Supported long-chain fluorine-containing aryl borate, and preparation method and application thereof

Abstract

The invention discloses loaded long-chain fluorine-containing aryl borate as well as a preparation method and application thereof. The preparation method comprises the following steps: A, reacting an amine compound and hydrochloric acid in a solvent to generate quaternary ammonium salt; b, (4-bromophenoxy) alkylsilane, magnesium chips and 1, 2-dibromoethane are heated in a solvent for a reaction, and a Grignard reagent is generated; c, reacting the Grignard reagent with perfluoroaryl borane in the presence of a solvent to generate fluorine-containing aryl borate; d, the fluorine-containing aryl borate and quaternary ammonium salt react in a solvent to generate long-chain fluorine-containing aryl borate; e, reacting the silicon dioxide subjected to heat treatment with silane and triethylamine in a solvent to generate silane modified silicon dioxide; f, enabling the long-chain fluorine-containing aryl borate and the silane modified silicon dioxide to generate loaded long-chain fluorine-containing aryl borate in the presence of a solvent; by using the loaded long-chain fluorine-containing aryl borate, the activity of the catalyst, the molecular weight of the polymer and the insertion rate of a comonomer can be improved; in addition, the loaded long-chain fluorine-containing aryl borate can use aluminum alkyl with low price, so that expensive MAO / MMAO is avoided, and the production cost is reduced.

Description

Technical Field

[0001] The present invention relates to fluorine-containing aryl borate, and in particular to a loaded long-chain fluorine-containing aryl borate, a preparation method and application thereof. Background Art

[0002] Polyolefins are one of the most important synthetic materials, accounting for 60% of the total output of synthetic resins. Catalyst development is driving the progress of the polyolefin industry. The discovery of metallocene catalysts in the 1980s ushered in a new era for the industry. However, metallocenes require expensive MAO / MMAO catalysts, and the large amounts of MAO / MMAO added also introduce significant amounts of ash into the polyolefins. To address this issue, supported metallocene catalysts were developed, imparting new properties while avoiding the need for large amounts of MAO / MMAO. However, this approach reduces catalyst activity. Summary of the Invention

[0003] In order to solve the above technical problems, the present invention provides a preparation method of a supported long-chain fluorine-containing aryl borate. The supported long-chain fluorine-containing aryl borate can improve the morphology of the polymer while ensuring the activity of the metallocene catalyst, uses inexpensive alkyl aluminum, and avoids the use of MAO / MMAO.

[0004] In one aspect, the present invention provides a method for preparing a supported long-chain fluorine-containing aryl borate, the method comprising the following steps:

[0005] A: Amine compounds and hydrochloric acid react in a solvent to form quaternary ammonium salts;

[0006] B: (4-Bromophenoxy)alkylsilane, magnesium chips and 1,2-dibromoethane are heated in a solvent to react to generate a Grignard reagent;

[0007] C: Grignard reagent and perfluoroarylborane react in a solvent to form fluorinated aryl borate;

[0008] D: Fluorine-containing aryl borate and quaternary ammonium salt react in a solvent to form a long-chain fluorine-containing aryl borate;

[0009] E: reacting the heat-treated silica with silane and triethylamine in a solvent to generate silane-modified silica;

[0010] F: Long-chain fluorine-containing aryl borate and silane-modified silica generate supported long-chain fluorine-containing aryl borate in solvent;

[0011]

[0012] In the present invention, the structural formula of the amine compound is Wherein R1 is independently selected from hydrogen and C1-C18 alkyl, R2 and R3 are independently selected from C1-C18 alkyl, preferably, R1 is independently selected from hydrogen and C8-C18 alkyl; R2 and R3 are independently selected from C8-C18 alkyl.

[0013] In the present invention, the structural formula of (4-bromophenoxy)alkylsilane is R4, R5, and R6 are independently selected from C1 to C18 alkyl groups. Preferably, R4, R5, and R6 are independently selected from C1 to C6 alkyl groups.

[0014] In the present invention, the structural formula of the silane in step E is SiH 4-n R n , R is independently selected from C1~C18 alkyl, phenyl, 1≤n≤2; preferably, R is independently selected from C1~C3 alkyl, phenyl, preferably, the silane is at least one of phenylsilane, diphenylsilane, methylphenylsilane, dimethylsilane, and diethylsilane.

[0015] In the present invention, the solvent in each step is selected from at least one of n-hexane, n-heptane, diethyl ether, cyclohexane, nonane, tetrahydrofuran, diethyl ether, deionized water and pentane.

[0016] In the present invention, the perfluoroaryl borane is at least one selected from tris(pentafluorophenyl)borane, tris(1,3,4,5,6,7,8-heptafluoro-2-naphthyl)borane, and tris(2,3,4,5,6,7,8-heptafluoro-1-naphthyl)borane.

[0017] In the present invention, the molar ratio of the amine compound to the hydrochloric acid in step A is 1:1 to 1:3.

[0018] In the present invention, in step B, the molar ratio of (4-bromophenoxy)alkylsilane to magnesium in magnesium chips is 1:1.3 to 1:1.5; the molar ratio of 1,2-dibromoethane to magnesium in magnesium chips is 1:17.2 to 1:17.5.

[0019] In the present invention, the molar ratio of the Grignard reagent to the perfluoroaryl borane in step C is 1:1.05 to 1:1.10.

