Modified butadiene-based polymer and modifier useful for preparing the same

Abstract

The present invention provides a modified butadiene-based polymer capable of enhancing dispersability of an inorganic filler when used in a rubber composition, and enhancing viscoelasticity, a tensile property and processibility of the rubber composition in a balanced way from an interaction with the inorganic filler, and a modifier useful for preparing the same.

Claims

1. A modified butadiene-based polymer as a modified polymer of a lanthanide rare earth element-catalyzed butadiene-based polymer, the polymer comprising: a modifier-derived functional group of the following Chemical Formula 1: ##STR00019## wherein, in Chemical Formula 1, A is a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms including one or more heteroatoms selected from the group consisting of N, S and O; R.sup.1 and R.sup.2 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of a linear or branched 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.sup.3 to R.sup.5 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms; m is an integer of 0 to 3; and n is an integer of 1 or 2, but when A is the hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 2.

2. The modified butadiene-based polymer of claim 1, wherein, in Chemical Formula 1, A is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a phenoxyalkyl group having 7 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms and -[R.sup.11O].sub.xR.sup.12, wherein, R.sup.11 is an alkylene group having 2 to 10 carbon atoms, R.sup.12 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 16 carbon atoms and an arylalkyl group having 7 to 16 carbon atoms, and x is an integer of 2 to 10.

3. The modified butadiene-based polymer of claim 1, wherein, in Chemical Formula 1, A is any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms and -[R.sup.11O].sub.xR.sup.12, wherein, R.sup.11 is an alkylene group having 2 to 10 carbon atoms, R.sup.12 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 16 carbon atoms and an arylalkyl group having 7 to 16 carbon atoms, and x is an integer of 2 to 10; R.sup.1 and R.sup.2 are each independently an alkylene group having 1 to 5 carbon atoms; R.sup.3 and R.sup.4 are each independently an alkyl group having 1 to 5 carbon atoms; R.sup.5 is an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms; m is an integer of 0 to 2; and n is an integer of 1 or 2, but when A is the alkyl group having 1 to 10 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms, the aryl group having 6 to 12 carbon atoms or the arylalkyl group having 7 to 12 carbon atoms, n is an integer of 2.

4. The modified butadiene-based polymer of claim 1, wherein the modifier includes any one or a mixture of two or more selected from the group consisting of 2-methoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate, 2-phenoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate, 2-methoxyethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate, 2-ethoxyethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate, ethyl 3 -(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate, 2-phenoxyethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate, 2-methoxyethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate, 2-(dimethylamino)ethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate, 2,5,8,11,14,17,20,23,26-nonaoxaoctacosan-28-yl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate, 2-(2-(2-(2-phenoxyethoxy)ethoxy)ethoxy)ethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate, 2-(dimethylamino)ethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate, 2-(2-(2-(2-phenoxyethoxy)ethoxy)ethoxy)ethyl 3-(bis(3-(cyclohexyl(triethoxy)lsilyl)methyl)amino)propanoate,2-methoxyethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate and ethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate.

5. The modified butadiene-based polymer of claim 1, wherein A is any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms and a phenoxyalkyl group having 7 to 12 carbon atoms; R.sup.1 and R.sup.2 are each independently an alkylene group having 1 to 5 carbon atoms; R.sup.3 and R.sup.4 are each independently an alkyl group having 1 to 5 carbon atoms; m is an integer of 0 or 1; and n is an integer of 2.

6. The modified butadiene-based polymer of claim 1, which is prepared by modifying a butadiene-based polymer having an active organic metal site obtained by polymerizing a butadiene-based monomer using a catalyst including a lanthanide rare earth element-containing compound with the modifier.

7. The modified butadiene-based polymer of claim 6, wherein the butadiene-based polymer having an active organic metal site is a neodymium-catalyzed butadiene-based polymer including a 1,3-butadiene monomer-derived repeating unit.

