JP2006511625A5 - - Google Patents

Description

Ethylene is greater than 100 kPa (1 barg), preferably greater than 1000 kPa (10 barg), more preferably may be contacted with the catalyst system at a pressure above 3000 kPa (30 barg).

The method can be carried out at pressures from atmospheric to 50000 kPa (500 barg). An ethylene pressure in the range of 1000 to 7000 kPa (10 to 70 barg) is preferred. A particularly preferred pressure is in the range of 3000 to 5000 kPa (30 to 50 barg).

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (methyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 30.0 mg of (4- A solution of methoxyphenyl) ₂ PN (methyl) P (4-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 60 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 65 ° C. while maintaining the ethylene pressure at 3000 kPa (30 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.2254 g of polyethylene. GC analysis indicated that the reaction mixture contained 38.50 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (3-methoxyphenyl) ₂ PN (methyl) P (3-methoxyphenyl) ₂ and MAO In a Schlenk tube, 30.0 mg of (3- A solution of methoxyphenyl) ₂ PN (methyl) P (3-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 60 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 65 ° C. while maintaining the ethylene pressure at 3000 kPa (30 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.2269 g of polyethylene. GC analysis showed that the reaction mixture contained 9.71 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 36.1 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 60 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 65 ° C. while maintaining the ethylene pressure at 3000 kPa (30 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.7105 g of polyethylene. GC analysis showed that the reaction mixture contained 61.33 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 36.1 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 11.5 mg of chromium (III) acetylacetonate (0.033 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 12 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 2.3010 g of polyethylene. GC analysis indicated that the reaction mixture contained 73.53 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 16.4 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.03 mmol) in 10 ml cyclohexane was added to 5.2 mg chromium (III) acetylacetonate (0.015 mmol) in 10 ml cyclohexane. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of cyclohexane (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 11 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.9168 g of polyethylene. GC analysis showed that the reaction mixture contained 62.72 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 21 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.8280 g of polyethylene. GC analysis showed that the reaction mixture contained 69.17 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using CrCl ₃ THF ₃ , (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of (4-methoxyphenyl) A solution of ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to a solution of 5.6 mg CrCl ₃ THF ₃ (0.015 mmol) in 10 ml of toluene. . The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and then weighed to give a yield of 1.0831 g of polyethylene. GC analysis indicated that the reaction mixture contained 42.72 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) 2-ethylhexanoate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of A solution of (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to 10.2 mg of Cr (III) 2-ethylhexanoate (mineral oil). In 70 ml, 0.015 mmol) in 10 ml of toluene. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.52 g of polyethylene. GC analysis indicated that the reaction mixture contained 61.27 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) octanoate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to 10.3 mg of Cr (III) octanoate (70% in toluene, 0.015 mmol). ) In 10 ml of toluene. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 4.5 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 40 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.3773 g of polyethylene. GC analysis indicated that the reaction mixture contained 18.91 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 6.6 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.012 mmol) in 10 ml of toluene was added to 3.5 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 3.0 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 30 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.3958 g of polyethylene. GC analysis indicated that the reaction mixture contained 54.52 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO In a Schlenk tube, 9.8 mg of (4- A solution of methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.018 mmol) in 10 ml of toluene was added to 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml of toluene. In the solution. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane, 2.25 mmol). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 15 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.5010 g of polyethylene. GC analysis showed that the reaction mixture contained 70.87 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MMAO-3A In a Schlenk tube, 16.4 mg ( _{4-methoxyphenyl)} 10ml of 2 PN (isopropyl) P _{(4-methoxyphenyl)} 2 (a solution in toluene of 10ml of 0.03 mmol), chromium 5.2 mg (III) acetylacetonate (0.015 mmol) To a solution of toluene in toluene. The mixture was stirred at ambient temperature for 5 minutes, followed by addition to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MMAO-3A (modified methylaluminoxane in heptane, 4.5 mmol). Moved. The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 22 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.76 g of polyethylene. GC analysis indicated that the reaction mixture contained 50.42 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and EAO / TMA In a Schlenk tube, 36.1 mg ( 4-Methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.066 mmol) in 10 ml of toluene was added to 5.2 mg of chromium (III) acetylacetonate (0.015 mmol) in 10 ml. To a solution of toluene in toluene. The mixture was stirred at ambient temperature for 5 minutes, followed by 300 ml pressure reaction containing a mixture of toluene (80 ml) and EAO (ethylaluminoxane in toluene, 33 mmol) and TMA (trimethylaluminum, 8.25 mmol) at 40 ° C. Transferred to a vessel (autoclave). The pressure reactor was charged with ethylene, after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 60 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 0.189 g of polyethylene. GC analysis showed that the reaction mixture contained 40.97 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ and MAO in the presence of H _{2 in} a Schlenk tube. A solution of 16.4 mg (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ (0.03 mmol) in 10 ml toluene was added 5.2 mg chromium (III) acetylacetonate (0 .015 mmol) in 10 ml of toluene. The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol). The pressure reactor was initially charged with hydrogen to a pressure of about 250 kPa (2.5 barg), followed by ethylene to 4500 kPa (45 barg), after which the reactor temperature was maintained at 45 ° C., while the ethylene pressure was 4500 kPa ( 45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 15 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 1.2060 g of polyethylene. GC analysis showed that the reaction mixture contained 81.51 g of oligomer. The product distribution for this example is summarized in Table 1.

Tetramerization reaction of ethylene using Cr (III) acetylacetonate, (phenyl) ₂ PN (isopropyl) P (2-methoxyphenyl) ₂ and MAO In a Schlenk tube, 32.2 mg of (phenyl) ₂ PN ( A solution of isopropyl) P (2-methoxyphenyl) ₂ (0.066 mmol) in 10 ml toluene was added to a solution of 11.5 mg chromium (III) acetylacetonate (0.033 mmol) in 10 ml toluene. . The mixture was stirred at ambient temperature for 5 minutes and then transferred to a 300 ml pressure reactor (autoclave) containing a 40 ° C. mixture of toluene (80 ml) and MAO (methylaluminoxane in toluene, 4.5 mmol). The pressure reactor was initially charged with ethylene, after which the reactor temperature was maintained at 45 ° C. while the ethylene pressure was maintained at 4500 kPa (45 barg). A gas-entrained stirrer was used to ensure complete mixing from beginning to end with a mixing speed of 1100 RPM. The reaction was terminated after 15 minutes by cutting off the ethylene feed to the reactor and the reactor was cooled below 10 ° C. After releasing excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for analysis by GC-FID in the liquid phase. A small sample of the organic layer was dried over anhydrous sodium sulfate and subsequently analyzed by GC-FID. The remainder of the organic layer was filtered to isolate a solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and subsequently weighed to give a yield of 6.82 g of polyethylene. GC analysis showed that the reaction mixture contained 38.33 g of oligomer. The product distribution for this example is summarized in Table 1.