[0020] In the present invention, the molar ratio of the fluorine-containing aryl borate to the quaternary ammonium salt in step D is 1:1.3 to 1:1.4.

[0021] In the present invention, the molar ratio of silicon dioxide to silane in step E is 1:4.0 to 1:5.0, and the molar ratio of silane to triethylamine in step E is 1:1.0 to 1:1.1.

[0022] In the present invention, the molar ratio of the long-chain fluorine-containing aryl borate to the silane-modified silica in step F is 1.1:1 to 1.3:1.

[0023] In the present invention, the amount of solvent added in step A is 100 to 150 ml, preferably 100 to 120 ml, per 1 g of reactants.

[0024] In the present invention, the reaction of the amine compound and hydrochloric acid in step A is carried out at room temperature for 2 to 8 hours, preferably 2 to 6 hours.

[0025] In the present invention, the heating temperature in step B is 70-100° C., preferably 75-85° C., and the reaction time is 1-4 h, preferably 1-2 h.

[0026] In the present invention, the amount of solvent added in step B is 10 to 15 ml, preferably 10 to 12 ml, per 1 g of reactants.

[0027] In the present invention, the reaction time in step C is 16 to 32 hours, preferably 16 to 24 hours, and the reaction temperature is 70 to 100° C., preferably 75 to 85° C.

[0028] In the present invention, the amount of solvent added in step C is 10 to 15 ml, preferably 12 to 14 ml, per 1 g of reactants.

[0029] In the present invention, the reaction time in step D is 16 to 32 hours, preferably 16 to 24 hours, and the reaction temperature is 101 to 110° C., preferably 101 to 106° C.

[0030] In the present invention, the amount of solvent added in step D is 5 to 15 ml, preferably 5 to 10 ml, per 1 g of reactants.

[0031] In the present invention, the heat treatment in step E is performed at 150-850° C. for 10 minutes to 72 hours, preferably at 400-600° C. for 8-24 hours.

[0032] In the present invention, the specific surface area of ​​the silicon dioxide in step E is 100 to 1000 m 2 / g, preferably 400-600m 2 / g, pore volume 0.5~3m 3 / g, preferably 1 to 2 m 3 / g.

[0033] In the present invention, the reaction time in step E is 10 to 30 hours, preferably 12 to 24 hours, and the reaction temperature is 38 to 45° C., preferably 38 to 43° C.

[0034] In the present invention, in step E, the molar ratio of silicon dioxide to silane is 1:4.0 to 1:5.0, and the molar ratio of silane to triethylamine is 1:1.0 to 1:1.1.

[0035] In the present invention, the amount of solvent added in step E is 5 to 30 ml, preferably 10 to 15 ml, relative to 1 g of silica.

[0036] In the present invention, the reaction time in step F is 10 to 30 hours, preferably 15 to 24 hours, and the reaction temperature is 35 to 45° C., preferably 35 to 40° C.

[0037] In the present invention, in step F, the volume of the solvent added per gram of the long-chain fluorine-containing aryl borate is 100 to 200 ml, preferably 100 to 150 ml.

[0038] In the present invention, the molar ratio of the long-chain fluorine-containing aryl borate to the silane-modified silica in step F is 1.1:1 to 1.3:1.

[0039] On the other hand, the present invention provides a long-chain fluorine-containing aryl borate prepared by the above preparation method.

[0040] Finally, the present invention provides application of the long-chain fluorine-containing aryl borate in olefin polymerization.

[0041] The present invention has the following beneficial effects: the use of supported long-chain fluorine-containing aryl borate can improve the activity of the catalyst, the molecular weight of the polymer and the comonomer insertion rate; in addition, the supported long-chain fluorine-containing aryl borate can use inexpensive alkyl aluminum, avoid the use of expensive MAO / MMAO, and reduce production costs. DETAILED DESCRIPTION

[0042] In order to better understand the technical solutions of the present invention, the present invention is further described below with reference to the following embodiments, but the present invention is not limited to the following embodiments.

[0043] The raw materials used in the examples are all conventional raw materials in the art, and the purity specifications used are analytically pure or chemically pure.

[0044] Sources of main raw materials in the following examples:

[0045] 1. (4-Bromophenoxy)tert-butyldimethylsilane: Tokyo Chemical Industry Co., Ltd. (Shanghai), >98.0%;

[0046] 2. (4-Bromophenoxy)(2-methylpropyl)dimethylsilane: Tokyo Chemical Industry Co., Ltd. (Shanghai), >98.0%;

[0047] 3. (4-Bromophenoxy)triethylsilane: Tokyo Chemical Industry Development Co., Ltd. (Shanghai), >98.0%;

[0048] 4. (4-Bromophenoxy)trimethylsilane: Shanghai Aladdin Biochemical Technology Co., Ltd., >98.0%;

[0049] 5. Octadecylmethylamine: Tokyo Chemical Industry (Shanghai) Co., Ltd., >97.0%;

[0050] 6. Octadecylamine: Merck chemical reagent, >99.0%;

[0051] 7. Tridecylamine: Merck chemical reagent, ≥99.0%;

[0052] 8. N, N-dodecylaniline: Merck chemical reagent, ≥97.0%;

[0053] 9. N, N-hexadecylaniline: Merck chemical reagent, ≥98.0%;