8. The modified butadiene-based polymer of claim 1, which has molecular weight distribution (Mw/Mn) of 2.5 to 3.5.

9. The modified butadiene-based polymer of claim 1, which has a weight average molecular weight of 510.sup.5 g/mol to 1.210.sup.6 g/mol, and a number average molecular weight of 1.510.sup.5 g/mol to 3.510.sup.5 g/mol.

10. The modified butadiene-based polymer of claim 1, which has Mooney viscosity of 40 to 70 at 100 C.

11. A method for preparing the modified butadiene-based polymer of claim 1 comprising: modifying by reacting a butadiene-based polymer having a lanthanide rare earth element-catalyzed active organic metal site with a modifier of the following Chemical Formula 1: ##STR00020## wherein, in Chemical Formula 1, A is a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms including one or more heteroatoms selected from the group consisting of N, S and O; R.sup.1 and R.sup.2 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of a linear or branched 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.sup.3 to R.sup.5 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms; m is an integer of 0 to 3; and n is an integer of 1 or 2, but when A is the hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 2.

12. The method for preparing the modified butadiene-based polymer of claim 11, further comprising: preparing the butadiene-based polymer having an active organic metal site by polymerizing a butadiene-based monomer in an organic solvent using a catalyst for polymerization including a lanthanide rare earth element-containing compound prior to the modifying.

13. The method for preparing the modified butadiene-based polymer of claim 12, wherein the catalyst for polymerization includes a lanthanide rare earth element-containing compound, an alkylating agent and a halogen compound.

14. The method for preparing the modified butadiene-based polymer of claim 12, wherein the lanthanide rare earth element-containing compound includes a neodymium compound of the following Chemical Formula 4: ##STR00021## wherein, in Chemical Formula 4, R.sub.a to R.sub.c, are each independently a hydrogen atom, or a linear or branched alkyl group having 1 o 12 carbon atoms.

15. The method for preparing the modified butadiene-based polymer of claim 12, wherein the lanthanide rare earth element-containing compound includes a neodymium compound in which, in Chemical Formula 1, R.sub.a is a linear or branched alkyl group having 6 to 12 carbon atoms, and R.sub.b, and R.sub.c, are each independently a linear or branched alkyl group having 2 to 8 carbon atoms.

16. The method for preparing the modified butadiene-based polymer of claim 12, wherein the catalyst for polymerization further includes a diene-based monomer.

17. The method for preparing the modified butadiene-based polymer of claim 11, wherein the butadiene-based polymer having an active organic metal site is an end activated polymer.

18. The method for preparing the modified butadiene-based polymer of claim 11, wherein the butadiene-based polymer including an active organic metal site is a neodymium-catalyzed butadiene-based polymer including a 1,3-butadiene monomer-derived repeating unit.

19. The modified butadiene-based polymer of claim 1, wherein, in Chemical Formula 1, A is selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a phenoxyalkyl group having 7 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms and -[R.sup.11O].sub.xR.sup.12, wherein, R.sup.11 is an alkylene group having 2 to 10 carbon atoms, R.sup.12 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 16 carbon atoms and an arylalkyl group having 7 to 16 carbon atoms, and x is an integer of 2 to 10.

Description

PREPARATION EXAMPLE 1

Preparation of 2-methoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate

(1) In a 50 ml round bottom flask, 10 ml of ethanol was added to dissolve 0.823 mmol of bis(3-triethoxysilylpropyl)amine (Gelest, Inc.), then 11.364 mmol of ethyleneglycol methyl ether acrylate was added thereto, and the result was stirried for 8 hours at room temperature (25 C.) under nitrogen atmosphere to be reacted. After the reaction was complete, the solvent in the reaction material of the result was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 11.538 mmol of 2-methoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate (i) of the following structure (yield 96.9%). The obtained compound was purified, and 1H and 13C Nuclear Magnetic Resonance spectroscopic spectra were observed.