Claims (57)

A method of oligomerizing an olefin comprising the step of contacting an olefin feed stream with a catalyst system, wherein the catalyst system comprises a transition metal compound and the following general formula (R) _nABC (R) _m ( Wherein A and C are independently selected from the group consisting of phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium, and nitrogen, B is a linking group between A and C, and R Are the same or different and each R is independently selected from homohydrocarbyl and heterohydrocarbyl groups, at least one of R is substituted with a polar substituent, and n and m for each R are A combination of heteroatom ligands independently represented by the respective valences and oxidation states of A and C, provided that the heteroatom ligand is represented by the following general formula (R ¹ ) ( R ²⁾ A-B ^{C (R 3) (R 4} ) ( in the formula, A and C are independently phosphorus, arsenic, antimony, is selected from the group consisting of bismuth and nitrogen, B is a linking group between A and C Each of R ¹ , R ² , R ³ and R ⁴ is independently selected from the group consisting of a non-aromatic group, an aromatic group and a heterocyclic aromatic group, and R ¹ , R ² , R ^When at least one of ³ and R ⁴ is aromatic, it is substituted with a polar substituent on an atom that is the second or more away from the atom bonded to A or C, and R ¹ , R ² , R ³ And R ⁴ , when they are all aromatic, any polar substituents thereof are not represented on the atom adjacent to the atom bound to A or C)) And how to. The heteroatom ligand has the following general formula (R ¹ ) (R ² ) ABC (R ³ ) (R ⁴ ) (where A and C are independently phosphorus, arsenic, , Antimony, bismuth and nitrogen, B is a linking group between A and C, and each of R ¹ , R ² , R ³ and R ⁴ is independently a non-aromatic group , Selected from the group consisting of an aromatic group and a heterocyclic aromatic group. The method according to claim 2, wherein up to 4 of R ¹ , R ² , R ³ and R ⁴ have a substituent on the atom adjacent to the atom bonded to A or C. The oligomerization method is a tetramerization method, and each R ¹ , R ² , R ³ and R ⁴ is an aromatic including a heterocyclic aromatic, but not all R ¹ , R ² , The method of claim 2, wherein R ³ and R ⁴ are substituted with an optional substituent on an atom adjacent to the atom bonded to A or C. The method of claim 4, more than two R ^1, R ^2, R ³ and R ⁴ has a substituent on the atom adjacent to the atom bound to A or C. One or more of R ^1, R ^2, any polar substituents on R ³ and R ^4, method according to any one of claims 2 to 5 which is an electron-donating.   6. A process according to claim 4 or 5 wherein the feed stream comprises alpha-olefin and the product stream comprises at least 30% tetramerized alpha-olefin monomer.   8. The method of claim 7, wherein the olefin feed stream comprises ethylene and the product stream comprises at least 30% 1-octene. The olefin feed stream comprises ethylene, and the ratio of (C ₆ + C ₈ ) :( C ₄ + C ₁₀ ) in the product stream is greater than 2.5: 1. Method. Wherein wherein the olefin feed stream to ethylene, C ₈ of the product _stream: The method according to the ratio of C ₆ is greater than one according to claim 1 or 4.   The method according to claim 1, wherein the pressure exceeds 100 kPa (10 barg).   11. A process according to any one of claims 8 to 10 wherein ethylene is contacted with the catalyst system at a pressure in excess of 1000 kPa (10 barg).   13. A method according to any one of claims 1 to 12, wherein A and / or C are potential electron donors for coordination with the transition metal. B is an organic linking group comprising hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl; an inorganic linking group comprising a single atom linking spacer; and methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene, 1 , 2-propane, 1,2-catechol, ^{1,2-dimethylhydrazine, -B (R 5) -,} - Si (R 5) 2 -, - P (R 5) - and -N ^(R 5) - (R ⁵ is hydrogen, hydrocarbyl or substituted hydrocarbyl, a heteroatom and a halogen to replace) the method according to any one of claims 1 to 13 selected from the group consisting of radicals containing.   