Arylaminosilane compound, propylene polymerization catalyst and preparation thereof

Abstract

The present disclosure discloses an arylaminosilane compound, a propylene polymerization catalyst and preparation thereof. The arylaminosilane compound has a structure of ##STR00001##
wherein R.sub.1 is a C.sub.1-C.sub.8 alkyl group or a C.sub.1-C.sub.8 silanyl group; R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each independently H or a C.sub.1-C.sub.12 alkyl group; R.sub.7, R.sub.8 and R.sub.9 are each independently a C.sub.1-C.sub.8 alkyl group or a C.sub.1-C.sub.8 alkoxy group. When the arylaminosilane compound is used as an external electron donor of a propylene polymerization catalyst in propylene polymerization reaction, the catalyst has good hydrogen response.

Claims

1. An arylaminosilane compound, wherein the arylaminosilane compound is (N-methylanilino)methyldiethoxysilane.

2. A method for preparing an arylaminosilane compound according to claim 1, wherein a first method of the preparing method includes the following steps: reacting an arylamine represented by Formula II with an alkyl lithium in an organic solvent under a protective gas atmosphere at −80° C. to 30° C.; adding R.sub.7R.sub.8R.sub.9SiCl to the reaction system without separation and reacting at −80° C. to 30° C., so as to obtain the arylaminosilane compound after the completion of the reaction; ##STR00010## or, a second method includes the following steps: reacting an arylamine represented by Formula II with an alkyl lithium in an organic solvent under a protective gas atmosphere at −80° C. to 30° C.; adding (R.sub.7).sub.mSiCl.sub.4-m to the reaction system without separation to continue the reaction, to obtain an intermediate represented by Formula III after the completion of the reaction; wherein R.sub.7 is methyl and m is 0 or 1; ##STR00011## dissolving the intermediate represented by formula III in an organic solvent, adding ROH thereto, and reacting at 0° C. to 60° C. to obtain a compound of formula IV; ##STR00012## wherein R is a C.sub.1-C.sub.8 alkyl group; wherein the arylamine is N-methylaniline; R.sub.7R.sub.8R.sub.9SiCl is CH.sub.3(C.sub.2H.sub.5O).sub.2SiCl.

3. The method according to claim 2, wherein in the first method or the second method, the molar ratio of the arylamine to the alkyl lithium is 1: (1 to 3).

4. The method according to claim 2, wherein in the first method, the molar ratio of the arylamine to R.sub.7R.sub.8R.sub.9SiCl is 1: (1 to 3); in the second method, the molar ratio of the arylamine to (R.sub.7).sub.mSiCl.sub.4-m is 1: (1 to 3).

5. The method according to claim 2, wherein in the first method, the arylamine is reacted with the alkyl lithium for 1 to 48 hours; after the addition of R.sub.7R.sub.8R.sub.9SiCl, the reaction is carried out for 1 to 48 hours; in the second method, the arylamine is reacted with the alkyl lithium for 1 to 48 hours; the (R.sub.7).sub.mSiCl.sub.4-m is added to continue the reaction for 24 hours; and the intermediate represented by formula III is reacted with ROH for 4 to 60 hours.

6. The method according to claim 2, wherein the alkyl lithium is butyl lithium.

7. The method according to claim 2, wherein the protective gas is nitrogen, helium or argon.

8. The method according to claim 2, wherein the organic solvent is one or a mixed solvent of toluene, benzene, diethyl ether, tetrahydrofuran, pentane, hexane, heptane and octane.

9. The method according to claim 2, wherein the molar ratio of the intermediate represented by Formula III to ROH is 1: (1 to 100).

10. The method according to claim 2, wherein m is 1 and R is methyl or ethyl.

11. A propylene polymerization catalyst, wherein the propylene polymerization catalyst includes a solid titanium catalyst component, an alkyl aluminum compound component, and the arylaminosilane compound component according to claim 1.

12. The propylene polymerization catalyst according to claim 11, wherein the ratio of the components in the propylene polymerization catalyst is 1: (5 to 1000): (1 to 500) in terms of the molar ratio of titanium: aluminum: silicon.