(2) ##STR00006##

(3) .sup.1H-NMR (500 MHz, CDCl.sub.3) 4.21-4.19 (t, 2H), 3.81-3.77 (m, 12H), 3.57-3.56 (t, 2H), 3.36 (s, 3H), 2.79-2.76 (t, 2H), 2.47-2.44 (t, 2H), 2.40-2.37 (t, 4H), 1.54-1.47 (m, 4H), 1.22-1.19 (t, 18H), 0.57-0.54 (t, 4H); .sup.13C NMR (125 mHz, CDCl.sub.3) 172.8, 77.2, 77.0, 76.7, 63.3, 58.9, 56.8, 49.3, 32.4, 18.2, 7.9

PREPARATION EXAMPLE 2

Preparation of 2-phenoxyethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate

(4) In a 50 ml round bottom flask, 5 ml of ethanol was added to dissolve 5.744 mmol of (N-cyclohexylaminomethyl)triethoxysilane (Gelest, Inc.), then 5.744 mmol of 2-phenoxyethyl acrylate (TCI Co., Ltd.) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 4.990 mmol of 2-phenoxyethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate (ii) (yield 91.4%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-phenoxyethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate are as follows.

(5) ##STR00007##

(6) .sup.1H-NMR (500 MHz, CDCl.sub.3) 7.49-7.23 (m, 2H), 6.97-6.86 (m, 3H), 4.40-4.36 (m, 2H), 4.16-4.03 (m, 4H), 3.87-3.81 (m, 3H), 2.78-2.75 (m, 2H), 2.50-2.41 (m, 4H), 2.17-2.11 (m, 3H), 1.72-1.56 (m, 7H), 1.26-1.16 (m, 12H)

PREPARATION EXAMPLE 3

Preparation of 2-methoxyethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate

(7) In a 50 ml round bottom flask, 5 ml of ethanol was added to dissolve 8.468 mmol of (N-cyclohexylaminomethyl)triethoxysilane (Gelest, Inc.), then 8.468 mmol of ethylene glycol methyl ether acrylate (Acros Organics) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 8.19 mmol of 2-methoxyethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate (iii) (yield 96.7%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-methoxyethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate are as follows.

(8) ##STR00008##

(9) .sup.1H-NMR (500 MHz, CDCl.sub.3) 4.18-4.16 (t, 2H), 3.84-3.79 (m, 3H), 3.55-3.54 (t, 2H), 3.35 (s, 3H), 2.76-2.73 (m, 2H), 2.48-2.45 (m, 4H), 2.14-2.08 (m, 3H), 1.73-1.71 (m, 7H), 1.22-1.18 (m, 13H)

PREPARATION EXAMPLE 4

Preparation of 2-(dimethylamino)ethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate

(10) In a 50 ml round bottom flask, 5 ml of ethanol was added to dissolve 6.586 mmol of (N-cyclohexylaminomethyl)triethoxysilane (Gelest, Inc.), then 6.586 mmol of 2-(dimethylamino)ethyl acrylate (Sigma-Aldrich Co. LLC.) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 6.24 mmol of 2-(dimethylamino)ethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate (iv) (yield 94.8%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-(dimethylamino)ethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate are as follows.

(11) ##STR00009##

(12) .sup.1H-NMR (500 MHz, CDCl.sub.3) 4.16-4.08 (m, 3H), 2.76-2.73 (m, 2H), 2.53-2.50 (m, 3H), 2.47-2.41 (m, 3H), 2.25-2.23 (m, 10H), 2.11-2.08 (t, 2H), 1.73-1.72 (m, 9H), 1.54-1.47 (m, 4H), 1.24-1.16 (m, 10H)

PREPARATION EXAMPLE 5

Preparation of 2,5,8,11,14,17,20,23,26-nonaoxaoctacosan-28-yl 3-(bis(3-(triethoxysily)propyl)amino)propanoate

(13) In a 50 ml round bottom flask, 5 ml of ethanol was added to dissolve 2.279 mmol of bis(3-triethoxysilylpropyl)amine (Gelest, Inc.), then 2.279 mmol of poly(ethylene glycol) methyl ether acrylate (Sigma-Aldrich Co. LLC., Mn 480) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 2.13 mmol of 2,5,8,11,14,17,20,23,26-nonaoxaoctacosan-28-yl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate (v) (yield 93.5%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2,5,8,11,14,17,20,23,26-nonaoxaoctacosan-28-yl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate are as follows.