[0054] 10. Trioctylamine: Merck chemical reagent, ≥98.0%;

[0055] 11. Phenylsilane: Merck chemical reagent, ≥97.0%;

[0056] 12. Methylphenylsilane: Merck chemical reagent, ≥95.0%;

[0057] 13. Dimethylsilane: Sagechem chemical reagent, ≥97.0%;

[0058] 14. Diethylsilane: Merck chemical reagent, ≥99.0%;

[0059] 15. Tris(pentafluorophenyl)borane: Merck chemical reagent, ≥98.0%;

[0060] 16. Tris(1,3,4,5,6,7,8-heptafluoro-2-naphthyl)borane: Atuo Chemical Co., Ltd., ≥95.0%;

[0061] 17. Pentane: Merck chemical reagent, ≥99.0%;

[0062] 18. Ether: Merck chemical reagent, ≥99.0%;

[0063] 19. Hydrochloric acid: Merck Chemical Reagent, 1 M in ether;

[0064] 20. Tetrahydrofuran: Merck chemical reagent, ≥99.0%;

[0065] 21. Hexane: Merck chemical reagent, ≥99.0%;

[0066] 22. Magnesium chips: Merck chemical reagent, size 0.06-0.3mm;

[0067] 23. Silica: Deshan (Chemical) Zhejiang Co., Ltd., specific surface area 400-600 m2 / g, pore volume 1-2 m3 / g;

[0068] Example 1

[0069] 1a. Quaternary ammonium salt (C 18 H 37 )2NMeHCl preparation

[0070] 1.5 g of octadecylmethylamine (2.8 mmol) was dissolved in 150 ml of hexane, and HCl (1 M, 2.8 mL) in ether was added via syringe. The mixture was stirred for 2 hours, filtered, and the filtered solid was washed with hexane and dried under vacuum.

[0071] 1b. Preparation of MgBr-C6H4-p-OSiMe3

[0072] Add 1.2 g of magnesium chips (49.4 mmol) to 12 ml of tetrahydrofuran, then mix with 1,2-dibromoethane (2.87 mmol). After mixing, add 93 ml of (4-bromophenoxy)trimethylsilane (38.0 mmol) in tetrahydrofuran solution. Heat to 75 ° C for 1 hour, cool to room temperature and filter to obtain the product solution.

[0073] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.20 (s, 9H, -CH3).

[0074] 1c.[MgBr·2THF] + [(C6F5)3B-C6H4-p-OSiMe3] - preparation

[0075] 97 ml of MgBr-C6H4-p-OSiMe3 (30.0 mmol) tetrahydrofuran solution and 192 ml of tris(pentafluorophenyl)borane (31.5 mmol) ether solution were heated to 75 ° C and reacted for 16 hours. After the reaction, 288 ml of pentane was added, stirred and shaken for 30 minutes, and allowed to stand. The lower layer was then taken out and this operation was repeated twice. The solvent was drained to obtain a solid.

[0076] 1H NMR (CDCl3, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.20 (s, 9H, -CH3).

[0077] 19F NMR (CDCl3, 500MHz), δ: -130.7 (m, 6F, oF), -163.6 (t, 3F, pF), -166.7 (t, 6F, mF)

[0078] 1d.[(C 18 H 37)2MeNH] + [(C6F5)3B-C6H4-p-OH] - preparation

[0079] [MgBr·2THF] + [(C6F5)3B-C6H4-p-OSiMe3] - (23.90 mmol) and (C 18 H 37 )2NMeHCl (31.07 mmol) was added to 186 ml of deionized water, heated to 101°C and stirred for 16 h, filtered, and the filtered solid was washed with 186 ml of deionized water and 186 ml of pentane, respectively, and dried under vacuum.

[0080] 1H NMR (CDCl3, TMS, 500MHz), δ: 2.46 (d, 3H, -CH3), 1.29-1.26 (t, 68H, -CH2-), 0.35 (s, 1H, -OH), 0.88 (s, 6H, -CH3).

[0081] 19F NMR (CDCl3, 500MHz), δ: -130.7 (m, 6F, oF), -163.6 (t, 3F, pF), -166.7 (t, 6F, mF)

[0082] 1e. Preparation of Silica-O-SiH2Ph

[0083] At room temperature and nitrogen atmosphere, phenylsilane (20.1 mmol), triethylamine (20.1 mmol) and 10 g of silica (heated at 400°C for 24 h, hydroxyl content 0.50 mmol / g) were reacted in 120 ml of pentane solution for 12 h, filtered, and the filtered solid was washed with 120 ml of pentane and dried under vacuum.

[0084] IR:v(Si-H)2178cm-1

[0085] 21 Si:CPMASδ-23ppm

[0086] 1f.[(C 18 H 37 )2MeNH] + [(C6F5)3B-C6H4-pO-SiHPh-O-Silica] - preparation

[0087] At room temperature and nitrogen atmosphere, 528 ml of [(C 18 H 37 )2MeNH] +[(C6F5)3B-C6H4-p-OH] - Mix 100 ml of ether solution of Silica-O-SiH2Ph (4.57 mmol) and ether solution of Silica-O-SiH2Ph (5.0 mmol) and heat to 35 ° C for 15 h, filter, wash the filtered solid with 628 ml of ether and 628 ml of pentane, respectively, and dry under vacuum.

