2 to 30 carbon atoms, a heterocycloalkyl group of 2 to 30 carbon atoms, or a heteroaryl group of 3 to 30 carbon atoms, where each of R a to R d is unsubstituted or substituted with a substituent comprising one or more heteroatoms selected from N, O, S, Si and F atoms, and R a and R b may be connected with each other to form an aliphatic hydrocarbon ring of 5 to 20 carbon atoms, an aromatic hydrocarbon ring of 6 to 20 carbon atoms, or a heterocycle of 3 to 20 carbon atoms, which are unsubstituted or substituted with an alkyl group of 1 to 30 carbon atoms,
M-R 1 [Formula 2]
in Formula 2,
M is an alkali metal, and
R 1 is hydrogen, an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkynyl group of 2 to 30 carbon atoms, a cycloalkyl group of 5 to 30 carbon atoms, or an aryl group of 6 to 30 carbon atoms.
2. The modified polymerization initiator of claim 1 , wherein
in Formula 1,
X is —NR a R b , —OR c , or —SR d , and
R a to R d are each independently an 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, a heteroalkyl group of 1 to 20 carbon atoms, a heteroalkenyl group of 2 to 20 carbon atoms, a heteroalkynyl group of 2 to 20 carbon atoms, a heterocycloalkyl group of 2 to 20 carbon atoms, or a heteroaryl group of 3 to 20 carbon atoms, where each of R a to R d is unsubstituted or substituted with a substituent comprising one or more heteroatoms selected from N, O, S, Si and F atoms, and R a and R b may be connected with each other to form an aliphatic hydrocarbon ring of 5 to 20 carbon atoms, an aromatic hydrocarbon ring of 6 to 20 carbon atoms, or a heterocycle of 3 to 20 carbon atoms, which are unsubstituted or substituted with an alkyl group of 1 to 20 carbon atoms, and
in Formula 2,
R 1 is hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 10 carbon atoms.
3. The modified polymerization initiator of claim 1 , wherein
in Formula 1,
X is selected from substituents represented by the following Formula 1a to Formula 1c:
in Formula 1a to Formula 1c,
R 2 , R 3 , R 6 , R 8 and R 9 are each independently an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, a heteroalkyl group of 1 to 10 carbon atoms, a heteroalkenyl group of 2 to 10 carbon atoms, a heteroalkynyl group of 2 to 10 carbon atoms, a heterocycloalkyl group of 3 to 10 carbon atoms, or a heteroaryl group of 3 to 10 carbon atoms, where R 2 and R 3 , and R 8 and R 9 each may be connected with each other to form an aliphatic hydrocarbon ring of 5 to 20 carbon atoms, or an aromatic hydrocarbon ring of 6 to 20 carbon atoms, and each of R 2 , R 3 , R 6 , R 8 and R 9 is unsubstituted or substituted with a substituent comprising one or more heteroatoms selected from N, O and S atoms,
R 4 , R 5 and R 7 are each independently an alkylene group of 1 to 10 carbon atoms, the alkylene group being unsubstituted or substituted with an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, a heteroatom selected from N and O atoms or a substituent comprising the heteroatom, and
Z is one selected from N, O and S atoms, where if Z is O or S, R 6 is not present.
4. The modified polymerization initiator of claim 1 , wherein the modified polymerization initiator comprises one or more selected from the group consisting of a compound represented by the following Formula 3 and the isomers thereof:
in Formula 3,
X is the same as defined in Formula 1,
M is Na, K or Li, and
R 1 is hydrogen or an alkyl group of 1 to 10 carbon atoms.
5. The modified polymerization initiator of claim 4 , wherein the isomer is one or more selected from compounds represented in the following Formula 3-1 to Formula 3-3:
in Formula 3-1 to Formula 3-3,
X is the same as defined in Formula 1,
M is Na, K or Li, and
R 1 is hydrogen or an alkyl group of 1 to 10 carbon atoms.
6. The modified polymerization initiator of claim 1 , wherein the initiator comprises one or more selected from a dimer, a trimer and an oligomer of each of a compound represented by the following Formula 3 and the isomers thereof:
in Formula 3,
X is the same as defined in Formula 1,
M is Na, K or Li, and
R 1 is hydrogen or an alkyl group of 1 to 10 carbon atoms.
7. A modified conjugated diene-based polymer comprising a repeating unit derived from a conjugated diene-based monomer and a functional group derived from the modified polymerization initiator of claim 1 in at least one terminal, the modified polymerization initiator comprising one or more units derived from a compound represented by the following Formula 1 and a unit derived from a compound represented by the following Formula 2:
in Formula 1,
X is —NR a R b , —OR c , or —SR d , and
R a to R d are each independently an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkynyl group of 2 to 30 carbon atoms, a cycloalkyl group of 3 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, a heteroalkyl group of 1 to 30 carbon atoms, a heteroalkenyl group of 2 to 30 carbon atoms, a heteroalkynyl group of 2 to 30 carbon atoms, a heterocycloalkyl group of 2 to 30 carbon atoms, or a heteroaryl group of 3 to 30 carbon atoms, where each of R a to R d is unsubstituted or substituted with a substituent comprising one or more heteroatoms selected from N, O, S, Si and F atoms, and R a and R b may be connected with each other to form an aliphatic hydrocarbon ring of 5 to 20 carbon atoms, an aromatic hydrocarbon ring of 6 to 20 carbon atoms, or a heterocycle of 3 to 20 carbon atoms, which are unsubstituted or substituted with an alkyl group of 1 to 30 carbon atoms,
M-R 1 [Formula 2]
in Formula 2,
M is an alkali metal, and
R 1 is hydrogen, an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkynyl group of 2 to 30 carbon atoms, a cycloalkyl group of 5 to 30 carbon atoms, or an aryl group of 6 to 30 carbon atoms.