13. The propylene polymerization catalyst according to claim 11, wherein the alkyl aluminum compound is trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, chlorodiethylaluminum, chlorodiisobutylaluminum or dichloroethylaluminum; the solid titanium catalyst is a solid titanium catalyst with titanium, magnesium, and halogen as main components; the solid titanium catalyst with titanium, magnesium, and halogen as the main components refers to magnesium halide, and a titanium compound having at least one Ti-halide bond and an internal electron donor compound supported thereon; the internal electron donor compound is a polycarboxylic acid ester, an acid anhydride, a ketone, an ether, or a sulfonyl compound.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a .sup.1H NMR spectrum of (N-methylanilino)trimethoxysilane in Example 1 of the present disclosure.

(2) FIG. 2 is a .sup.13C NMR spectrum of (N-methylanilino)trimethoxysilane in Example 1 of the present disclosure.

(3) FIG. 3 is a .sup.1H NMR spectrum of (N-methylanilino)methyldimethoxysilane in Example 2 of the present disclosure.

(4) FIG. 4 is a .sup.13C NMR spectrum of (N-methylanilino)methyldimethoxysilane in Example 2 of the present disclosure.

(5) FIG. 5 is a .sup.1H NMR spectrum of (N-methylanilino)triethoxysilane in Example 3 of the present disclosure.

(6) FIG. 6 is a .sup.13C NMR spectrum of (N-methylanilino)triethoxysilane in Example 3 of the present disclosure.

(7) FIG. 7 is a .sup.1H NMR spectrum of (N-methylanilino)methyldiethoxysilane in Example 4 of the present disclosure.

(8) FIG. 8 is a .sup.13C NMR spectrum of (N-methylanilino)methyldiethoxysilane in Example 4 of the present disclosure.

(9) FIG. 9 is a .sup.1H NMR spectrum of (2,6-diisopropyl-N-trimethylsilylanilino)trimethoxysilane in Example 5 of the present disclosure.

(10) FIG. 10 is a .sup.13C NMR spectrum of (2,6-diisopropyl-N-trimethylsilylanilino)trimethoxysilane in Example 5 of the present disclosure.

(11) FIG. 11 is a .sup.1H NMR spectrum of (2,6-diisopropyl-N-trimethylsilylanilino)methyldimethoxysilane in Example 6 of the present disclosure.

(12) FIG. 12 is a .sup.13C NMR spectrum of (2,6-diisopropyl-N-trimethylsilylanilino)methyldimethoxysilane in Example 6 of the present disclosure.

(13) FIG. 13 is a .sup.1H NMR spectrum of (2,6-diisopropyl-N-trimethylsilylanilino)triethoxysilane in Example 7 of the present disclosure.

(14) FIG. 14 is a .sup.13C NMR spectrum of (2,6-diisopropyl-N-trimethylsilylanilino)triethoxysilane in Example 7 of the present disclosure.

(15) FIG. 15 is a .sup.1H NMR spectrum of (2,6-diisopropyl-N-trimethylsilylanilino)methyldiethoxysilane in Example 8 of the present disclosure.

(16) FIG. 16 is a .sup.13C NMR spectrum of (2,6-diisopropyl-N-trimethylsilylanilino)methyldiethoxysilane in Example 8 of the present disclosure.

DETAILED DESCRIPTION

(17) In order to explain the present disclosure more clearly, the present disclosure is further described below with reference to preferred examples. Those skilled in the art should understand that what is specifically described below is illustrative and not restrictive, which should not limit the protection scope of the present disclosure.

(18) Test Methods:

(19) 1. The structure of the synthesized external donor compound is determined by nuclear magnetic resonance method.

(20) 2. The isotacticity of the polymerization product is determined by a method of boiling n-heptane extraction according to the national standard GB/T 2412-2008.

(21) 3. The melt index of the polymer product is determined according to the national standard GB/T 3682-2000.