[0088] Example 2

[0089] 2a. Quaternary ammonium salt (C 18 H 37 )2NH2Cl preparation

[0090] Octadecanamine (2.8 mmol) was dissolved in 150 ml of hexane, and HCl (1 M, 4.2 mL) in diethyl ether was added via syringe. The mixture was stirred for 3 hours, filtered, and the filtered solid was washed with hexane and dried under vacuum.

[0091] 2b.MgBr-C6H4-p-OSiMe2 t Bu Preparation

[0092] Add 1.2 g of magnesium chips (49.4 mmol) to 13 ml of tetrahydrofuran, then mix with 1,2-dibromoethane (2.86 mmol). After mixing, add 115 ml of (4-bromophenoxy)tert-butyldimethylsilane (36.6 mmol) in tetrahydrofuran solution, heat to 78 ° C for 1.2 h, cool to room temperature and filter to obtain the product solution.

[0093] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.20 (s, 9H, -CH3), 0.20 (s, 6H, -CH3).

[0094] 2c.[MgBr·2THF] + [(C6F5)3B-C6H4-p-OSiMe2 t Bu] - preparation

[0095] 121 ml MgBr-C6H4-p-OSiMe2 t A solution of Bu (30.0 mmol) in tetrahydrofuran and a solution of tris(pentafluorophenyl)borane (31.8 mmol) in ether were heated to 78°C and reacted for 18 h. After the reaction, 232 ml of pentane was added, stirred and shaken for 30 min, and allowed to stand. The lower layer was then taken out and this operation was repeated twice. The solvent was then drained to obtain a solid.

[0096] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.20 (s, 9H, -CH3), 0.20 (s, 6H, -CH3).

[0097] 19F NMR (CDCl3, 500MHz), δ: -130.7 (m, 6F, oF), -163.6 (t, 3F, pF), -166.7 (t, 6F, mF)

[0098] 2d.[(C 18 H 37 )2HNH] + [(C6F5)3B-C6H4-p-OH] - preparation

[0099] [MgBr·2THF] + [(C6F5)3B-C6H4-p-OSiMe2 t Bu] - (23.9 mmol) and (C 18 H 37 )2NH2Cl (31.0 mmol) was added to 228 ml of deionized water, heated to 102°C and stirred for 18 h, filtered, and the filtered solid was washed with 228 ml of deionized water and 228 ml of pentane, respectively, and dried under vacuum.

[0100] 1H NMR (CDCl3, TMS, 500MHz), δ: 2.46 (d, 3H, -CH3), 1.29-1.26 (t, 68H, -CH2-), 0.35 (s, 1H, -OH), 0.10 (s, 1H, -NH).

[0101] 19F NMR (CDCl3, 500MHz), δ: -130.7 (m, 6F, oF), -163.6 (t, 3F, pF), -166.7 (t, 6F, mF)

[0102] 2e. Preparation of Silica-O-SiHPhMe

[0103] At room temperature and nitrogen atmosphere, methylphenylsilane (20.1 mmol), triethylamine (21.1 mmol) and 9.56 g of silica (heated at 450°C for 20 h, hydroxyl content 0.50 mmol / g) were reacted in 132 ml of pentane solution for 15 h, filtered, and the filtered solid was washed with 132 ml of pentane and dried under vacuum.

[0104] IR:v(Si-H)2135cm-1

[0105] 21 Si:CPMASδ-15ppm

[0106] 2f.[(C 18 H 37 )2NH2] + [(C6F5)3B-C6H4-pO-SiPhMe-O-Silica] - preparation

[0107] At room temperature and nitrogen atmosphere, 522 ml of [(C 18 H 37 )2NH2] + [(C6F5)3B-C6H4-p-OH] - Mix 105 ml of Silica-O-SiHPhMe (4.78 mmol) ether solution and 105 ml of ether solution and heat to 36 ° C for 18 h, filter, wash the filtered solid with 627 ml of ether and 627 ml of pentane, respectively, and dry under vacuum.

[0108] Example 3

[0109] 3a. Quaternary ammonium salt (C 12 H 25 )3NHCl preparation

[0110] Tridodecylamine (2.8 mmol) was dissolved in 166 ml of hexane, and HCl (1 M, 5.6 mL) in ether was added via syringe. The mixture was stirred for 4 hours, filtered, and the filtered solid was washed with hexane and dried under vacuum.

[0111] 3b. Preparation of MgBr-C6H4-p-OSi(CH3)2CH2CH(CH3)2

[0112] Add 1.2 g of magnesium chips (49.4 mmol) to 12 ml of tetrahydrofuran, then mix with 1,2-dibromoethane (2.84 mmol). After mixing, add 120 ml of (4-bromophenoxy)(2-methylpropyl)dimethylsilane (35.3 mmol) in tetrahydrofuran solution, heat to 80 ° C for 1.4 h, cool to room temperature and filter to obtain the product solution.

[0113] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.80 (t, 1H, -CH-), 1.00 (t, 2H, -CH2-), 0.90 (s, 6H, -CH3), 0.20 (s, 6H, -CH3).