(14) ##STR00010##

(15) .sup.1H-NMR (500 MHz, CDCl.sub.3) 4.17-4.15 (t, 2H), 3.78-3.73 (m, 12H), 3.60-3.59 (m, 32H), 3.50-3.48 (m, 2H), 3.32 (s, 3H), 2.74-2.71 (m, 2H), 2.37-2.34 (t, 6H), 1.50-1.43 (m, 4H), 1.19-1.15 (t, 18H), 0.54-0.50 (m, 4H)

PREPARATION EXAMPLE 6

Preparation of 2-(2-(2-(2-phenoxyethoxy)ethoxy)ethoxy)ethyl 3-(bis(3-(triethoxysilyl)propyl) amino)propanoate

(16) In a 50 ml round bottom flask, 5 ml of ethanol was added to dissolve 2.279 mmol of bis(3-triethoxysilylpropyl)amine, then 2.279 mmol of poly(ethylene glycol) phenyl ether acrylate (Sigma-Aldrich, Co. LLC. Mn 324) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 2.15 mmol of 2-(2-(2-(2-phenoxyethoxy)ethoxy)ethoxy)ethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate (vi) (yield 93.7%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-(2-(2-(2-phenoxyethoxy)ethoxy)ethoxy)ethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate are as follows.

(17) ##STR00011##

(18) .sup.1H-NMR (500 MHz, CDCl.sub.3) 7.26-7.22 (t, 2H), 6.92-6.87 (m, 3H), 4.20-4.17 (t, 2H), 4.11-4.07 (m, 3H), 3.84-3.82 (m, 2H), 3.81-3.75 (m, 10H), 3.71-3.60 (m, 10H), 2.77-2.74 (t, 2H), 2.39-2.36 (t, 6H), 1.52-1.46 (m, 4H), 1.21-1.78 (m, 18H), 0.57-0.53 (m, 4H)

PREPARATION EXAMPLE 7

Preparation of 2-phenoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate

(19) In a 50 ml round bottom flask, 5 ml of ethanol was added to dissolve 4.557 mmol of bis(3-triethoxysilylpropyl)amine (Gelest, Inc.), then 4.557 mmol of 2-phenoxyethyl acrylate (TCI Co., Ltd.) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 4.17 mmol of 2-phenoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate (vii) (yield 91.6%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-phenoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate are as follows.

(20) ##STR00012##

(21) .sup.1H-NMR (500 MHz, CDCl.sub.3) 7.26-7.23 (m, 2H), 6.94-6.84 (m, 3H), 4.39-4.37 (t, 2H), 4.14-4.12 (t, 3H), 3.79-3.75 (m, 12H), 2.78-2.75 (t,2H), 2.46-2.43 (t, 2H), 2.39-2.36 (t, 4H), 1.63-1.43 (m, 4H), 1.20-1.17 (m, 18H), 0.56-0.52 (m, 4H)

PREPARATION EXAMPLE 8

Preparation of 2-methoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate

(22) In a 50 ml round bottom flask, 5 ml of ethanol was added to dissolve 4.557 mmol of bis(3-triethoxysilylpropyl)amine (Gelest, Inc.), then 4.557 mmol of ethylene glycol methyl ether acrylate (Acros Organics) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 4.430 mmol of 2-methoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate (i) (yield 97.3%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-methoxyethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate are as follows.