EXAMPLE 1

(22) (1) Synthesis of (N-methylanilino)trimethoxysilane

(23) 8 g of N-methylaniline and 80 mL of THF were added to a 200 mL Schlenk flask. The temperature was dropped to 0° C., and 60 mL of n-butyl lithium (1.6 M solution in n-hexane) was slowly added dropwise. After 2 hours of reaction, 15 g of trimethoxychlorosilane was added dropwise, and the reaction mixture was naturally warmed to room temperature and reacted for 24 hours. The solvent was removed by vacuo, and 100 mL of n-hexane was added for filtration. Then n-hexane was removed by vacuo, and the residue was subjected to distillation under reduced pressure, and a fraction of 140-141° C. was collected to give 8.2 g of yellow liquid with a yield of 42%.

(24) .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 7.28 (t, 2H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 7.10 (d, 2H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 6.90 (t, 1H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 3.64 (s, 3H, N(OCH.sub.3), 3.62 (s, 6H, N(OCH.sub.3), 3.06 (s, 3H, NCH.sub.3).

(25) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 148.50, 128.90, 119.43, 51.30, 50.92, 34.06. NMR spectra are shown in FIGS. 1 and 2.

(26) (2) Preparation of Titanium-Containing Solid Catalyst

(27) 5.0 g of MgCl.sub.2.Math.2.85C.sub.2H.sub.5OH spherical support was added to a glass reaction flask containing 150 mL of TiCl.sub.4 and pre-cooled to 25° C. with stirring, gradually warmed to 80° C., and 2 mmol of internal electron donor diisobutyl phthalate was added. The temperature was kept for 30 minutes, and then the temperature was raised to 130° C. to react for 2 hours. It was filtered, and 120 mL of TiCl.sub.4 was added, and it was reacted at 130° C. for 2 hours, and filtered. The above steps of adding TiCl.sub.4 and filtering were repeated once. It was washed with n-hexane for six times. Finally, the solid was dried under vacuum to obtain 3.2 g of the spherical solid catalyst component of the present disclosure.

(28) (3) Propylene Polymerization Experiment

(29) A stainless steel reactor with a volume of 2 L was fully substituted with gas propylene, and then 5 mL of a triethylaluminum solution with a concentration of 2.4 mol/L, 0.9 mmol of the synthesized external electron donor compound N-methylanilinotrimethoxysilane, and 30 mg of the titanium-containing solid catalyst component prepared above were sequentially added, and 500 g of liquid propylene was introduced. The temperature was raised to 70° C., and the reaction was maintained at this temperature for 0.5 hour. The temperature was lowered and the pressure was released to obtain a polypropylene product. The results of the catalyst polymerization experiment are shown in Table 1.

EXAMPLE 2

(30) (1) Synthesis of (N-methylanilino)methyldimethoxysilane:

(31) 10 g of N-methylaniline and 80 mL of THF were added to a 200 mL Schlenk flask. The temperature was dropped to 0° C., and 60 mL of n-butyl lithium (1.6 M solution in n-hexane) was slowly added dropwise. After 2 hours of reaction, 16 g of methyl dimethoxychlorosilane was added dropwise, and the reaction mixture was naturally warmed to 25° C. and reacted for 24 hours. The solvent was removed by vacuo, and 100 mL of n-hexane was added for filtration. Then n-hexane was removed by vacuo, and the residue was subjected to distillation under reduced pressure to give 8.8 g of yellow liquid with a yield of 49%.

(32) .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 7.28 (t, 2H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 7.10 (d, 2H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 6.90 (t, 1H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 3.64 (s, 3H, N(OCH.sub.3), 3.62 (s, 6H, N(OCH.sub.3), 3.06 (s, 3H,NCH.sub.3).

(33) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 148.50, 128.90, 119.43, 51.30, 50.92, 34.06. NMR spectra are shown in FIGS. 3 and 4.

(34) (2) Preparation of Titanium-Containing Solid Catalyst: the Same as in Example 1.

