1-OCTENE COMPOSITION

Abstract

The present invention relates to a 1-octene composition. The 1-octene composition according to the present invention is prepared by ethylene oligomerization and comprises a high content of 1-octene and monomers useful for copolymerization of 1-octene at the same time.

Claims

1-4. (canceled)

5. A method of preparing 1-octene composition, the method comprising the step of multimerizing ethylene in the presence of a catalyst system for olefin oligomerization comprising a ligand compound, a transition metal source, and a cocatalyst, the 1-octene composition comprising 90% by weight or more of 1-octene and 0.01 to 10% by weight of three or more of compounds represented by the following Chemical Formulae 1 to 4: ##STR00010## wherein the ligand compound comprises i) two or more of a group represented by the following Chemical Formula 5 in the molecule, in which the two or more of the group are linked via four carbon atoms by a group selected from the group consisting of an aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, or is ii) a compound represented by the following Chemical Formula 6, ##STR00011## wherein R.sub.1 to R.sub.4 are each independently C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl, or C.sub.7-20 alkoxyaryl, ##STR00012## wherein R.sub.5 to R.sub.8 are each independently C.sub.6-20 aryl, or C.sub.7-20 alkylaryl, R.sub.9 and R.sub.10 are each independently C.sub.1-20 alkyl, with the proviso that R.sub.9 and R.sub.10 are not the same as each other, R.sub.11 to R.sub.13 are each independently hydrogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.7-20 arylalkyl, C.sub.7-20 arylalkenyl, C.sub.3-20 cycloalkyl, C.sub.3-20 cycloalkenyl, C.sub.9-20 arylcycloalkyl, C.sub.9-20 arylcycloalkenyl, C.sub.6-20 aryl, or C.sub.7-20 alkylaryl.

6. The method of claim 5, wherein the transition metal source is any one or more selected from the group consisting of chromium(III)acetylacetonoate, tris(tetrahydrofuran)chromium trichloride, chromium(III)-2-ethylhexanoate, chromium(III)tris(2,2,6,6-tetramethyl-3,5-heptanedionate), chromium(III)benzoylacetonate, chromium(III)hexafluoro-2,4-pentanedionate, and chromium(III)acetate hydroxide.

7. The method of claim 5, wherein the ligand compound is ##STR00013## ##STR00014##

8. The method of claim 5, wherein the cocatalyst is one or more selected from the group consisting of compounds represented by the following Chemical Formulae 7 to 9:
[Al(R.sub.14)O].sub.c[Chemical Formula 7] wherein R.sub.14 is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbyl radical having 1 to 20 carbon atoms, and c is an integer of 2 or more,
D(R.sub.15).sub.3 [Chemical Formula 8] wherein D is aluminium or boron, R.sub.15 is the same as or different from each other, and each independently hydrogen or halogen, hydrocarbyl having 1 to 20 carbon atoms, or halogen-substituted hydrocarbyl having 1 to 20 carbon atoms,
[L-H].sup.+[Q(E)4].sup.[Chemical Formula 9] wherein L is a neutral Lewis base, [L-H].sup.+ is a Bronsted acid, Q is boron or aluminium in the +3 oxidation state, and E is each independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, in which one or more hydrogen atoms are substituted or unsubstituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, an alkoxy functional group or a phenoxy functional group.

9. The method of claim 5, wherein the method further comprises the step of separating a C8 liquid composition having a boiling point of 110 to 140 C. at atmospheric pressure.

10. The method of claim 5, wherein the 1-octene composition comprises 0.1 to 1% by weight of three or more of the compounds represented by Chemical Formulae 1 to 4.

11. The method of claim 5, wherein the 1-octene composition comprises 99% by weight or more of 1-octene.

12. The method of claim 5, the 1-octene composition comprises all of the compounds represented by Chemical Formulae 1 to 4.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0060] FIG. 1 shows the result of analyzing an octene composition prepared in an exemplary embodiment of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0061] Hereinafter, the present invention will be explained in more detail with reference to the following Examples. However, these Examples are only to illustrate the invention, and the scope of the invention is not limited thereto.

