Method for Producing Block Copolymer Composition

Abstract

A method for producing a block copolymer composition including a diblock copolymer and a triblock copolymer each containing a polyolefin-based block and a polystyrene-based block is disclosed herein. In some embodiments, the method includes reacting an organic zinc compound with one or more kinds of olefin-based monomers in the presence of a transition metal catalyst to form an intermediate having an olefin-based polymer block, reacting the intermediate styrene-based monomer in the presence of an alkyllithium compound to form a product having a styrene-based polymer block, and reacting the product with water, oxygen, or an organic acid to form a block copolymer wherein the number of moles of the alkyllithium compound used to form the product is larger than the number of moles of the organic zinc compound used to form the intermediate.

Claims

1. A method for producing a polyolefin-polystyrene block copolymer composition, comprising: reacting an organic zinc compound with one or more kinds of olefin-based monomers in the presence of a transition metal catalyst to form an intermediate having an olefin-based polymer block; and reacting the intermediate with a styrene-based monomer in the presence of an alkyllithium compound to form a product including a styrene-based polymer block, wherein the number of moles of the alkyllithium compound used in to form the styrene-based polymer block is larger than the number of moles of the organic zinc compound used to form the intermediate, and wherein the polyolefin-polystyrene block copolymer composition includes a diblock copolymer and a triblock copolymer each of the diblock and triblock copolymers including a polyolefin-based block and a polystyrene-based block, wherein the content of the diblock copolymer is 19 wt % or less, based on the total weight of the polyolefin-polystyrene block copolymer composition.

2. The method of claim 1, wherein the olefin-based monomer forms a first block including a repeating unit represented by Formula 1 below: ##STR00018## in Formula 1 above, R.sub.1 is hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl, arylalkyl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms substituted with silyl, and n is an integer of 1 to 10,000.

3. The method of claim 2, wherein the first block comprises a repeating unit represented by Formula 2 below: ##STR00019## in Formula 2 above, R.sub.1 and R.sub.1 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl, arylalkyl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms substituted with silyl, wherein R1 and R.sub.1 are different from each other, 0<p<1, and n is an integer of 10 to 10,000.

4. The method of claim 1, wherein the one or more kinds of olefin-based monomer comprises ethylene and one or more kinds of alpha-olefin-based monomers, and the alpha-olefin-based monomer is an aliphatic olefin having 2 to 20 carbon atoms.

5. The method of claim 1, wherein the organic zinc compound is a compound represented by Formula 3 below: ##STR00020## in Formula 3 above, A is alkylene having 1 to 20 carbon atoms, arylene having 6 to 20 carbon atoms, or arylene having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, and B is arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 12 carbon atoms.

6. The method of claim 5, wherein A is alkylene having 1 to 12 carbon atoms, arylene having 6 to 12 carbon atoms, or arylene having 6 to 12 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, and B is arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 8 carbon atoms.

7. The method of claim 1, wherein in the olefin-based monomer is inserted between Zn and A of the organic zinc compound and polymerized to form the olefin-based polymer block.

8. The method of claim 7, wherein the styrene-based monomer is inserted between Zn of the intermediate and the olefin-based polymer block and polymerized to form a styrene-based polymer block.

9. The method of claim 1, wherein the intermediate is represented by Formula 4 below: ##STR00021## in Formula 4 above, R.sub.1 is hydrogen, alkyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms substituted with silyl, arylalkyl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms substituted with silyl, A is alkylene having 1 to 20 carbon atoms, arylene having 6 to 20 carbon atoms, or arylene having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, B is arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 12 carbon atoms, and n is an integer of 10 to 10,000.

10. The method of claim 1, wherein the styrene-based monomer forms a second block including a repeating unit represented by Formula 6 below: ##STR00022## in the formula above, R.sub.2 is aryl having 6 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, and 1 is an integer of 10 to 1,000.