(35) (3) Propylene Polymerization Experiment

(36) A stainless steel reactor with a volume of 2 L was fully substituted with gas propylene, and then 5 mL of a triethylaluminum solution with a concentration of 2.4 mol/L, 0.9 mmol of the synthesized external electron donor compound N-(methylanilino)methyldimethoxysilane, and 30 mg of the titanium-containing solid catalyst component prepared above were sequentially added, and 500 g of liquid propylene was introduced. The temperature was raised to 70° C., and the reaction was maintained at this temperature for 0.5 hour. The temperature was lowered and the pressure was released to obtain a polypropylene product. The results of the catalyst polymerization experiment are shown in Table 1.

EXAMPLE 3

(37) (1) Synthesis of (N-methylanilino)triethoxysilane:

(38) 6.5 g of N-methylaniline and 50 mL of THF were added to a 200 mL Schlenk flask. The temperature was dropped to 0° C., and 50 mL of n-butyl lithium (1.6 M solution in n-hexane) was slowly added dropwise. After 2 hours of reaction, 18 g of triethoxychlorosilane was added dropwise, and the reaction mixture was naturally warmed to 25° C. and reacted for 24 hours. The solvent was removed by vacuo, and 100 mL of n-hexane was added for filtration. Then n-hexane was removed by vacuo, and the residue was subjected to distillation under reduced pressure to give 8.5 g of orange liquid with a yield of 51%.

(39) .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 7.22 (t, 2H, .sup.3J.sub.H-H=6.8 Hz, Ar—H), 7.07 (d, 2H, .sup.3J.sub.H-H=8.8 Hz, Ar—H), 6.83 (t, 1H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 3.83 (q, 6H, .sup.3J.sub.H-H7.2 Hz, OCH.sub.2CH.sub.3), 3.02 (s, 3H, NCH.sub.3), 1.22 (t, 9H, .sup.3J.sub.H-H=6.8 Hz, OCH.sub.2CH.sub.3).

(40) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 148.76, 128.70, 119.05, 116.84, 58.91, 34.13, 18.02. NMR spectra are shown in FIGS. 5 and 6.

(41) (2) Preparation of Titanium-Containing Solid Catalyst: the Same as in Example 1.

(42) (3) Propylene Polymerization Experiment

(43) A stainless steel reactor with a volume of 2 L was fully substituted with gas propylene, and then 5 mL of a triethylaluminum solution with a concentration of 2.4 mol/L, 0.9 mmol of the synthesized external electron donor compound N-(methylanilino)triethoxysilane, and 30 mg of the titanium-containing solid catalyst component prepared above were sequentially added, and 500 g of liquid propylene was introduced. The temperature was raised to 70° C., and the reaction was maintained at this temperature for 0.5 hour, and the temperature was lowered and the pressure was released to obtain a polypropylene product. The results of the catalyst polymerization experiment are shown in Table 1.

EXAMPLE 4

(44) (1) Synthesis of (N-methylanilino)methyldiethoxysilane:

(45) 5.7 g of N-methylaniline and 40 mL of THF were added to a 100 mL Schlenk flask. The temperature was dropped to 0° C., and 33.5 mL of n-butyl lithium (2.5 M solution in n-hexane) was slowly added dropwise. After 2 hours of reaction, 14 g of methyldiethoxychlorosilane was added dropwise, and the reaction mixture was naturally warmed to room temperature and reacted overnight. The solvent was removed by vacuo, and 100 mL of n-hexane was added for filtration. Then n-hexane was removed by vacuo, and the residue was subjected to distillation under reduced pressure to give 7.4 g of yellow liquid with a yield of 58%.

(46) .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 7.26 (t, 2H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 7.09 (d, 2H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 6.86 (t, 1H, .sup.3J.sub.H-H=8.0 Hz, Ar—H), 3.84 (m, 4H, N(OCH.sub.2CH.sub.3)), 3.02 (s, 3H, NCH.sub.3), 1.26 (t, 6H, .sup.3J.sub.H-H=8.0 Hz, N(OCH.sub.2CH.sub.3)), 0.32 (s, 3H, SiCH.sub.3).

(47) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 149.25, 128.75, 118.90, 117.05, 58.23, 33.70, 18.13, −5.23. NMR spectra are shown in FIGS. 7 and 8.

(48) (2) Preparation of Titanium-Containing Solid Catalyst: the Same as in Example 1.