15. A method according to claim 14, wherein B is a single atom bond spacer. B is —N (R ⁵ ) — (R ⁵ is hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonyl 15. The method of claim 14, wherein the method is selected from the group consisting of amino, dialkylamino, silyl groups or derivatives thereof, and aryl substituted with any of these substituents.   17. A and / or C are independently oxidized with S, Se, N or O (the valence of A and / or C enables said oxidation). The method described.   A method according to any one of claims 1 to 16, wherein A and C are independently phosphorus or phosphorus oxidized with S or Se or N or O. R ¹ , R ² , R ³ and R ⁴ are independently benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, 3. The thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, dimethylhydrazyl, methyl, ethyl, ethenyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl groups. the method of. The ligand is (3-methoxyphenyl) ₂ PN (methyl) P (3-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (methyl) P (4-methoxyphenyl) ₂ , (3-methoxy Phenyl) ₂ PN (isopropyl) P (3-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (2-ethylhexyl) P (4-methoxyphenyl) ₂ , (3-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) ₂ and (4-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) ₂ , (3-methoxy Phenyl) (phenyl) PN (methyl) P (3-methoxyphenyl) (phenyl), (4-methoxyphenyl) (phenyl) ) PN (methyl) P (4-methoxyphenyl) (phenyl), _{(3-methoxyphenyl)} 2 PN (methyl) P _{(phenyl) 2} and _{(4-methoxyphenyl)} 2 PN (methyl) P _(phenyl) 2, (4-Methoxyphenyl) ₂ PN (1-cyclohexylethyl) P (4-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (2-methylcyclohexyl) P (4-methoxyphenyl) ₂ , (4-methoxy Phenyl) ₂ PN (decyl) P (4-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (pentyl) P (4-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (benzyl) P (4 - _{methoxyphenyl)} 2, _{(4-methoxyphenyl)} 2 PN (phenyl) P _{(4-methoxyphenyl)} 2, (4- _Ruorofeniru) 2 PN (methyl) P _{(4-fluorophenyl)} 2, _{(2-fluorophenyl)} 2 PN (methyl) P _{(2-fluorophenyl)} 2, (4-dimethylamino - _phenyl) 2 PN (methyl) P (4-dimethylamino-phenyl) ₂ , (4-methoxyphenyl) ₂ PN (allyl) P (4-methoxyphenyl) ₂ , (phenyl) ₂ PN (isopropyl) P (2-methoxyphenyl) ₂ , (4- The group consisting of (4-methoxyphenyl) -phenyl) ₂ PN (isopropyl) P (4- (4-methoxyphenyl) -phenyl) ₂ and (4-methoxyphenyl) (phenyl) PN (isopropyl) P (phenyl) ₂ 3. A method according to claim 1 or 2 selected from.   21. A process according to any one of the preceding claims, wherein the catalyst system is prepared by combining a heteroatom ligand with a transition metal compound and an activator in any order.   23. The method of claim 21, comprising the step of adding a preformed coordination complex prepared using a heteroatom ligand and a transition metal precursor to a reaction mixture containing an activator.   The method of claim 21, comprising generating a heteroatom coordination complex in situ from the transition metal compound and the heteroatom ligand.   The method according to any one of claims 1 to 23, wherein the transition metal in the transition metal compound is selected from the group consisting of chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium.   The method of claim 24, wherein the transition metal is chromium.   26. The method according to any one of claims 1 to 25, wherein the transition metal compound is selected from the group consisting of inorganic salts, organic salts, coordination complexes and organometallic complexes.   The transition metal compound is composed of chromium trichloride tris-tetrahydrofuran complex, (benzene) tricarbonyl chromium, chromium octanoate (III), acetylacetonate chromium (III), hexacarbonyl chromium and 2-ethylhexanoate chromium (III). 27. The method of claim 26, selected from the group.   28. The method of claim 27, wherein the transition metal compound is selected from a complex selected from chromium (III) acetylacetonate and chromium (III) 2-ethylhexanoate.   The transition metal derived from the transition metal compound and the heteroatom ligand are combined to provide a metal / ligand ratio of about 0.01: 100 to 10000: 1. The method according to any one of the above.   