11. The method of claim 1, wherein the styrene-based monomer forms a second block including a repeating unit represented by Formula 6 below and a third block represented by Formula 9 below, respectively. ##STR00023## in Formulas 6 and 9 above, R.sub.2 and R.sub.3 are each independently aryl having 6 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, and 1 and m are each independently an integer of 10 to 1,000.

12. The method of claim 1, wherein the product is represented by Formula 10 below: ##STR00024## in Formula 10 above, R.sub.1 is hydrogen, unsubstituted or substituted alkyl having 1 to 20 carbon atoms, wherein the substituent is silyl, or unsubstituted or substituted arylalkyl having 7 to 20 carbon atoms, is silyl, R.sub.2 and R.sub.3 are each independently unsubstituted or substituted aryl having 6 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms substituted with wherein the substituent is halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms or aryl having 6 to 12 carbon atoms, 1 and m are each independently an integer of 10 to 1,000, and n is an integer of 10 to 10,000.

13. The method of claim 1, wherein a molar ratio of the organic zinc compound to the alkyllithium compound is 1:1.05 to 1:4.

14. The method of claim 1, which further comprises reacting the product with water, oxygen, or an organic acid to convert the product into a block copolymer.

Description

MODE FOR CARRYING OUT THE INVENTION

Examples

[0102] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art may easily carry out the present invention. The present invention may, however, be embodied in many different forms and is not limited to the embodiments set forth herein.

Preparation Example: Preparing Organic Zinc Compound

[0103] ##STR00016##

[0104] Borane dimethyl sulfide (1.6 mL, 3.2 mmol) was slowly introduced to triethyl borane (0.6 g) in stirring and then reacted for 90 minutes. The mixture was slowly introduced to divinylbenzen (3.8 g) dissolved in anhydrous diethyl ether (10 mL) cooled to -20 C. and then stirred overnight. A solvent was removed with a vacuum pump and then diethyl zinc (0.8 g) was added. A reaction was performed at 0 C. for 5 hours while removing triethyl borane generated through reduced pressure distillation. At 40 C., excess divinylbenzene and diethylzinc were removed by reduced pressure distillation. Methylcyclohexane (150 mL) was added to dissolve a product again, and then a solid compound produced as a by-product was filtered using celite and removed to prepare an organic zinc compound represented by Formula 16 above.

Example 1

[0105] 15 mL of 1-hexene and 240 mol of an organic zinc compound {(CH.sub.2=CHC.sub.6H.sub.4CH.sub.2CH.sub.2).sub.2Zn} dissolved in 100 g of methylcyclohexane was introduced into a high-pressure reactor, and then the temperature of the reactor was raised to 80 C.

[0106] A solution (5 mol) containing a transition metal compound represented by Formula 17 below and [(C.sub.18H.sub.37)N(Me)H.sup.+[B(C.sub.6F.sub.5).sub.4].sup. which is a cocatalyst at a ratio of 1:1 was injected into the high-pressure reactor, and then ethylene was immediately injected thereto to maintain the pressure at 20 bar.

[0107] A polymerization process was performed at a temperature of 95 C. to 100 C. for 45 minutes, and then unreacted gas was discharged. Me.sub.3SiCH.sub.2Li and N,N,N,N,N-pentamethyldiethylenetriamine (PMDETA) were mixed at a ratio of 1:1 (420 mol) in methylcyclohexane, and the mixture was injected to the reactor and then stirred for 30 minutes. The stirring temperature was maintained at 90 C. to 100 C. 8.5 mL of styrene was injected to the high-pressure reactor and then, while maintaining the temperature between 90 C. and 100 C., was reacted over 5 hours to convert all the styrene monomers. After the complete conversion of the styrene, acetic acid and ethanol were continuously injected. A polymer composition obtained therefrom was dried overnight in a vacuum oven of

##STR00017##

Examples 2 to 9

[0108] A polymer composition was produced in the same manner as in Example 1 except that 1-hexene, styrene, an organic zinc compound, methylcyclohexane, a transition metal compound/cocatalyst solution, Me.sub.3SiCH.sub.2Li and PMDETA were used in the amounts shown in Table 1 below.