(49) (3) Propylene Polymerization Experiment

(50) A stainless steel reactor with a volume of 2 L was fully substituted with gas propylene, and then 5 mL of a triethylaluminum solution with a concentration of 2.4 mol/L, 0.9 mmol of the synthesized external electron donor compound N-(methylanilino)methyldiethoxysilane, and 30 mg of the titanium-containing solid catalyst component prepared above were sequentially added, and 500 g of liquid propylene was introduced. The temperature was raised to 70° C., and the reaction was maintained at this temperature for 0.5 hour. The temperature was lowered and the pressure was released to obtain a polypropylene product. The results of the catalyst polymerization experiment are shown in Table 1.

EXAMPLE 5

(51) (1) Synthesis of (2,6-diisopropyl-N-trimethylsilylanilino)trimethoxysilane

(52) 75 g of 2,6-diisopropylaniline and 300 mL of THF were added to a 1000 mL Schlenk flask substituted with nitrogen. The temperature was dropped to 0° C., and 350 mL of n-butyl lithium (1.6 M solution in n-hexane) was slowly added dropwise. When no bubble was generated, 50 g of trimethylchlorosilane was added dropwise in 1 hour. After the dropwise addition, the reaction was performed at room temperature for 2 hours. Then it was filtered, and the solvent was removed under vacuum, and the remaining oily liquid was distilled under reduced pressure to give 86.7 g of 2,6-diisopropyl-N-trimethylsilylaniline as light yellow oily substance with a yield of 85%.

(53) 40 g of 2,6-diisopropyl-N-trimethylsilylaniline synthesized above and 150 mL of THF were added to a 500 mL Schlenk flask, and 130 mL of n-BuLi (1.6 M solution in n-hexane) was slowly added dropwise at 0° C. When the dropwise addition was completed and no bubble was generated, the reaction was continued for 2 hours, and then 35 g of silicon tetrachloride was added dropwise. The mixture was naturally warmed to room temperature and stirred overnight. The solvent was removed by vacuo, and 150 mL of n-hexane was added, followed by filtration, concentration under vacuo and freeze crystallization, to give 48.6 g (2,6-diisopropyl-N-trimethylsilylanilino)trichlorosilane as a white solid with a yield of 79%.

(54) 10 g of (2,6-diisopropyl-N-trimethylsilylanilino)trichlorosilane synthesized above and 200 mL of toluene were added to a 500 mL Schlenk flask, and then 15 g of anhydrous methanol and 30 g of triethylamine in toluene were added dropwise, and the reaction was carried out for 12 h. The solvent was removed under vacuum, and n-hexane was added for filtration. It was concentrated under vacuum until a solid was just generated, and then placed in a refrigerator for crystallization, to give 7.0 g of (2,6-diisopropyl-N-trimethylsilylanilino)trimethoxysilane as a white solid, with a yield of 73%, melting point: 132-135° C. .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 7.10 (d, 1H, .sup.3J.sub.H-H=5.2 Hz, Ar—H), 7.07 (t, 2H, .sup.3J.sub.H-H=6.0 Hz, Ar—H), 3.57 (m, 2H, .sup.3J.sub.H-H7.2 Hz, CH(CH.sub.3).sub.2), 3.46 (s, 9H, OCH.sub.3), 1.22 (q, 12H, .sup.3J.sub.H-H=4.8 Hz, CH(CH.sub.3).sub.2), 0.11 (s, 9H, Si(CH.sub.3).sub.3).

(55) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 137.35, 123.49, 122.30, 49.83, 26.32, 23.46, 0.01. NMR spectra are shown in FIGS. 9 and 10.

(56) (2) Preparation of Titanium-Containing Solid Catalyst: the Same as in Example 1.

(57) (3) Propylene Polymerization Experiment

(58) A stainless steel reactor with a volume of 2 L was fully substituted with gas propylene, and then 5 mL of a triethylaluminum solution with a concentration of 2.4 mol/L, 0.9 mmol of the synthesized external electron donor compound 2,6-diisopropylanilino(N-trimethylsilyl)trimethoxysilane, and 30 mg of the titanium-containing solid catalyst component prepared above were sequentially added, and 500 g of liquid propylene was introduced. The temperature was raised to 70° C., and the reaction was maintained at this temperature for 0.5 hour. The temperature was lowered and the pressure was released to obtain a polypropylene product. The results of the catalyst polymerization experiment are shown in Table 1.