(23) .sup.1H-NMR (500 MHz, CDCl.sub.3) 4.21-4.19 (t, 2H), 3.81-3.77 (m, 12H), 3.57-3.56 (t, 2H), 3.36 (s, 3H), 2.79-2.76 (t, 2H), 2.47-2.44 (t, 2H), 2.40-2.37 (t, 4H), 1.54-1.47 (m, 4H), 1.22-1.19 (t, 18H), 0.57-0.54 (t, 4H)

PREPARATION EXAMPLE 9

Preparation of 2-(dimethylamino)ethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate

(24) In a 50 ml round bottom flask, 5 ml of ethanol was added to dissolve 4.5573 mmol of bis(3-triethoxysilylpropyl)amine (Gelest, Inc.), then 4.55764 mmol of 2-(dimethylamino)ethyl acrylate (Sigma-Aldrich Co. LLC.) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 4.18 mmol of 2-(dimethylamino)ethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate (viii) (yield 91.7%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-(dimethylamino)ethyl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate are as follows.

(25) ##STR00013##

(26) .sup.1H-NMR (500 MHz, CDCl.sub.3) 4.12-4.09 (t, 2H), 3.78-3.74 (m, 12H), 2.75-2.73 (t, 2H), 2.51-2.49 (t, 3H), 2.42-2.40 (t, 2H), 2.37-2.34 (t, 3H), 2.22-2.19 (m, 6H), 1.54-1.44 (m, 4H), 1.18-1.15 (m, 18H), 0.52-0.50 (m, 4H)

PREPARATION EXAMPLE 10

Preparation of 2-(2-(2-(2-phenoxyethoxy)ethoxy)ethoxy)ethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate

(27) In a 50 ml round bottom flask, 50 ml of ethanol was added to dissolve 3.449 mmol of (N-cyclohexylaminomethyl)triethoxysilane, then 3.449 mmol of poly(ethylene glycol) phenylether acrylate (Sigma-Aldrich Co. LLC., Mn 324) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 3.13 mmol of 2-(2-(2-(2-phenoxyethoxy)ethoxy)ethoxy)ethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate (ix) (yield 91.1%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-(2-(2-(2-phenoxyethoxy)ethoxy)ethoxy)ethyl 3-(cyclohexyl((triethoxysilyl)methyl)amino)propanoate are as follows.

(28) ##STR00014##

(29) .sup.1H-NMR (500 MHz, CDCl.sub.3) 7.26-7.24 (m, 2H), 6.93-6.88 (m, 3H), 4.18-4.16 (m, 2H), 4.11-4.09 (m, 3H), 3.85-3.80 (m, 6H), 3.71-3.61 (m, 12H), 2.76-2.72 (m, 2H), 2.50-2.39 (m, 3H), 2.10-2.09 (m, 2H), 1.74-1.72 (m, 4H), 1.58-1.59 (m, 1H) 1.24-1.15 (m, 12H), 1.03-1.00 (m, 1H)

PREPARATION EXAMPLE 11

Preparation of 2-methoxyethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate

(30) In a 100 ml round bottom flask, 20 ml of ethanol was added to dissolve 73.03 mmol of bis(methyldiethoxysilylpropyl)amine (Gelest, Inc.), then 73.03 mmol of ethylene glycol methyl ether acrylate (Acros Organics) was added thereto, and the result was stirred for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 120 C. to obtain 71.77 mmol of 2-methoxyethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate (x) (yield 98.327%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified 2-methoxyethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate are as follows.