TABLE-US-00001 TABLE 1 Amount used Transition metal Organic compound/ Alpha- zinc Methyl- Cocatalyst olefin Styrene compound cyclohexane solution Me.sub.3SiCH.sub.2 (mL) (mL) (mol) (g) (mol) Li/PMDETA Example 1 1-hexene 8.5 240 100 5 420 15 Example 2 1-hexene 8.5 300 100 5 420 15 Example 3 1-hexene 8.5 179 100 5 420 15 Example 4 1-hexene 6.5 357 100 5 420 30 Example 5 1-hexene 6.5 357 100 5 420 25 Example 6 1-hexene 8.5 357 100 5 420 30 Example 7 1-hexene 10 357 100 5 420 30 Example 8 1-hexene 13 714 200 5 815 50 Example 9 1-hexene 13 714 200 5 815 60 Comparative Propylene 7.8 150 100 4 150 Example 5 30 Comparative Propylene 7.8 150 100 4 150 Example 6 35 Comparative 1-hexene 7.8 150 100 4 150 Example 7 10 Comparative 1-hexene 7.8 150 100 4 150 Example 8 15

Comparative Examples 1 to 4

[0109] As Comparative Examples 1 to 4, Product# G1650, G1651, G1652, and G1654 of Kraton Company, which are commercially available SEBS, were used, respectively.

[0110] Comparative Example 5

[0111] 30 mL of 1-propylene and 150 mol of an organic zinc compound {(CH.sub.2=CHC.sub.6H.sub.4CH.sub.2CH.sub.2).sub.2Zn} dissolved in 100 g of methylcyclohexane was introduced into a high-pressure reactor, and then the temperature of the reactor was raised to 80 C.

[0112] A solution (4 mol) containing 1:1 ratio of a transition metal compound represented by Formula 17 and [(C.sub.18H.sub.37)N(Me)H.sup.+[B(C.sub.6F.sub.5).sub.4].sup. which is a cocatalyst was injected into the high-pressure reactor, and then 30 g of propylene was immediately injected thereto, followed by ethylene to bring the pressure to 20 bar. The pressure was maintained at 20 bar.

[0113] A polymerization process was performed for 45 minutes at a temperature of 95 C. to 110 C., and then unreacted gas was discharged. Me.sub.3SiCH.sub.2Li and N,N,N,N,N-pentamethyldiethylenetriamine (PMDETA) were mixed at a ratio of 1:1 (150 mol) in methylcyclohexane, and the mixture was injected to the reactor and then stirred for 30 minutes. The stirring temperature was maintained at 90 C. to 110 C. 7.8 g of styrene was injected to the high-pressure reactor and then, while maintaining the temperature between 90 C. and 110 C., was reacted over 5 hours to convert all the styrene monomers. After the complete conversion of the styrene, acetic acid and ethanol were continuously injected. A polymer composition obtained therefrom was dried overnight in a vacuum oven of 80 C.

Comparative Example 6

[0114] A polymer composition was produced in the same manner as in Comparative Example 5 except that 35 mL of propylene was injected, followed by ethylene to bring the pressure to 20 bar and the pressure was maintained at 20 bar.

Comparative Example 7

[0115] 10 mL of 1-hexene and 150 mol of an organic zinc compound {(CH.sub.2=CHC.sub.6H.sub.4CH.sub.2CH.sub.2).sub.2Zn} dissolved in 100 g of methylcyclohexane was introduced into a high-pressure reactor, and then the temperature of the reactor was raised to 80 C.

[0116] A solution (4 mol) containing 1:1 ratio of a transition metal compound represented by Formula 17 and [(C.sub.18H.sub.37)N(Me)H.sup.+[B(C.sub.6F.sub.5).sub.4].sup. which is a cocatalyst was injected into the high-pressure reactor, and then 30 g of propylene was immediately injected thereto, followed by ethylene to bring the pressure to 20 bar. The pressure was maintained at 20 bar.

