Modifier, Modified Conjugated Diene-Based Polymer and Method for Preparing the Same

Abstract

A modifier useful for modifying a polymer providing a functional group having affinity with a filler, particularly, a silica-based filler is provided. A modified conjugated diene-based polymer including a functional group derived from the modifier having excellent affinity with a filler and improved compounding properties, and a method for preparing the same are also provided.

Claims

1. A modifier represented by the following Formula 1: ##STR00014## wherein, X is an alkylene group of 1 to 20 carbon atoms, a cycloalkylene group of 5 to 20 carbon atoms or an arylene group of 6 to 20 carbon atoms, L.sub.1 and L.sub.2 are each independently an alkylene group of 1 to 20 carbon atoms, a cycloalkylene group of 5 to 20 carbon atoms or an arylene group of 6 to 20 carbon atoms, R.sub.1 to R.sub.4 are each independently an alkyl group of 1 to 20 carbon atoms, and a and b are each independently an integer of 1 to 3.

2. The modifier according to claim 1, wherein X is an alkylene group of 1 to 12 carbon atoms, L.sub.1 and L.sub.2 are each independently an alkylene group of 1 to 12 carbon atoms, R.sub.1 to R.sub.4 are each independently an alkyl group of 1 to 12 carbon atoms, and a and b are each independently an integer of 2 or 3.

3. The modifier according to claim 1, wherein X is an alkylene group of 1 to 4 carbon atoms, L.sub.1 and L.sub.2 are each independently an alkylene group of 1 to 6 carbon atoms, R.sub.1 to R.sub.4 are each independently an alkyl group of 1 to 4 carbon atoms, and a and b are each independently an integer of 2 or 3.

4. The modifier according to claim 1, wherein the modifier represented by Formula 1 is a compound represented by the following Formula 1-1: ##STR00015##

5. A modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following Formula 1: ##STR00016## wherein, X is an alkylene group of 1 to 20 carbon atoms, a cycloalkylene group of 5 to 20 carbon atoms or an arylene group of 6 to 20 carbon atoms, L.sub.1 and L.sub.2 are each independently an alkylene group of 1 to 20 carbon atoms, a cycloalkylene group of 5 to 20 carbon atoms or an arylene group of 6 to 20 carbon atoms, R.sub.1 to R.sub.4 are each independently an alkyl group of 1 to 20 carbon atoms, and a and b are each independently an integer of 1 to 3.

6. The modified conjugated diene-based polymer according to claim 5, wherein a number average molecular weight is from 100,000 to 1,000,000 g/mol.

7. The modified conjugated diene-based polymer according to claim 5, wherein a weight average molecular weight is from 300,000 to 1,500,000 g/mol.

8. The modified conjugated diene-based polymer according to claim 5, wherein molecular weight distribution is from 1.1 to 4.0.

9. The modified conjugated diene-based polymer according to claim 5, wherein a Mooney viscosity at 100° C. is from 20 to 100.

10. A method for preparing a modified conjugated diene-based polymer, comprising: polymerizing a conjugated diene-based monomer in a presence of a catalyst composition comprising a neodymium compound in a hydrocarbon solvent to prepare an active polymer; and reacting the active polymer and a modifier represented by the following Formula 1: ##STR00017## wherein, X is an alkylene group of 1 to 20 carbon atoms, a cycloalkylene group of 5 to 20 carbon atoms or an arylene group of 6 to 20 carbon atoms, L.sub.1 and L.sub.2 are each independently an alkylene group of 1 to 20 carbon atoms, a cycloalkylene group of 5 to 20 carbon atoms or an arylene group of 6 to 20 carbon atoms, R.sub.1 to R.sub.4 are each independently an alkyl group of 1 to 20 carbon atoms, and a and b are each independently an integer of 1 to 3.

11. The method according to claim 10, wherein the neodymium compound is from 0.1 to 0.5 mmol based on 100 g of the conjugated diene-based monomer.

12. The method according to claim 10, wherein the modifier represented by Formula 1 is from 1 to 20 mol based on 1 mol of the neodymium compound.

13. The method according to claim 10, wherein the neodymium compound is a compound represented by the following Formula 4: ##STR00018## wherein, R.sub.a to R.sub.c are each independently hydrogen or an alkyl group of 1 to 12 carbon atoms, where R.sub.a to R.sub.c are not hydrogen at the same time.

14. The method according to claim 10, wherein the polymerization is performed at a temperature of 20 to 200° C.

Description

EXAMPLES

[0153] Hereinafter, the present invention will be described in more detail according to examples. However, the following examples are merely presented to exemplify the present invention, and the scope of the present invention is not limited thereto.