(31) ##STR00015##

(32) .sup.1H-NMR (500 MHz, CDCl.sub.3) 4.23-4.21 (t, 2H), 3.78-3.74 (m, 8H), 3.60-3.58 (t, 2H), 3.39 (s, 3H), 2.81-2.78 (t, 2H), 2.49-2.46 (t, 2H), 2.42-2.39 (t, 3H), 1.51-1.45 (m, 5H), 1.23-1.20 (t, 18H), 0.57-0.54 (t, 4H), 0.12 (s, 6H)

PREPARATION EXAMPLE 12

Preparation of ethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate

(33) In a 100 ml round bottom flask, 20 ml of ethanol was added to dissolve 72.99 mmol of bis(methyldiethoxysilylpropyl)amine (Gelest, Inc.), then 72.99 mmol of ethyl acrylate (Sigma-Aldrich Co. LLC.) was added thereto, and the result was stirried for 8 hours at room temperature under nitrogen atmosphere. After the reaction was complete, the solvent was removed under vacuum, and the result was vacuum distilled at 80 C. to obtain 72.18 mmol of ethyl 3-(bis(3-(diethyoxy(methyl)silyl)propyl)amino)propanoate (xi) (yield 98.9%). 1H Nuclear Magnetic Resonance spectroscopic data of the purified ethyl 3-(bis(3-(diethoxy(methyl)silyl)propyl)amino)propanoate are as follows.

(34) ##STR00016##

(35) .sup.1H-NMR (500 MHz, CDCl.sub.3) 4.14-4.10 (m, 2H), 3.78-3.74 (m, 8H), 2.80-2.79 (t, 2H), 2.43-2.39 (m, 6H), 1.52-1.54 (m, 4H), 1.27-1.20 (m, 15H), 0.58-0.54 (t, 4H), 0.11 (s, 6H)

EXAMPLE 1-1

Preparation of Modified Butadiene Polymer

(36) Under nitrogen atmosphere, 4.2 kg of hexane and 500 g of 1,3-butadiene were placed in a 15 L reactor, and the temperature was raised to 70 C. A catalyst for polymerization prepared through a reaction of 1.0 mmol of neodymium versatate (NdV) hexane solution, 9.2 mmol of diisobutylaluminum hydride (DIBAH), 2.4 mmol of diethylaluminum chloride and 33 mmol of 1,3-butadiene was added to the 15 L reactor, and the result was polymerized for 60 minutes. A conversion rate of the 1,3-butadiene to polybutadiene was approximately 100%.

(37) After completing the polymerization reaction of the 1,3-butadiene, a hexane solution including 7.0 mmol of an aminosilane-based modifier was added to the above polymerized solution, and the result was reacted for 30 minutes at 70 C. Through the addition of a hexane solution including 1.0 g of a reaction terminating agent and a hexane solution including 1.0 g of an antioxidant, a modified butadiene polymer was prepared.

EXAMPLES 1-2 to 1-12

Preparation of Modified Butadiene Polymer

(38) Modified butadiene polymers were prepared in the same manner as in Example 1-1 except that the modifiers prepared in Preparation Examples 2 to 12 were each used as the modifier in Example 1-1.

EXAMPLES 1-13

Preparation of Modified Butadiene Polymer

(39) A modified butadiene polymer was prepared in the same manner as in Example 1-1 except that Nd(2,2-dihexyl decanoate).sub.3 (xii) of the following structure was used instead of the neodymium versatate in the 1,3-butadiene polymerization reaction in Example 1-1.

(40) ##STR00017##

EXAMPLES 1-14 to 1-24

Preparation of Modified Butadiene Polymer

(41) Modified butadiene polymers were prepared in the same manner as in Example 1-1 except that Nd(2,2-dihexyl decanoate).sub.3 was used instead of the neodymium versatate in the 1,3-butadiene polymerization reaction, and the modifiers prepared in Preparation Examples 2 to 12 were each used instead of the modifier in Example 1-1.

COMPARATIVE EXAMPLE 1-1

(42) As non-modified ND-BR, Nd60 (manufactured by Kumho Petrochemical) was used.

COMPARATIVE EXAMPLE 1-2

(43) As modified ND-BR, BR54 (manufactured by JSR Corporation) was used.

COMPARATIVE EXAMPLE 1-3

Preparation of Butadiene Polymer

(44) A butadiene polymer was prepared in the same manner as in Example 1-1 except that no modifier was used.