[0117] A polymerization process was performed at a temperature of 95 C. to 110 C. for 45 minutes, and then unreacted gas was discharged. Me.sub.3SiCH.sub.2Li and N,N,N,N,N-pentamethyldiethylenetriamine (PMDETA) were mixed at a ratio of 1:1 (150 mol) in methylcyclohexane, and the mixture was injected to the reactor and then stirred for 30 minutes. The stirring temperature was maintained at 90 C. to 110 C. 7.8 g of styrene was injected to the high-pressure reactor and then, while maintaining the temperature between 90 C. and 110 C., was reacted over 5 hours to convert all the styrene monomers. After the complete conversion of the styrene, acetic acid and ethanol were continuously injected. A polymer composition obtained therefrom was dried overnight in a vacuum oven of 80 C.

Comparative Example 8

[0118] A polymer composition was produced in the same manner as in Comparative Example 8 except that 15 mL of 1-hexene was injected, followed by ethylene to bring the pressure to 20 bar and the pressure was maintained at 20 bar.

Experimental Examples

[0119] The physical properties of the block copolymer composition of each of Examples 1 to 9 and Comparative Examples 1 to 8 were measured according to the following methods, and the results are shown in Table 2 below.

1) Content of 1-Hexene, Branch, and Styrene

[0120] The measurement was performed through nuclear magnetic resonance (NMR). Using Bruker 600 MHz AVANCE III HD NMR device, 1H NMR was measured under the condition of ns=16, d1=3s, solvent=TCEd2, and 373K, and then the TCEd2 solvent peak was calibrated to 6.0 ppm. CH.sub.3 of 1-propylene was confirmed at 1 ppm and a CH.sub.3-related peak (triplet) of a butyl branch by 1-hexene was confirmed near 0.96 ppm to calculate the contents. In addition, the content of styrene was calculated using an aromatic peak near 6.5 to 7.5 ppm.

[0121] 2) Weight Average Molecular Weight (Mw, g/mol) and Polydispersity Index (PDI)

[0122] The weight average molecular weight (Mw, g/mol) and the number average molecular weight (Mn, g/mol) were measured by gel permeation chromatography (GPC), respectively, and the weight average molecular weight was divided by the number average molecular weight to calculate the polydispersity index (PDI).

[0123] Column: PL Olexis

[0124] Solvent: TCB(Trichlorobenzene)

[0125] Flow rate: 1.0 ml/min

[0126] Sample concentration: 1.0 mg/ml

[0127] Injection amount: 200

[0128] Column temperature: 160 C.

[0129] Detector: Agilent High Temperature RI detector

[0130] Use polystyrene standard

[0131] Calculate molecular weight by Universal calibration using the Mark-house equation (K=40.810.sup.5, =0.7057)

[0132] 3) Measurement of Tensile Strength, 300% Modulus, and Elongation

[0133] Using the polymer composition of each of Examples 1 to 9 and Comparative Examples 1 to 8, a molded product was prepared into a dumbbell shaped specimens according to ASTM D-412. According to ASTM D638, a cross head was pulled at a cross head speed of 500 mm/min using a universal testing machine (UTM) device (Model name: 4466, Instron), and then the point at which each specimen was cut was measured. The tensile strength was calculated by Equation 1 below. Also, the elongation (%) was calculated by Equation 2 below, and the 300% modulus (stress at 300%) was obtained by measuring the tensile strength when a specimen was stretched to three times the initial length.

[00001]$\begin{array}{cc}\mathrm{Tensile}.Math..Math.\mathrm{strength}.Math..Math.\left(\mathrm{kgf}.Math.\text{/}.Math.{\mathrm{mm}}^2\right)=\frac{\mathrm{Load}.Math..Math.\mathrm{value}.Math..Math.\left(\mathrm{kgf}\right)}{\mathrm{Thickness}.Math..Math.\left(\mathrm{mm}\right)\mathrm{Width}.Math..Math.\left(\mathrm{mm}\right)}& \left[\mathrm{Equation}.Math..Math.1\right]\\ \mathrm{Elongation}=\frac{\mathrm{Length}.Math..Math.\mathrm{after}.Math..Math.\mathrm{elongation}}{\mathrm{Initial}.Math..Math.\mathrm{length}}& \left[\mathrm{Equation}.Math..Math.2\right]\end{array}$