EXAMPLE 6

(59) (1) Synthesis of (2,6-diisopropyl-N-trimethylsilylanilino)methyldimethoxysilane

(60) 38 g of the intermediate 2,6-diisopropyl-N-trimethylsilylaniline synthesized in Example 5 and 150 mL of THF were added to a 500 mL Schlenk flask, and 150 mL of n-BuLi (1.6 M solution in n-hexane) was slowly added dropwise at 0° C. When the dropwise addition was completed and no bubble was generated, the reaction was continued for 2 hours. The temperature was lowered to −78° C. and 26 g of methyltrichlorosilane was added dropwise. The reaction mixture was naturally warmed to room temperature and stirred overnight. It was concentrated under vacuum until a solid was just generated, and placed in a refrigerator for crystallization, to give 40 g of (2,6-diisopropyl-N-trimethylsilylanilino)methyldichlorosilane as a white solid with a yield of 70%.

(61) .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 7.188 (t, 1H, .sup.3J.sub.H-H=6.0 Hz, Ar—H), 7.188 (d, 2H, .sup.3J.sub.H-H=6.8 Hz, Ar—H), 3.465 (m, 2H, .sup.3J.sub.H-H=6.8 Hz, CH(CH.sub.3).sub.2), 1.24 (m, 12H, .sup.3J.sub.H-H=6.8 Hz, CH(CH.sub.3).sub.2), 0.550 (s, 3H, SiCl.sub.2CH.sub.3), 0.242 (s, 9H, Si(CH.sub.3).sub.3).

(62) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 145.238, 137.336, 124.077, 122.353, 25.969, 23.291, 22.937, 4.653.

(63) 10.8 g of (2,6-diisopropyl-N-trimethylsilylanilino)methyldichlorosilane and 200 mL of toluene were added to a 500 mL Schlenk flask, and then 35 g of anhydrous methanol and 13.8 g of triethylamine in toluene were added dropwise, and the reaction was carried out for 24 h. The solvent was removed under vacuum, and 150 mL of n-hexane was added for filtration. It was concentrated under vacuum until a solid was just generated, and placed in a refrigerator for crystallization, to give 7 g of a white solid, with a yield of 65%, melting point of 96-98° C.

(64) .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 7.188 (t, 1H, .sup.3J.sub.H-H=6.0 Hz, Ar—H), 7.188 (d, 2H, .sup.3J.sub.H-H=6.8 Hz, Ar—H), 3.465 (m, 2H, .sup.3J.sub.H-H=6.8 Hz, CH(CH.sub.3).sub.2), 1.24 (m, 12H, .sup.3J.sub.H-H=6.8 Hz, CH(CH.sub.3).sub.2), 0.550 (s, 3H, SiCl.sub.2CH.sub.3 ), 0.242 (s, 9H, Si(CH.sub.3).sub.3).

(65) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 145.238, 137.336, 124.077, 122.353, 25.969, 23.291, 22.937, 4.653. NMR spectra are shown in FIGS. 11 and 12.

(66) (2) Preparation of Titanium-Containing Solid Catalyst: the Same as in Example 1.

(67) (3) Propylene Polymerization Experiment

(68) A stainless steel reactor with a volume of 2 L was fully substituted with gas propylene, and then 5 mL of a triethylaluminum solution with a concentration of 2.4 mol/L, 0.9 mmol of the synthesized external electron donor compound 2,6-diisopropylanilino(N-trimethylsilyl)methyldimethoxysilane, and 30 mg of the titanium-containing solid catalyst component prepared above were sequentially added, and 500 g of liquid propylene was introduced. The temperature was raised to 70° C., and the reaction was maintained at this temperature for 0.5 hour. The temperature was lowered and the pressure was released to obtain a polypropylene product. The results of the catalyst polymerization experiment are shown in Table 1.