PREPARATION OF MODIFIER

Preparation Example 1

[0154] ##STR00010##

[0155] To a 250 ml, dried round-bottom flask (RBF), 10 g (50 mmol) of dibromopropane and 110 g (250 mmol) of (3-aminopropyl)triethoxysilane were put and reacted at 100° C. for 4 hours. After finishing the reaction, the temperature was lowered to room temperature, 500 ml of hexane was injected for dilution, and the resultant product was filtered. The filtrates thus obtained were collected and concentrated. The mixture thus concentrated was distilled in vacuum at 140° C., and an excessive amount of (3-aminopropyl)triethoxysilane was removed to obtain 24 g (>99%) of N.sup.1,N.sup.3-bis(3-triethoxysilyl)propyl)propane-1,3-diamine.

[0156] To a 100 ml, dried RBF, 2.9 g (6 mmol) of N.sup.1, N.sup.3-bis(3-triethoxysilyl)propyl)propane-1,3-diamine obtained above, and 14.4 mmol of acryloyl chloride were put and dissolved in DCM (30 ml). At 0° C., 15.6 mmol of triethylamine was added dropwisely and reacted at room temperature for 2 hours. After finishing the reaction, MTBE (30 ml) was injected for dilution, and the resultant product was filtered. The filtrates were collected and concentrated to obtain a modifier (3.3 g, 92%).

[0157] .sup.1H NMR(500 MHz, CDCl.sub.3): δ6.62-6.57(m, 2 H), 6.38-6.29(m, 2 H), 5.70-5.64(m, 2 H), 3.82(q, J=7.0 Hz, 12 H), 3.42-3.31(m, 8 H), 1.85(q, J=7.5 Hz, 2 H), 1.69-1.65(m, 4H), 1.23(t, J=7.0 Hz, 18 H), 0.62-0.55(m, 4 H)

Comparative Preparation Example 1

[0158] ##STR00011##

[0159] To a 250 ml, dried RBF, 5 g (58 mmol) of piperazine and 24 g (174 mmol) of potassium carbonate were put and dissolved in toluene (50 ml). At 0° C., 139 mmol of acryloyl chloride was added dropwisely and reacted at room temperature overnight. After finishing the reaction, a solid material was filtered, and filtrates were separately collected and concentrated to obtain the modifier (8.8 g, 78%).

Comparative Preparation Example 2

[0160] ##STR00012##

[0161] 1) Preparation of N.sup.1-methyl-N.sup.3-(3-(trimethoxysilyl)propyl)propan-1,3-diamine

[0162] In a 250 ml, dried RBF, to 10 g (113 mmol) of an N-methyl-1,3-diaminopropane solution, 33.7 g (170 mmol) of (3-chloropropyl)trimethoxysilane was injected and reacted at 90° C. for 6 hours. After finishing the reaction, 100 ml of toluene was added, and the solid fraction thus produced was filtered by a filter. After concentrating under a reduced pressure, through distillation in vacuum, N.sup.1-methyl-N.sup.3-(3-(trimethoxysilyl)propyl)propan-1,3-diamine was obtained (25.5 g, 90%).

[0163] 2) Preparation of N-methyl-N-(3-(N-(3-(trimethoxysilyl)propyl)acrylamido)propyl)acrylamide

[0164] To a 250 ml, dried RBF, 27.7 g (102 mol) of N.sup.1-methyl-N.sup.3-(3-(trimethoxysilyl)propyl)propan-1,3-diamine, and 25.8 g (225 mol) of triethylamine were put and dissolved in 100 ml of dichloromethane. At 0° C., 128 mmol of acryloyl chloride was slowly added dropwisely and reacted at room temperature for 3 hours. After finishing the reaction, 100 ml of hexane was added, a solid fraction was precipitated and filtered. The filtrate was concentrated to obtain the modifier (32.2 g, 88%).

Comparative Preparation Example 3

[0165] ##STR00013##

[0166] To a 250 ml, dried RBF, 4 g (46 mmol) of 1-methylimidazolidine and 4.4 g (43 mol) of triethylamine were put and dissolved in 30 ml of acetonitrile. 10.7 g (54 mmol) of (3-chloropropyl)trimethoxysilane was injected and reacted at 120° C. overnight. After finishing the reaction, the solvent was removed under a reduced pressure, 50 ml of hexane was injected and stirred. A solid was filtered using a filter, a hexane layer was concentrated to obtain the modifier (8.8 g, 77%).

PREPARATION OF MODIFIED CONJUGATED DIENE-BASED POLYMER

Example 1

[0167] To a 6 L, well-dried autoclave reactor, n-hexane (2700 g) and 1,3-butadiene (300 g) were put, and the internal temperature of the reactor was elevated to 60° C. A catalyst composition prepared by mixing a neodymium compound (neodymium versatate, NdV), diisobutylaluminum hydride (DIBAH), diethylalminum chloride and a small amount of 1,3-butadiene (1,3-BD) in a molar ratio of 1:9.7:2.5:34.7 was injected in a ratio of 0.18 mmol of neodymium compound/100 g of 1,3-butadiene, and polymerized for 30 minutes while stirring at 300 rpm.