[0134] 4) Content of Residual Double Bond

[0135] The measurement was performed through nuclear magnetic resonance (NMR). Using Bruker 600 MHz AVANCE III HD NMR device, 1H NMR was measured under the condition of ns=16, d1=3s, solvent=TCE-d2, and 373K, and then the TCEd2 solvent peak was calibrated to 6.0 ppm. CH.sub.2 of a double bond was confirmed at 5-5.5 ppm to calculate the content.

[0136] 5) Content of Diblock Copolymer

[0137] A peak deconvolution was carried out between a GPC curve obtained using gel permeation chromatography (GPC) and two Gaussian curves.

[0138] As a program for peak deconvolution, Origin was used, and in the analysis, Multiple Peak Fit was used. Specifically, a measured molecular weight was assumed to be the molecular weight of the triblock copolymer and 75% of the measured molecular weight was assumed to be the molecular weight of the diblock copolymer, and two peaks of Gaussian curves were fitted. A weight percentage was calculated on the basis of a derived area percentage and the measured molecular weight.

TABLE-US-00002 TABLE 2 Molecular Physical Residual Content of Composition weight properties double diblock Ethylene Branch Styrene Mw Elongation T 300% bond copolymer (wt %) (wt %) (wt %) (g/mol) PDI (%) (MPa) m (MPa) (wt %) (wt %) Example 1 51.5 20.1 28.4 102,700 1.7 1,201 26.4 6.7 0 14.8 Example 2 55.1 22.0 22.9 82,000 1.6 1,301 22.4 5.5 0 13.2 Example 3 49.0 21.3 29.7 98,500 1.5 1,253 25.4 5.9 0 11.8 Example 4 47.7 25.8 26.5 76,700 1.6 1,603 23.4 3.3 0 13.8 Example 5 50.8 20.7 28.5 77,900 1.6 1,356 30.6 6.2 0 11.5 Example 6 48.3 27.7 24 78,400 1.7 1,845 24.1 3.5 0 9.6 Example 7 49.1 20.9 30.1 101,200 1.7 1,139 29.3 6.1 0 11.8 Example 8 46.9 28.7 24.4 79,700 1.7 1,779 23.0 3.3 0 13.8 Example 9 48.4 31.6 22.0 76,100 1.9 2,208 21.2 2.4 0 10.2 Comparative 44.3 26.2 29.5 54,600 1.1 1,305 29.9 2.9 0.99 0 Example 1 Comparative 43.4 24.8 31.8 139,300 1.1 0.42 0 Example 2 Comparative 44.6 26.6 28.8 44,100 1.1 1,325 30.7 3.3 0.24 0 Example 3 Comparative 43.3 25.5 31.2 95,600 1.1 1,584 30.6 2.2 0.42 0 Example 4 Comparative 39.3 18.6 42.1 111,000 1.7 850 9.5 4.5 0 21.7 Example 5 Comparative 45.5 22.5 32.0 109,000 1.7 1390 8.2 2.5 0 20.2 Example 6 Comparative 45.2 21.3 33.5 69,000 1.6 802 16.5 7.7 0 19.8 Example 7 Comparative 47.7 16.4 35.9 68,000 1.5 1,294 21.4 5.9 0 20.9 Example 8

[0139] Referring to Table 1, the polymer composition of each of Examples 1 to 9 has a polydispersity index (PDI) value relatively higher than that of SEBS of each of Comparative Examples 1 to 4, and thus, is expected to exhibit excellent processability. In addition, the polymer of each of Examples 1 to 9 has a high polydispersity index (PDI) value as well as excellent values of elongation, 300% modulus which represents elasticity, and tensile strength. From the results, it can be confirmed that the polymers of Examples 1 to 9 have excellent physical properties that are different from the physical properties of the polymers of Comparative Examples 1 to 8, which are not good in one or more physical properties.