The catalyst system is an organoaluminum compound, an organoboron compound, an organic salt (such as methyl lithium bromide and methyl magnesium bromide), an inorganic acid and an inorganic salt (tetrafluoroborate etherate, silver tetrafluoroborate and hexafluoroantimonic acid) 24. A method according to any one of claims 21 to 23 comprising an activator selected from any one of the group consisting of sodium and the like.   32. The method of claim 30, wherein the activator is an alkylaluminoxane.   32. The method of claim 31, wherein the transition metal and aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 1000: 1. Transition metal compounds and the following general formula (R) _n ABC (R) _m , wherein A and C are independently phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium, and nitrogen Wherein B is a linking group between A and C, R is the same or different, each R is independently selected from a homohydrocarbyl group and a heterohydrocarbyl group; At least one of which is substituted with a polar substituent, and n and m for each R are independently determined by the respective valences and oxidation states of A and C). Combination (wherein the heteroatom ligand is represented by the following general formula (R ¹ ) (R ² ) ABC (R ³ ) (R ⁴ ) (where A and C are independently From phosphorus, arsenic, antimony, bismuth and nitrogen Is selected from the group, B is a linking group between A and C, R ^{1, R 2,} R ^3, and each R ^4, independently, a non-aromatic group, an aromatic group and heterocyclic When selected from the group consisting of aromatic groups and at least one of R ¹ , R ² , R ^3, and R ⁴ is aromatic, on an atom that is at least a second away from an atom bonded to A or C When substituted by a polar substituent and R ¹ , R ² , R ³ and R ⁴ are all aromatic, any polar substituent is adjacent to the atom bound to A or C A tetramerization catalyst system characterized by comprising: The heteroatom ligand has the following general formula (R ¹ ) (R ² ) ABC (R ³ ) (R ⁴ ) (where A and C are independently phosphorus, arsenic, , Antimony, bismuth and nitrogen, B is a linking group between A and C, and each of R ¹ , R ² , R ³ and R ⁴ is independently a non-aromatic group 34. The catalyst system of claim 33, wherein the catalyst system is selected from the group consisting of: aromatic groups and heterocyclic aromatic groups. Each R ¹ , R ² , R ³ and R ⁴ is an aromatic, including a heterocyclic aromatic, but not all R ¹ , R ² , R ³ and R ⁴ are bonded to A or C 35. The catalyst system of claim 34, wherein the catalyst system is substituted with an optional substituent on an atom adjacent to the atom. More than two R ^1, R ^2, R ³ and R ^4, the catalyst system according to claim 35 having a substituent on the atom adjacent to the atom bound to A or C. One or more of R ^1, R ^2, any polar substituents on R ³ and R ^4, the catalyst system according to any one of claims 34 to 36 which is an electron-donating.   38. A catalyst system according to any one of claims 33 to 37, wherein A and / or C are potential electron donors for coordination with the transition metal. B is an organic linking group comprising hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl; an inorganic linking group comprising a single atom linking spacer; and methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene, 1 , 2-propane, 1,2-catechol, ^{1,2-dimethylhydrazine, -B (R 5) -,} - Si (R 5) 2 -, - P (R 5) - and -N ^(R 5) - (R ⁵ is hydrogen, hydrocarbyl or substituted hydrocarbyl, a heteroatom and a halogen to substituted) catalyst system according to any one of claims 33 to 38 selected from the group consisting of radicals containing.   40. The method of claim 39, wherein B is a single atom bond spacer. B is —N (R ⁵ ) — (R ⁵ is hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonyl 40. The method of claim 39, wherein the method is selected from the group consisting of amino, dialkylamino, silyl groups or derivatives thereof, and aryl substituted by any of these substituents.   42. In any one of claims 33 to 41, A and / or C are independently oxidized with S, Se, N or O (the valence of A and / or C enables the oxidation). The catalyst system described.   