COMPARATIVE EXAMPLE 1-4

Preparation of Modified Butadiene Polymer

(45) A modified butadiene polymer was prepared in the same manner as in Example 1-1 except that 3-glycidoxypropyltrimethoxysilane (GPMOS) (xiii) of the following structure was used as the modifier.

(46) ##STR00018##

Test Example 1

(47) For the polymers prepared in Example 1-1, 1-13 and Comparative Examples 1-1 to 1-4, the modification status, the weight average molecular weight (Mw), the number average molecular weight (Mn), the molecular weight distribution (MWD), and the Mooney viscosity (MV) were each measured as follows.

(48) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (MWD): measured using gel permeation chromatography for the polymers prepared in Example 1-1 and Comparative Examples 1-1 to 1-4.

(49) Mooney viscosity (MV) (ML1+4, @100 C.) (MU): measured using a Large Rotor of MV2000E manufactured by Monsanto under a condition of Rotor Speed 20.02 rpm at 100 C. Herein, the used sample was left unattended for 30 minutes or longer at room temperature (233 C.), 273 g thereof was collected, and inside a die cavity is filled with the sample, and Mooney viscosity was measured while operating a Platen.

(50) TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Comparative Example Example Example Example Example Example 1-1 1-2 1-3 1-4 1-1 1-13 Type of Modifier Nd60 BR54 GPMOS Compound Compound (Kumho (JSR (i) (i) Petrochemical) .sup.1) Corporation) .sup.2) Modification Status Non- Modified Non- Modified Modified Modified modified modified GPC Mn (10.sup.5 2.56 N/A 3.03 2.99 3.00 3.15 Result g/mol) (gel formed) Mw (10.sup.5 8.99 9.45 10.31 9.57 9.52 g/mol) Mw/Mn 3.51 3.11 3.45 3.18 3.02 MV (ML1 + 4, @100 C.) (MU) 62.9 69.9 59.8 64.7 62.8 61.9 In Table 1, 1) and 2) are polymers, N/A means unmeasurable.

(51) In the test results, weight average, number average molecular weights and molecular weight distribution measured by GPC were difficult to be measured for the butadiene polymer of Comparative Example 1-2 using an existing modifier due to gelation.

(52) Meanwhile, the modified butadiene-based polymers of Examples 1-1 and 1-13 modified using the modifiers according to the present invention exhibited narrower molecular weight distribution (Mw/Mn) compared to the modified butadiene-based polymer of Comparative Example 1-4 prepared using GPMOS as the modifier, and the modified butadiene-based polymer of Example 1-13 prepared using Nd(2,2-dihexyl decanoate).sub.3 as the Nd-based catalyst exhibited far narrower molecular weight distribution. From such a test result, it may be predicted that a modified butadiene copolymer using the modifier according to the present invention is capable of exhibiting improved effects in terms of viscoelasticity and a tensile property in a balanced way.

EXAMPLE 2-1

Preparation of Rubber Composition

(53) A rubber composition was prepared by mixing butadiene rubber in 100 parts by weight, silica in 70 parts by weight, bis(3-triethoxysilylpropyl)tetrasulfide in 6 parts by weight as a silane coupling agent, process oil in 30 parts by weight, an antiaging agent (TMDQ) in 4 parts by weight, zinc oxide (ZnO) in 3 parts by weight and stearic acid in 2 parts by weight, with respect to 100 parts by weight of the modified butadiene-based polymer prepared in Example 1-1. To the prepared rubber composition, 2 parts by weight of sulfur powder, 2 parts by weight of a vulcanization accelerator (CZ) and 2 parts by weight of a vulcanization accelerator (DPG) were added, and the result was vulcanized for t90 minutes at 150 C. to prepare a rubber specimen. Herein, as the silica, silica having a nitrogen adsorption specific surface area of 175 m.sup.2/g and a CTAB adsorption value of 160 m.sup.2/g was used.