[0114] 3c.[MgBr·2THF] + [(C6F5)3B-C6H4-p-OSi(CH3)2CH2CH(CH3)2] - preparation

[0115] Heat 130 ml of MgBr-C6H4-p-OSi(CH3)2CH2CH(CH3)2 (30.0 mmol) tetrahydrofuran solution and 229 ml of tris(pentafluorophenyl)borane (32.1 mmol) ether solution to 80 ° C and react for 20 hours. After the reaction, add 359 ml of pentane, stir and shake for 30 minutes, let it stand, then take out the lower layer, repeat this operation twice, and drain the solvent to obtain a solid.

[0116] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.80 (t, 1H, -CH-), 1.00 (t, 2H, -CH2-), 0.90 (s, 6H, -CH3), 0.20 (s, 6H, -CH3).

[0117] 19F NMR (CDCl3, 500MHz), δ: -130.7 (m, 6F, oF), -163.6 (t, 3F, pF), -166.7 (t, 6F, mF)

[0118] 3d.[(C 12 H 25 )3NH] + [(C6F5)3B-C6H4-p-OH] - preparation

[0119] [MgBr·2THF] + [(C6F5)3B-C6H4-p-OSi(CH3)2CH2CH(CH3)2] - (23.9 mmol) and (C 12 H 25 )3NHCl (33.4 mmol) was added to 251 ml of deionized water, heated to 103°C and stirred for 20 h, filtered, and the filtered solid was washed with 251 ml of deionized water and 251 ml of pentane, respectively, and dried under vacuum.

[0120] 1H NMR (CDCl3, TMS, 500MHz), δ: 2.46 (d, 3H, -CH3), 1.29-1.26 (t, 66H, -CH2-) 0.35 (s, 1H, -OH).

[0121] 19F NMR (CDCl3, 500MHz), δ: -130.7 (m, 6F, oF), -163.6 (t, 3F, pF), -166.7 (t, 6F, mF)

[0122] 3e. Preparation of Silica-O-SiHMe2

[0123] At room temperature and nitrogen atmosphere, dimethylsilane (20.1 mmol), triethylamine (22.1 mmol) and 9.12 g of silica (heated at 500°C for 16 h, hydroxyl content 0.50 mmol / g) were reacted in 133 ml of pentane solution for 18 h, filtered, and the filtered solid was washed with 133 ml of pentane and dried under vacuum.

[0124] IR:v(Si-H)2158cm-1

[0125] 21 Si:CPMASδ-1.3ppm

[0126] 3f.[(C 12 H 25 )3NH] + [(C6F5)3B-C6H4-pO-SiMe2-O-Silica] - preparation

[0127] At room temperature and nitrogen atmosphere, 490 ml of [(C 12 H 25 )3NH] + [(C6F5)3B-C6H4-p-OH] - Mix 109 ml of Silica-O-SiHMe2 (3.81 mmol) ether solution and 109 ml of Silica-O-SiHMe2 (4.57 mmol) ether solution and heat to 37 ° C for 21 hours, filter, wash the filtered solid with 599 ml of ether and 599 ml of pentane, and dry under vacuum.

[0128] Example 4

[0129] 4a. Quaternary ammonium salt (C 12 H 25 )2PhNHCl Preparation

[0130] N, N-dodecylaniline (2.8 mmol) was dissolved in 139 ml of hexane, and HCl (1 M, 7.0 mL) in ether was added via syringe. The mixture was stirred for 5 hours and filtered. The filtered solid was washed with hexane and dried under vacuum.

[0131] 4b. Preparation of MgBr-C6H4-p-OSiEt3

[0132] Add 1.2 g of magnesium chips (49.4 mmol) to 12 ml of tetrahydrofuran, then mix with 1,2-dibromoethane (2.82 mmol). After mixing, add 97 ml of (4-bromophenoxy)triethylsilane (34.0 mmol) in tetrahydrofuran, heat to 82 ° C for 1.6 h, cool to room temperature and filter to obtain the product solution.

[0133] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.06 (t, 6H, -CH2-), 0.90 (s, 9H, -CH3).

[0134] 4c.[MgBr·2THF] + [(C6F5)3B-C6H4-p-OSiEt3] - preparation

[0135] Heat 112 ml of MgBr-C6H4-p-OSiEt3 (30.0 mmol) tetrahydrofuran solution and 196 ml of tris(pentafluorophenyl)borane (32.4 mmol) ether solution to 82 ° C for 22 h. After the reaction, add 308 ml of pentane, stir and shake for 30 min, let it stand, then take out the lower layer, repeat this operation twice, and drain the solvent to obtain a solid.

[0136] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.06 (t, 6H, -CH2-), 0.90 (s, 9H, -CH3).

[0137] 19F NMR (CDCl3, 500MHz), δ: -130.7 (m, 6F, oF), -163.6 (t, 3F, pF), -166.7 (t, 6F, mF).

[0138] 4d.[(C 12 H 25 )2PhNH] + [(C6F5)3B-C6H4-p-OH] - preparation

[0139] [MgBr·2THF] + [(C6F5)3B-C6H4-p-OSiEt3] - (23.9 mmol) and (C 12 H 25)2PhNHCl (32.2 mmol) was added to 257 ml of deionized water, heated to 104 ° C and stirred for 22 h, filtered, and the filtered solid was washed with 257 ml of deionized water and 257 ml of pentane, respectively, and dried under vacuum.