[0062] Hereinafter, all the reactions were progressed using a Schlenk technique or a Glove box under an argon atmosphere. The synthesized compounds were analyzed by .sup.1H (500 MHz) and .sup.31P (202 MHz) NMR spectra using a Varian 500 MHz spectrometer. Shift was expressed in ppm, downfield from TMS, with a residual solvent peak as a reference. A phosphorous probe was calibrated with aqueous H.sub.3PO.sub.4.

Preparation Example 1

[0063] ##STR00007##

[0064] Under an argon atmosphere, 3-(aminomethyl)-3,5,5-trimethylcyclohexaneamine (5 mmol) and triethylamine (3-10 equivalents) were dissolved in dichloromethane (80 mL), While the flask was immersed in a water bath, chlorodiphenylphosphine (20 mmol) was slowly added, and the mixture was stirred overnight. The solvent was removed under vacuum, and then THF was added, the mixture was sufficiently stirred, and triethylammonium chloride salt was removed with an air-free glass filter. The solvent was removed from the filtrate to obtain a target compound.

[0065] .sup.31P NMR (202 MHz, CDCl.sub.3): 45.6 (br s). 56.2 (br s)

Preparation Example 2

[0066] ##STR00008##

[0067] Under an argon atmosphere, 2-ethyl-6-methylaniline (10 mmol) and triethylamine (3 equivalents) were dissolved in dichloromethane (80 mL). While the flask was immersed in a water bath, chlorodiphenylphosphine (20 mmol) was slowly added, and the mixture was stirred overnight. The solvent was removed under vacuum, and then THF was added, the mixture was sufficiently stirred, and triethylammonium chloride salt was removed with an air-free glass filter. The solvent was removed from the filtrate to obtain a target compound.

[0068] .sup.31P NMR (202 MHz, CDCl.sub.3): 59.2 (br s)

Preparation Example 3

[0069] ##STR00009##

[0070] Under an argon atmosphere, 2-ethyl-6-methylaniline (10 mmol) and triethylamine (3 equivalents) were dissolved in dichlorornethane (80 mL). While the flask was immersed in a water bath, chlorobis(3,5-dimethylphenyl)phosphine (20 mmol) was slowly added, and the mixture was stirred overnight. The solvent was removed under vacuum, and then THF was added, the mixture was sufficiently stirred, and triethylammonium chloride salt was removed with an air-free glass filter. The solvent was removed from the filtrate to obtain a target compound.

[0071] .sup.31P NMR(202 MHz, CDCl.sub.3): 57.2 (br s)

Example 1

[0072] Step 1

[0073] Under argon gas, Cr(acac).sub.3 (17.5 mg, 0.05 mmol) and the compound prepared in Preparation Example 1 (0.025 mmol) were added into a flask, methylcyclohexane (100 mL) was added, and the mixture was stirred to prepare a 0.5 mM solution (based on Cr).

[0074] Step 2

[0075] Vacuum was applied to 600 mL-Parr reactor for 2 hours at 120 C., then the internal atmosphere was replaced with argon, and the temperature was lowered to 60 C. 175 mL of methylcyclohexane and 2 mL of MMAO (isoheptane solution, Al/Cr=1200) were added, and 5 mL of 0.5 mM solution (2.5 umol) was added into the reactor. The mixture was stirred at 500 rpm for 1 minute, a valve of an ethylene line adjusted to 60 bar was opened to fill the inside of the reactor with ethylene, and then the temperature was controlled to 60 C. and the mixture was stirred at 500 rpm for 15 minutes. The ethylene line valve then was closed, the reactor was cooled to 0 C. with a dry ice/acetone bath, non-reacted ethylene was slowly vented, and 0.5 mL of nonane (GC internal standard) was added. After stirring for 10 seconds, 2 mL of the liquid part of the reactor was taken and quenched with water, and the organic part was filtered with a PTFE syringe filter to make a sample. The sample was analyzed by GC-MS and GC-FID as in the following Experimental Example, and quantified by GC-FID.

[0076] Step 3

[0077] 400 mL of ethanol/HCl (10 vol %) was added to the remaining reaction solution, and the mixture was stirred and filtered to obtain a polymer. The obtained polymer was dried overnight in a vacuum oven at 65 C., and the weight was measured.