[0168] After that, the modifier represented by Formula 1-1 of Preparation Example 1 was injected into the reactor (in a molar ratio of modifier:NdV =3.0:1.0), and modification reaction was performed for 15 minutes.

[0169] After finishing the modification reaction, polyoxyethylene glycol phosphate (0.2 phr) as a reaction quenching agent, and 2,6-di-t-butyl-p-cresol (1.0 phr) as an antioxidant were injected to terminate the reaction, and solvents were removed through steam stripping. Then, remaining solvents and water were removed by roll drying to prepare a modified butadiene polymer.

Example 2

[0170] A modified butadiene polymer was prepared by the same method in Example 1 except for changing the reaction conditions as in Table 1 below.

Comparative Example 1

[0171] A modified butadiene polymer was prepared by the same method in Example 1 except for changing the reaction conditions as in Table 1 below.

Comparative Example 2

[0172] GND-45 (LG Chem, Co.) was used as an unmodified butadiene polymer.

Comparative Example 3

[0173] CB22 (Arlanxeo Co.) was used as an unmodified butadiene polymer.

Comparative Examples 4 to 6

[0174] Modified butadiene polymers were prepared by the same method in Example 1 except for changing the reaction conditions as in Table 1 below.

TABLE-US-00001 TABLE 1 Comparative Example Example 4 5 6 1 2 Comparative Comparative Comparative Preparation Preparation Preparation Preparation Preparation Division Example Example 1 2 3 Example Example Example Modifier 1 1 — — — 1 2 3 NdV 0.18 0.24 0.16 — — 0.28 0.18 0.18 (mmol/1,3- BD 100 g) Molar 3.0:1.0 3.5:1.0 — — — 5.2:1.0 6.0:1.0 6.0:1.0 ratio of modifier: NdV

Experimental Example 1

[0175] With respect to the polymers of the Examples and the Comparative Examples, physical properties were measured according to the methods below, and the results are shown in Table 1.

[0176] (1) Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn) and Molecular Weight Distribution (MWD)

[0177] Each polymer was dissolved in tetrahydrofuran (THF) for 30 minutes under 40° C. conditions, and then loaded on gel permeation chromatography (GPC) and flown. In this case, two columns of PLgel Olexis and one column of PLgel mixed-C (trade name, Polymer Laboratories Co.) were used in combination. Also, newly replaced columns were all mixed bed type columns, and polystyrene was used as a gel permeation chromatography (GPC) standard material.

[0178] (2) Mooney Viscosity (RP, Raw polymer)

[0179] The Mooney viscosity (ML1+4, @100° C.) (MU) was measured by using Large Rotor of MV2000E of Monsanto Co. at a rotor speed of 2±0.02 rpm at 100° C. A specimen used was stood at room temperature (23±5° C.) for 30 minutes or more, and 27±3 g of the specimen was collected and put in a die cavity, and then, Platen was operated, and the Mooney viscosity was measured while applying torque.

[0180] (3) Modification Ratio

[0181] The modification ratio was calculated using a chromatogram obtained from the measurement of chromatography. Particularly, each polymer was dissolved in tetrahydrofuran (THF) under 40° C. conditions to prepare a specimen, and each specimen was injected into gel permeation chromatography, tetrahydrofuran was flown as an eluent to obtain a chromatogram, and from the chromatogram thus obtained, the modification ratio was calculated by Mathematical Formula 1 below.

Modification ratio (%)=[(peak area of derived unit of conjugated diene-based monomer coupled with functional group derived from modifier)/(total peak area of modified conjugated diene-based polymer)]×100  [Mathematical Formula 1]

TABLE-US-00002 TABLE 2 Example Comparative Example Division 1 2 1 2 3 4 5 6 GPC Mn (×10.sup.5 2.71 2.59 2.53 2.30 3.15 2.45 2.61 2.49 Results g/mol) Mw (×10.sup.5 7.91 7.70 6.73 6.66 7.63 8.02 6.63 5.78 g/mol) MWD (Mw/Mn) 2.92 2.97 2.66 2.89 2.42 3.27 2.54 2.32 Mooney viscosity 70 66 43 44 63 69 62 42 (RP) (M.sub.1+4, @ 100° C.) (MU) Modification ratio 61 63 — — — 38 41 5 (%)

[0182] As shown in Table 2 above, it was confirmed that the modified butadiene polymers of Examples 1 and 2, prepared using the modifier represented by Formula 1 according to the present invention showed high modification ratios and were prepared into structures including a large number of functional groups derived from the modifier represented by Formula 1.