[0140] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.79-6.76 (t, 3H, Ph-H), 3.78-3.75 (t, 4H, -CH2-), 1.49-1.25 (t, 40H, -CH2-), 0.88 (s, 6H, -CH3).

[0141] 19F NMR (CDCl3, 500MHz), δ: -130.7 (m, 6F, oF), -163.6 (t, 3F, pF), -166.7 (t, 6F, mF).

[0142] 4e. Preparation of Silica-O-SiHEt2

[0143] At room temperature and nitrogen atmosphere, diethylsilane (20.1 mmol), triethylamine (21.1 mmol) and 8.72 g of silica (heated at 550°C for 12 h, hydroxyl content 0.50 mmol / g) were reacted in 140 ml of pentane solution for 20 h. The mixture was filtered, and the filtered solid was washed with 140 ml of pentane and dried under vacuum.

[0144] IR:v(Si-H)2141cm-1

[0145] 21 Si:CPMASδ+5ppm

[0146] 4f.[(C 12 H 25 )2PhNH] + [(C6F5)3B-C6H4-pO-SiEt2-O-Silica] - preparation

[0147] At room temperature and nitrogen atmosphere, 483 ml of [(C 12 H 25 )2PhNH] + [(C6F5)3B-C6H4-p-OH] - A mixture of (3.50 mmol) ether solution and 113 ml of Silica-O-SiHEt2 (4.37 mmol) ether solution was heated to 38°C and reacted for 24 h. The mixture was filtered, and the filtered solid was washed with 596 ml of ether and 596 ml of pentane, respectively, and dried under vacuum.

[0148] Example 5

[0149] 5a. Quaternary ammonium salt (C 16 H 33 )2PhNHCl Preparation

[0150] N,N-hexadecylaniline (2.8 mmol) was dissolved in 150 ml of hexane, and HCl (1 M, 8.4 mL) in ether was added via syringe. The mixture was stirred for 6 hours and filtered. The filtered solid was washed with hexane and dried under vacuum.

[0151] 5b. Preparation of MgBr-C6H4-p-OSiMe3

[0152] Add 1.2 g of magnesium chips (49.4 mmol) to 13 ml of tetrahydrofuran, then mix with 1,2-dibromoethane (2.87 mmol). After mixing, add 89 ml of (4-bromophenoxy)trimethylsilane (32.9 mmol) in tetrahydrofuran solution. Heat to 85 ° C for 2 h, cool to room temperature and filter to obtain the product solution.

[0153] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.20 (s, 9H, -CH3).

[0154] 5c.[MgBr·2THF] + [(C 10 F7)3B-C6H4-p-OSiMe3] - preparation

[0155] 105 ml of MgBr-C6H4-p-OSiMe3 (30.0 mmol) tetrahydrofuran solution and 327 ml of tri(1,3,4,5,6,7,8-heptafluoro-2-naphthyl)borane (32.7 mmol) ether solution were heated to 85 ° C and reacted for 24 hours. After the reaction, 432 ml of pentane was added, stirred and shaken for 30 minutes, and allowed to stand. The lower layer was then taken out and this operation was repeated twice. The solvent was drained to obtain a solid.

[0156] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.20 (s, 9H, -CH3).

[0157] 19F NMR (CDCl3, 500MHz), δ: -125.7 (t, 6F), -160.1 (t, 3F), -170.2 (t, 12F).

[0158] 5d.[(C 16 H33 )2PhNH] + [(C 10 F7)3B-C6H4-p-OH] - preparation

[0159] [MgBr·2THF] + [(C 10 F7)3B-C6H4-p-OSiEt3] - (23.9 mmol) and (C 16 H 33 )2PhNHCl (31.0 mmol) was added to 363 ml of deionized water, heated to 105 °C and stirred for 16 h, filtered, and the filtered solid was washed with 363 ml of deionized water and 363 ml of pentane, respectively, and dried under vacuum.

[0160] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.79-6.76 (t, 3H, Ph-H), 3.78-3.75 (t, 4H, -CH2-), 1.49-1.25 (t, 56H, -CH2-), 0.88 (s, 6H, -CH3).

[0161] 19F NMR (CDCl3, 500MHz), δ: -125.7 (t, 6F), -160.1 (t, 3F), -170.2 (t, 12F).

[0162] 5e. Preparation of Silica-O-SiHMe2

[0163] At room temperature and nitrogen atmosphere, dimethylsilane (20.1 mmol), triethylamine (22.1 mmol) and 8.36 g of silica (heated at 600°C for 10 h, hydroxyl content 0.50 mmol / g) were reacted in 144 ml of pentane solution for 12 h, filtered, and the filtered solid was washed with 144 ml of pentane and dried under vacuum.

[0164] IR:v(Si-H)2158cm-1

[0165] 21 Si:CPMASδ-1.3ppm

[0166] 5f.[(C 16 H 33 )2PhNH] + [(C 10 F7)3B-C6H4-pO-SiMe2-O-Silica] - preparation

[0167] At room temperature and nitrogen atmosphere, 646 ml of [(C 16 H 33 )2PhNH] + [(C 10 F7)3B-C6H4-p-OH] - A mixture of (3.22 mmol) ether solution and 117 ml of Silica-O-SiHEt2 (4.19 mmol) ether solution was heated to 39 ° C for 15 h, filtered, and the filtered solid was washed with 763 ml of ether and 763 ml of pentane, respectively, and dried under vacuum.