42. A catalyst system according to any one of claims 33 to 41, wherein A and C are independently phosphorus or phosphorus oxidized with S or Se or N or O. The ligand is (3-methoxyphenyl) ₂ PN (methyl) P (3-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (methyl) P (4-methoxyphenyl) ₂ , (3-methoxy Phenyl) ₂ PN (isopropyl) P (3-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (isopropyl) P (4-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (2-ethylhexyl) P (4-methoxyphenyl) ₂ , (3-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) ₂ and (4-methoxyphenyl) (phenyl) PN (methyl) P (phenyl) ₂ , (3-methoxy Phenyl) (phenyl) PN (methyl) P (3-methoxyphenyl) (phenyl), (4-methoxyphenyl) (phenyl) ) PN (methyl) P (4-methoxyphenyl) (phenyl), _{(3-methoxyphenyl)} 2 PN (methyl) P _{(phenyl) 2} and _{(4-methoxyphenyl)} 2 PN (methyl) P _(phenyl) 2, (4-Methoxyphenyl) ₂ PN (1-cyclohexylethyl) P (4-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (2-methylcyclohexyl) P (4-methoxyphenyl) ₂ , (4-methoxy Phenyl) ₂ PN (decyl) P (4-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (pentyl) P (4-methoxyphenyl) ₂ , (4-methoxyphenyl) ₂ PN (benzyl) P (4 - _{methoxyphenyl)} 2, _{(4-methoxyphenyl)} 2 PN (phenyl) P _{(4-methoxyphenyl)} 2, (4- _Ruorofeniru) 2 PN (methyl) P _{(4-fluorophenyl)} 2, _{(2-fluorophenyl)} 2 PN (methyl) P _{(2-fluorophenyl)} 2, (4-dimethylamino - _phenyl) 2 PN (methyl) P (4-dimethylamino-phenyl) ₂ , (4-methoxyphenyl) ₂ PN (allyl) P (4-methoxyphenyl) ₂ , (phenyl) ₂ PN (isopropyl) P (2-methoxyphenyl) ₂ , (4- The group consisting of (4-methoxyphenyl) -phenyl) ₂ PN (isopropyl) P (4- (4-methoxyphenyl) -phenyl) ₂ and (4-methoxyphenyl) (phenyl) PN (isopropyl) P (phenyl) ₂ 44. The catalyst system according to any one of claims 33 to 43, selected from:   45. A catalyst system according to any one of claims 33 to 44, wherein the transition metal in the transition metal compound is selected from the group consisting of chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium.   46. The catalyst system of claim 45, wherein the transition metal is chromium.   47. A catalyst system according to any one of claims 33 to 46, wherein the transition metal compound is selected from the group consisting of inorganic salts, organic salts, coordination complexes and organometallic complexes.   The transition metal compound is composed of chromium trichloride tris-tetrahydrofuran complex, (benzene) tricarbonyl chromium, chromium octanoate (III), acetylacetonate chromium (III), hexacarbonyl chromium and 2-ethylhexanoate chromium (III). 48. The catalyst system of claim 47, selected from the group.   49. The catalyst system of claim 48, wherein the transition metal compound is selected from a complex selected from chromium (III) acetylacetonate and chromium (III) 2-ethylhexanoate.   50. The transition metal of claim 33 to 49, wherein the transition metal derived from the transition metal compound and the heteroatom ligand are combined to provide a metal / ligand ratio of about 0.01: 100 to 10,000: 1. A catalyst system according to any one of the preceding claims.   51. A catalyst system according to any one of claims 33 to 50 comprising an activator.   The activator is an organoaluminum compound, an organoboron compound, an organic salt (such as methyllithium bromide and methylmagnesium bromide), an inorganic acid and an inorganic salt (tetrafluoroborate etherate, silver tetrafluoroborate and hexafluoroantimony) 52. The catalyst system according to claim 51 selected from the group consisting of sodium acid and the like.   32. The method of claim 30, wherein the activator is an alkylaluminoxane.   54. The catalyst system of claim 53, wherein the alkylaluminoxane is selected from the group consisting of methylaluminoxane (MAO), ethylaluminoxane (EAO) and modified alkylaluminoxanes (MMAO).   55. The catalyst system of claim 53 or 54, wherein the transition metal and aluminoxane are combined in a ratio that provides an Al / metal ratio of about 1: 1 to 1000: 1.   56. Use of the catalyst system according to any one of claims 33 to 55 for tetramerization of olefins.   56. Use of the catalyst system according to any one of claims 33 to 55 for tetramerization of ethylene.