Experimental Example 2

[0183] With respect to 100 parts by weight of each polymer of the Examples and the Comparative Examples, 95 parts by weight of silica (7000GR), 12.8 parts by weight of carbon black (X-50S), 40.0 parts by weight of a process oil (TDAE OIL), 3.0 parts by weight of zinc oxide (ZnO), 2.0 parts by weight of stearic acid, 2.0 parts by weight of an antiaging agent (6PPD), 1.5 parts by weight of an antioxidant (TMQ), and 2.0 parts by weight of wax were compounded to prepare each rubber composition.

[0184] Thereafter, 1.5 parts by weight of sulfur, 1.25 parts by weight of CBS, and 1.5 parts by weight of a vulcanization accelerator (DPG) were added to each rubber composition and gently mixed at 50° C. for 1.5 minutes at 50 rpm and then, a vulcanized mixture compound in a sheet shape was obtained using a roll of 50° C. The vulcanized mixture compound was vulcanized at 160° C. for 25 minutes to prepare a rubber specimen.

[0185] (1) Mooney Viscosity (FMB, Final Master Batch) and Mooney Viscosity Difference (AMV, FMB-RP)

[0186] The Mooney viscosity (ML1+4, @100° C.) (MU) was measured using the vulcanized mixture compound prepared above. Particularly, the Mooney viscosity (FMB) was measured using MV2000E of Monsanto Co. using Large Rotor at a rotor speed of 2±0.02 rpm at 100° C. In this case, a specimen used was stood at room temperature (23±5° C.) for 30 minutes or more, and 27±3 g of the specimen was collected and put in a die cavity, and then, Platen was operated, and the Mooney viscosity (FMB) was measured while applying torque.

[0187] In addition, the Mooney viscosity and the Mooney viscosity difference of the mixture compound (ΔMV, FMB-RP) of each polymer shown in the Table above were calculated. In this case, the small Mooney viscosity difference means excellent processability.

[0188] (2) Tensile Strength, M-300% (300% Modulus) and Elongation

[0189] After vulcanizing each rubber composition at 150° C. for t90 minutes, tensile strength (kg.Math.f/cm.sup.2) of a vulcanized product, modulus when elongated by 300% (M-300%, 300% modulus, kg.Math.f/cm.sup.2) and elongation of a vulcanized product when breaking (%) were measured according to ASTM D412.

[0190] (3) Abrasion Resistance (DIN Abrasion Test)

[0191] With respect to each rubber specimen, DIN abrasion test was conducted based on ASTM D5963 and represented by DIN wt loss index (loss volume index:abrasion resistance index (ARIA), Method A). The high index represents excellent abrasion resistance.

[0192] (4) Viscoelasticity Properties

[0193] For measuring Tan δ properties, that are the most important factors of low fuel consumption ratio, a viscoelasticity coefficient (Tan δ) was measured using DMTS 500N of Gabo Co. in Germany at a frequency of 10 Hz, prestrain of 3%, and dynamic strain of 3%. The Tan δ value at 0° C. represents road surface resistance, and the Tan δ value at 60° C. represents rotation resistance properties (fuel consumption ratio).

TABLE-US-00003 TABLE 3 Example Comparative Example Division 1 2 1 2 3 4 5 6 Mooney viscosity (FMB) 59.0 54.0 65.0 60.3 66.3 66.3 53.3 55.7 ΔMV (FMB-RP) −11.0 −12.0 22.0 16.3 3.3 −2.7 −8.7 13.7 Tensile 109 110 100 102 108 107 105 101 Tensile strength properties M-300% 113 109 100 101 107 104 108 103 Elongation 107 108 100 98 106 101 104 99 Abrasion resistance 113 114 100 102 108 112 110 103 Viscoelasticity Tanδ @ 0° C.  100 101 100 99 95 100 99 101 properties Tanδ @ 60° C. 106 105 100 99 105 104 104 102

[0194] In Table 3, the resultant values of the tensile properties, abrasion resistance and Tan δ value at 0° C. were calculated and indexed by Mathematical Formula 2 below based on the measured values of Comparative Example 1, and the Tan δ value at 60° C. was calculated and indexed by Mathematical Formula 3 below.

Index=(measured value/standard value)×100  [Mathematical Formula 2]

Index=(standard value/measured value)×100  [Mathematical Formula 3]

[0195] As shown in Table 3, the rubber specimens of the Examples manufactured using the modifier represented by Formula 1 according to the present invention showed excellent processability in contrast to the Comparative Examples, and at the same time, all the tensile properties, abrasion resistance and viscoelasticity properties were improved.