[0168] Example 6

[0169] 6a. Quaternary ammonium salt (C8H 17 )3NHCl preparation

[0170] Trioctylamine (2.8 mmol) was dissolved in 150 ml of hexane, and HCl (1 M, 5.6 mL) in diethyl ether was added via syringe. The mixture was stirred for 4 hours and filtered. The filtered solid was washed with hexane and dried under vacuum.

[0171] 6b.MgBr-C6H4-p-OSiMe2 t Bu Preparation

[0172] Add 1.2 g of magnesium chips (49.4 mmol) to 12 ml of tetrahydrofuran, then mix with 1,2-dibromoethane (2.82 mmol). After mixing, add 101 ml of (4-bromophenoxy)tert-butyldimethylsilane (35.3 mmol) in tetrahydrofuran solution, heat to 80 ° C for 2 h, cool to room temperature and filter to obtain the product solution.

[0173] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.20 (s, 9H, -CH3), 0.20 (s, 6H, -CH3).

[0174] 6c.[MgBr·2THF] + [(C 10 F7)3B-C6H4-p-OSiMe2 t Bu] - preparation

[0175] 130mlMgBr-C6H4-p-OSiMe2 tA solution of Bu (30.0 mmol) in tetrahydrofuran and a solution of tri(1,3,4,5,6,7,8-heptafluoro-2-naphthyl)borane (33.0 mmol) in ether were heated to 80°C and reacted for 24 h. After the reaction, 485 ml of pentane was added, stirred and shaken for 30 min, and allowed to stand. The lower layer was then taken out and this operation was repeated twice. The solvent was then drained to obtain a solid.

[0176] 1H NMR (CDCl3, TMS, 500MHz), δ: 7.49 (d, 2H, Ph-H), 6.76 (d, 2H, Ph-H), 1.20 (s, 9H, -CH3), 0.20 (s, 6H, -CH3).

[0177] 19F NMR (CDCl3, 500MHz), δ: -125.7 (t, 6F), -160.1 (t, 3F), -170.2 (t, 12F).

[0178] 6d.[(C8H 17 )3NH] + [(C 10 F7)3B-C6H4-p-OH] - preparation

[0179] [MgBr·2THF] + [(C 10 F7)3B-C6H4-p-OSiMe2 t Bu] - (23.9 mmol) and (C8H 17 )3NHCl (33.5 mmol) was added to 365 ml of deionized water, heated to 106°C and stirred for 24 h, filtered, and the filtered solid was washed with 365 ml of deionized water and 365 ml of pentane, respectively, and dried under vacuum.

[0180] 1H NMR (CDCl3, TMS, 500MHz), δ: 3.01-2.96 (d, 6H, -CH2-), 1.36-1.29 (t, 36H, -CH2-), 0.20 (s, 9H, -CH3).

[0181] 19F NMR (CDCl3, 500MHz), δ: -125.7 (t, 6F), -160.1 (t, 3F), -170.2 (t, 12F).

[0182] 6e. Preparation of Silica-O-SiHPhMe

[0183] At room temperature and nitrogen atmosphere, methylphenylsilane (20.1 mmol), triethylamine (20.1 mmol) and 8 g of silica (heated at 500°C for 8 h, hydroxyl content 0.50 mmol / g) were reacted in 155 ml of pentane solution for 12 h, filtered, and the filtered solid was washed with 155 ml of pentane and dried under vacuum.

[0184] IR:v(Si-H)2135cm -1

[0185] 21 Si:CPMASδ-15ppm

[0186] 6f.[(C 16 H 33 )2PhNH] + [(C 10 F7)3B-C6H4-pO-SiPhMe2-O-Silica] - preparation

[0187] At room temperature and nitrogen atmosphere, 632 ml of [(C8H 17 )3NH] + [(C 10 F7)3B-C6H4-p-OH] - Mix 120 ml of Silica-O-SiHPhMe (3.35 mmol) ether solution and 120 ml of Silica-O-SiHPhMe (4.00 mmol) ether solution, heat to 40 ° C and react for 15 hours, filter, wash the filtered solid with 752 ml of ether and 752 ml of pentane, respectively, and dry under vacuum.

[0188] Performance characterization:

[0189] Ethylene / 1-octene copolymerization was carried out in a 2000ml autoclave. The reactor was heated to 120°C and evacuated for 3 hours. After several nitrogen replacements and ethylene cooling to room temperature, 0.8L of Isopar E, 0.2L of 1-octene, 750μmol of cocatalyst (TIBA or MMAO), 2.5μmol of CGC catalyst, and 3μmol of borate were added in sequence. The temperature was then raised to 180°C, and 3MPa of ethylene was introduced to initiate polymerization. The reaction mixture was allowed to react for 10 minutes. The ethylene was then vented, and the reaction mixture was poured into ethanol. The precipitated solid was collected, dried to constant weight in a 60°C vacuum oven, and weighed. Sample analysis was performed (Table 1).

[0190] Table 1 Polymerization addition amount and product characterization

[0191]

[0192] Note: The borate used in Comparative Example 1 is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and the borate used in Comparative Example 2 is triphenylcarbon tetrakis(pentafluorophenyl)borate.