Example 2

[0078] The same process as in Example 1 was conducted to prepare a sample and a polymer, except that the compound prepared in Preparation Example 2 (0.05 mmol) was used instead of the compound prepared in Preparation Example 1.

Example 3

[0079] The same process as in Example 1 was conducted to prepare a sample and a polymer, except that the compound prepared in Preparation Example 3 (0.05 mmol) was used instead of the compound prepared in Preparation Example 1.

Example 4

[0080] The same process as in Example 1 was conducted to prepare a sample and a polymer, except that the compound prepared in Preparation Example 2 (0.05 mmol) was used instead of the compound prepared in Preparation Example 1 and n-heptane was used instead of methylcyclohexane as a solvent.

Comparative Example 1

[0081] 1-Octene (98%, 04806-1L) purchased from Sigma-Aldrich was used as Comparative Example 1.

Comparative Example 2

[0082] 1-Octene purchased from INEOS was used as Comparative Example 2.

Comparative Example 3

[0083] The same process as in Example 1 was conducted to prepare a sample and a polymer, except that a catalyst system prepared from Cr(acac).sub.3, Ph.sub.2PN(iPr)PPh.sub.2 and MMAO according to the literature (J. Am. Chem. Soc. 2005, 127. 10723-10730) was used.

Experimental Example

[0084] GC-FID analysis was conducted using 1-octene compositions of Examples and Comparative Examples as follows.

[0085] AT-5 column (0.32 mm ID30 mL) was used, and gases such as Column (He) 1.6 mL/min, Make-up (He) 30 mL/min, Hydrogen 40 mL/min, and Air 400 mL/min were applied and analyzed. During analysis, the program was as follows: the temperature of an oven was maintained at 35 C. for 5 minutes, and then raised at a rate of 1 C./min. At a moment when the temperature reached 50 C., the temperature was raised at a rate of 15 C./min. The temperature was maintained at 300 C. for 30 minutes and then terminated. Analysis was conducted at an injector temperature of 270 C., at a detector temperature of 280 C., and at an injector split of 25/1 with an injection volume of 0.2 uL.

[0086] The analysis results are given in the following Table 1, together with the catalytic activity.

TABLE-US-00001 TABLE 1 Catalytic 1-Hexene + C6 activity 1-Hexene 1-Octene 1-octene isomers (ton/molCr/hr) (wt %) (wt %) (wt %) (wt %) Ex. 1 196 39.0 45.3 84.3 3.6 Ex. 2 161 49.5 40.5 90.0 1.5 Ex. 3 156 39.2 52.6 91.9 1.0 Ex. 4 131 24.1 63.2 87.3 2.0

[0087] The C8 compositions or the compositions of by-products in Examples 1 to 4 and Comparative Examples 1 to 3 are given in the following Table 2, in which the by-products appeared around 1-octene peak expected to have a boiling point of 110 C. to 140 C. under atmospheric pressure.

[0088] Further, GC chromatogram of Example 1 is shown in FIG. 1.

TABLE-US-00002 TABLE 2 GC-FID Products in C8 elution time Ex. 1 Ex. 2 Ex. 3 Ex. 4 Com. Com. Com. # composition (min) (wt %) (wt %) (wt %) (wt %) Ex. 1 Ex. 2 Ex. 3 1 1-Octene 8.25-8.65 99.012 99.267 99.349 99.244 >98 wt % 85.7 wt % 2 n-Octane 8.699 0.122 0.016 0.022 0.000 .sup..sup.2) 3 2-Octene 8.824 0.104 0.059 0.048 0.120 4 2-Octene 8.942 0.026 0.019 0.035 0.000 5 Chemical 9.186 0.218 0.153 0.229 0.094 .sup.X.sup.3) X Formula 1 6 Chemical 9.637 0.113 0.078 0.123 0.045 X X Formula 2 7 Chemical 10.063 0.231 0.221 0.114 0.266 X X X Formula 3 8 Chemical 10.589 0.174 0.187 0.079 0.232 Trace X X Formula 4 1 + 2 + 3 + 4.sup.1) 0.736 0.639 0.545 0.637 Sum 100 100 100 100 .sup.1)Sum of Chemical Formulae 1 to 4 .sup.2)detected .sup.3)undetected