EXAMPLES 2-2 to 2-24

Preparation of Rubber Composition

(54) Rubber compositions were prepared in the same manner as in Example 2-1 except that each of the modified butadiene-based polymers prepared in Examples 1-2 to 1-24 was used instead of the modified butadiene-based polymer of Example 1-1.

COMPARATIVE EXAMPLES 2-1 to 2-4

Preparation of Rubber Composition

(55) Rubber compositions were prepared in the same manner as in Example 2-1 except that the polymers prepared in Comparative Examples 1-1 to 1-4 were used instead of the modified butadiene-based polymer prepared in Example 1-1.

Test Example 2

(56) For the rubber compositions of Examples 2-1 and 2-13 and Comparative Examples 2-1 to 2-4, a vulcanizing property and tensile properties were evaluated.

(57) In detail, for the prepared rubber compositions, a vulcanizing property, viscoelasticity, and tensile properties including hardness, 300% modulus, tensile strength, elongation and toughness strength were each measured. Among these, viscoelasticity, 300% modulus, tensile strength, elongation and toughness strength were indexed with the measurement value of Comparative Example 3 as 100. The results are shown in the following Table 2.

(58) Vulcanizing property (t90): maximum torque (MH) value and time taken for 90% vulcanization (t90) were measured when vulcanized for 50 minutes at 150 C. using a moving die rheometer (MDR).

(59) Viscoelasticity (tan @60 C.): viscoelasticity coefficient (tan ) at 60 C. was measured with 10 Hz frequency and 3% strain rate.

(60) Hardness (Type A): type A harness was measured in accordance with the ASTM D2240.

(61) Tensile strength (kg.Math.f/cm.sup.2), 300% modulus (kg.Math.f/cm.sup.2), elongation (%): each of the rubber compositions was vulcanized for t90 minutes at 150 C., and tensile strength of the vulcanized material, modulus at 300% elongation, and elongation of the vulcanized material when fractured were measured in accordance with the ASTM D412.

(62) Toughness: area under the tensile graph when fractured was measured.

(63) TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Comparative Example Example Example Example Example Example 2-1 2-2 2-3 2-4 2-1 2-13 Type of Polymer Comparative Comparative Comparative Comparative Example Example Example Example Example Example 1-1 1-13 1-1 1-2 1-3 1-4 Vulcanizing t90 (minutes) 12.16 12.28 11.45 11.71 10.09 10.01 Property Visco- tan @60 C. 92 97 100 109 112 117 elasticity (DMTS, 10 Hz) 3% strain Tensile Hardness 61 59 61 62 62 62 Property (Type A) 300% Modulus 98 98 100 110 122 128 (Kg .Math. f/cm.sup.2) Tensile 95 97 100 110 115 118 Strength (Kg .Math. f/cm.sup.2) Elongation 98 98 100 102 102 102 (%) Toughness 92 95 100 114 125 129 (Kg .Math. f/cm.sup.2)

(64) The rubber compositions of Example 2-1 including the modified butadiene-based polymer of Example 1-1; and Example 2-13 including the modified butadiene-based polymer of Example 1-13, both modified using the modifier according to the present invention, exhibited significantly improved effects compared to the rubber compositions including Comparative Examples 1-1 and 1-3, which are non-modified butadiene-based polymers, and Comparative Examples 1-2 and 1-4 using existing modifiers. From the above, it was seen that the rubber composition including the modified butadiene-based polymer of Example 1-1 exhibited more excellent fuel efficiency properties.

(65) In addition, in the hardness property among the tensile properties, the rubber compositions including the polymers of Comparative Examples 1-1 to 1-4, or Example 1-1 and Example 1-13 exhibited an equal level of hardness regardless of modification. However, in 300% modulus, tensile strength, elongation and a toughness property, the rubber compositions including the modified butadiene copolymers of Example 1-1 and Example 1-13 exhibited significantly improved effects compared to the rubber compositions including Comparative Examples 1 and 3, which are non-modified butadiene-based polymers, and Comparative Examples 2-2 and 2-4 using existing modifiers.