EXAMPLE 7

(69) (1) Synthesis of (2,6-diisopropyl-N-trimethylsilylanilino)triethoxysilane:

(70) 12.5 g of the intermediate 2,6-diisopropyl-N-trimethylsilylaniline synthesized in

(71) Example 5 and 100 mL of THF were added to a 200 mL Schlenk flask. The temperature was dropped to 0° C., and 50 mL of n-butyl lithium (1.6 M solution in n-hexane) was slowly added dropwise. The reaction mixture was naturally warmed to room temperature and reacted for 2 hours and then 8.7 g of triethoxychlorosilane was added dropwise, and the reaction was carried out for 24 hours. The solvent was removed by vacuo, 100 mL of n-hexane was added for filtration, and the solvent in the filtrate was removed by vacuo. Then it was separated by column chromatography to give 9.5 g of an orange solid with a yield of 57% and a melting point of 150-152° C.

(72) .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 6.97 (t, 1H, .sup.3J.sub.H-H=5.2 Hz, Ar—H), 6.94 (t, 2H, .sup.3J.sub.H-H=5.6 Hz, Ar—H), 3.63 (q, 2H, .sup.3J.sub.H-H=7.2 Hz, OCH.sub.2CH.sub.3), 3.58 (t, 4H, .sup.3J.sub.H-H=7.2 Hz, OCH.sub.2CH.sub.3), 3.49 (m, 2H, .sup.3J.sub.H-H=7.2 Hz, CH(CH.sub.3).sub.2), 1.10 (q, 12H, .sup.3J.sub.H-H=6.8 Hz, CH(CH.sub.3).sub.2), 1.02 (t, 6H, .sup.3J.sub.H-H=6.8 Hz, OCH.sub.2CH.sub.3), 1.01 (t, 3H, .sup.3J.sub.H-H=6.8 Hz, OCH.sub.2CH.sub.3), 0.00 (s, 9H, Si(CH.sub.3).sub.3).

(73) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 144.99, 137.36, 121.85, 120.83, 56.25, 24.91, 22.26, 15.51, −1.19. NMR spectra are shown in FIGS. 13 and 14.

(74) (2) Preparation of Titanium-Containing Solid Catalyst: the Same as in Example 1.

(75) (3) Propylene Polymerization Experiment

(76) A stainless steel reactor with a volume of 2 L was fully substituted with gas propylene, and then 5 mL of a triethylaluminum solution with a concentration of 2.4 mol/L, 0.9 mmol of the synthesized external electron donor compound 2,6-diisopropylanilino(N-trimethylsilyl)triethoxysilane, and 30 mg of the titanium-containing solid catalyst component prepared above were sequentially added, and 500 g of liquid propylene was introduced. The temperature was raised to 70° C., and the reaction was maintained at this temperature for 0.5 hour. The temperature was lowered and the pressure was released to obtain a polypropylene product. The results of the catalyst polymerization experiment are shown in Table 1.

EXAMPLE 8

(77) (1) Synthesis of (2,6-diisopropyl-N-trimethylsilylanilino)methyldiethoxysilane:

(78) 10.8 g of the compound 2,6-diisopropyl(N-trimethylsilyl)anilinomethyldichlorosilane synthesized in Example 6 and 15.5 g of anhydrous ethanol were added to a 200 mL Schlenk flask, and then 15 g of triethylamine was added dropwise and reacted for 7 hours. The solvent was removed under vacuum, 150 mL of n-hexane was added for filtration, and the solvent was removed under vacuum to give 7 g of an orange liquid with a yield of 41%.

(79) .sup.1H NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 7.09 (d, 2H, .sup.3J.sub.H-H=5.2 Hz, Ar—H), 7.07 (t, 1H, .sup.3J.sub.H-H=5.2 Hz, Ar—H), 3.74 (q, 4H, .sup.3J.sub.H-H=6.8 Hz, Si(OCH.sub.2CH.sub.3)), 3.62 (m, 2H, .sup.3J.sub.H-H=6.8 Hz, CH(CH.sub.3).sub.2), 1.21 (d, 12H, .sup.3J.sub.H-H=6.8 Hz, CH(CH.sub.3).sub.2), 1.19 (t, 6H, .sup.3J.sub.H-H=6.8 Hz, Si(OCH.sub.2CH.sub.3)), 0.13 (s, 9H, Si(CH.sub.3).sub.3), 0.01 (s, 3H, SiCH.sub.3).