Claims

1. A method for preparing a supported long-chain fluorine-containing aryl borate, the method comprising the following steps: A: Amine compounds and hydrochloric acid react in a solvent to form quaternary ammonium salts; B: (4-Bromophenoxy)alkylsilane, magnesium chips and 1,2-dibromoethane are heated in a solvent to react to generate a Grignard reagent; C: Grignard reagent and perfluoroarylborane react in a solvent to form fluorinated aryl borate; D: Fluorine-containing aryl borate and quaternary ammonium salt react in a solvent to form a long-chain fluorine-containing aryl borate; E: reacting the heat-treated silica with silane and triethylamine in a solvent to generate silane-modified silica; F: Long-chain fluorine-containing aryl borate and silane-modified silica are reacted in a solvent to generate supported long-chain fluorine-containing aryl borate.

2. The preparation method according to claim 1, wherein The structural formula of the amine compound in step A is wherein R1 is independently selected from hydrogen and C1-C18 alkyl, R2 and R3 are independently selected from C1-C18 alkyl, preferably, R1 is independently selected from hydrogen and C8-C18 alkyl; R2 and R3 are independently selected from C8-C18 alkyl; and / or, the structural formula of the (4-bromophenoxy)alkylsilane in step B is R4, R5, and R6 are independently selected from C1 to C18 alkyl groups. Preferably, R4, R5, and R6 are independently selected from C1 to C6 alkyl groups.

3. The preparation method according to claim 1 or 2, wherein The structural formula of the silane in step E is SiH 4- n R n , R is independently selected from C1~C18 alkyl, phenyl, 1≤n≤2; preferably, R is independently selected from C1~C3 alkyl, phenyl, preferably, the silane is at least one of phenylsilane, diphenylsilane, methylphenylsilane, dimethylsilane, and diethylsilane; and / or, the perfluoroarylborane in step C is selected from at least one of tris(pentafluorophenyl)borane, tris(1,3,4,5,6,7,8-heptafluoro-2-naphthyl)borane, and tris(2,3,4,5,6,7,8-heptafluoro-1-naphthyl)borane.

4. The preparation method according to any one of claims 1 to 3, wherein The molar ratio of the amine compound to the hydrochloric acid in step A is 1:1 to 1:3; and / or, the molar ratio of (4-bromophenoxy)alkylsilane to magnesium in magnesium chips in step B is 1:1.3 to 1:1.5; the molar ratio of 1,2-dibromoethane to magnesium in magnesium chips is 1:17.2 to 1:17.5; and / or, the molar ratio of the Grignard reagent to perfluoroarylborane in step C is 1:1.05 to 1:1.

10.

5. The preparation method according to any one of claims 1 to 4, characterized in that The molar ratio of the fluorine-containing aryl borate to the quaternary ammonium salt in step D is 1:1.3 to 1:1.4; and / or, the molar ratio of silica to silane in step E is 1:4.0 to 1:5.0, and the molar ratio of silane to triethylamine in step E is 1:1.0 to 1:1.1; and / or, the molar ratio of the long-chain fluorine-containing aryl borate to silane-modified silica in step F is 1.1:1 to 1.3:

1.

6. The preparation method according to any one of claims 1 to 5, characterized in that The reaction of the amine compound and hydrochloric acid in step A is carried out at room temperature for 2 to 8 hours, preferably 2 to 6 hours; and / or, the heating temperature in step B is 70 to 100° C., preferably 75 to 85° C., and the reaction time is 1 to 4 hours, preferably 1 to 2 hours; and / or, the reaction time in step C is 16 to 32 hours, preferably 16 to 24 hours, and the reaction temperature is 70 to 100° C., preferably 75 to 85° C.

7. The preparation method according to any one of claims 1 to 6, wherein The reaction time in step D is 16 to 32 hours, preferably 16 to 24 hours, and the reaction temperature is 101 to 110° C., preferably 101 to 106° C.; and / or, the heat treatment in step E is performed at 150 to 850° C. for 10 minutes to 72 hours, preferably at 400 to 600° C. for 8 to 24 hours; and / or, the specific surface area of ​​the silica in step E is 100 to 1000 m 2 / g, preferably 400-600m 2 / g, pore volume 0.5~3m 3 / g, preferably 1 to 2 m 3 / g; and / or, the reaction time in step E is 10 to 30 h, preferably 12 to 24 h, and the reaction temperature is 38 to 45 ° C, preferably 38 to 43 ° C.

8. The preparation method according to any one of claims 1 to 7, wherein In step E, the molar ratio of silica to silane is 1:4.0 to 1:5.0, and the molar ratio of silane to triethylamine is 1:1.0 to 1:1.1; and / or, the reaction time in step F is 10 to 30 hours, preferably 15 to 24 hours, and the reaction temperature is 35 to 45° C., preferably 35 to 40° C.; and / or, in step F, the amount of solvent added per gram of long-chain fluorine-containing aryl borate is 100 to 200 ml, preferably 100 to 150 ml; and / or, in step F, the molar ratio of long-chain fluorine-containing aryl borate to silane-modified silica is 1.1:1 to 1.3:

1.

9. A long-chain fluorine-containing aryl borate prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the long-chain fluorine-containing aryl borate prepared by the preparation method according to any one of claims 1 to 8 or the long-chain fluorine-containing aryl borate according to claim 9 in olefin polymerization.

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