(80) .sup.13C NMR (400 MHz, CDCl.sub.3, 25° C., TMS): δ(ppm) 145.65, 138.81, 122.68, 121.77, 56.47, 25.58, 23.26, 23.14, 16.50, −6.81. NMR spectra are shown in FIGS. 15 and 16.

(81) (2) Preparation of Titanium-Containing Solid Catalyst: the Same as in Example 1.

(82) (3) Propylene Polymerization Experiment

(83) A stainless steel reactor with a volume of 2 L was fully substituted with gas propylene, and then 5 mL of a triethylaluminum solution with a concentration of 2.4 mol/L, 0.9 mmol of the synthesized external electron donor compound 2,6-diisopropylanilino(N-trimethylsilyl)methyldiethoxysilane, and 30 mg of the titanium-containing solid catalyst component prepared above were sequentially added, and 500 g of liquid propylene was introduced. The temperature was raised to 70° C., and the reaction was maintained at this temperature for 0.5 hour. The temperature was lowered and the pressure was released to obtain a polypropylene product. The results of the catalyst polymerization experiment are shown in Table 1.

COMPARATIVE EXAMPLE 1

(84) The same titanium-containing solid catalyst component and propylene polymerization method were used as in Examples 1-8, except that the external electron donor compound was changed to cyclohexylmethyldimethoxysilane.

(85) From the results of the catalyst polymerization experiments in Table 1, it can be seen that the isotacticity of the polymerization product obtained by using the arylaminosiloxane compound of the present disclosure as an external electron donor is substantially the same as that of the known typical organosiloxane external electron donor used in Comparative Example 1. However, when the arylaminosiloxane compound of the present disclosure is used as the external electron donor, the melt index of the polypropylene obtained by polymerization reaction of propylene is significantly higher than the melt index of the polypropylene obtained by polymerization reaction of propylene when the known typical organosiloxane external electron donor in Comparative Example 1 was used as the external electron donor.

(86) Therefore, it is demonstrated that the propylene polymerization catalysts with the arylaminosiloxane compound as the external electron donor have good hydrogen response; moreover, the isotacticity of polypropylene is also relatively high, so it can be used to prepare polypropylene materials with high flowability and high isotacticity.

(87) TABLE-US-00001 TABLE 1 Results of catalyst polymerization experiments Catalytic Melt activity Iso- Index (g/10 (KgPP/ tacticity min, 2.16 Example External electron donor gCat/h) (%) Kg) Comparative cyclohexylmethyldime- 32.0 95.8 20.8 Example 1 thoxysilane Example 1 (N-methylanilino) 37.8 95.0 35.1 trimethoxysilane Example 2 (N-methylanilino) 31.7 95.2 125.3 methyldimethoxysilane Example 3 (N-methylanilino) 31.5 94.1 63.8 triethoxysilane Example 4 (N-methylanilino) 41.4 95.6 50.0 methyldiethoxysilane Example 5 (2,6-diisopropyl-N- 30.0 94.8 31.4 trimethylsilylanilino) trimethoxysilane Example 6 (2,6-diisopropyl-N- 33.5 95.3 103.3 trimethylsilylanilino) methyldimethoxysilane Example 7 (2,6-diisopropyl-N- 39.0 94.8 34.2 trimethylsilylanilino) triethoxysilane Example 8 (2,6-diisopropyl-N- 35.0 92.6 62.2 trimethylsilylanilino) methyldiethoxysilane

(88) It is apparent that the above Examples of the present disclosure are merely examples for clearly explaining the present disclosure, and are not intended to limit the embodiments of the present disclosure. For a person of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. Not all embodiments can be exhausted herein. Every obvious change or modification that is derived from the technical solution of the present disclosure is still within the protection scope of the present disclosure.