Fluorine-containing aryl borate compounds containing alkyl metal-based units, their preparation and use in catalyzing the polymerization of olefins

Abstract

The present application relates to fluorine-containing aryl borate compounds containing alkyl metal group units and preparation and application thereof in catalyzing olefin polymerization, the chemical structural formula of the fluorine-containing aryl borate compounds is {(F m Ar 1 ) 4‑n [F x Ar 2 -Q-Z-M(R) j ] n B} ‑ N + , which are obtained by introducing alkyl metal group units on the basis of fluorine-containing phenyl borate. Compared with the prior art, the fluorine-containing aryl borate compounds provided by the present application can interact with metallocene compound catalysts as cocatalysts, form catalyst systems and catalyze olefin polymerization, which not only can improve the stability of the catalyst system, but also is beneficial to widening the molecular weight distribution of polyolefins, improving the processing performance and the like.

Description

Technical Field

[0001] This invention belongs to the field of olefin polymerization cocatalyst technology, and relates to a fluorinated aryl borate compound containing alkyl metal group units, its preparation and its application in catalytic olefin polymerization. Background Technology

[0002] Fluorinated aryl borates are compounds in which four aromatic groups are attached to a boron atom, with at least one to three of them being fluorinated substituted aryl groups. The cations are inorganic cations such as Li, Na, and K, or ammonium and carbonaceous cations. Fluorinated aryl borates can be divided into two main categories: one is tetra(perfluorophenyl)borates, such as lithium tetra(perfluorophenyl)borate, and the other is borates containing both fluorinated substituted aryl groups and other aromatic groups.

[0003] Because the boron atom is surrounded by four aryl groups, the resulting boron anion has a large volume and is far from the equilibrium cation. This characteristic allows fluorinated arylborate compounds to play an important role in metallocene-catalyzed olefin polymerization reaction systems. The large boron anion activates and stabilizes the cationic coordination active sites of the metallocene catalyst, balancing the charge and increasing the distance between the boron center and the metal center (e.g., Ti, Zr, Hf), providing a loose environment conducive to catalytic polymerization. In polyolefin systems, fluorinated arylborate compounds are defined as noncoordinate anionic (NCA) cocatalysts. They are another important class of metallocene cocatalysts, distinct from methylaluminoxane (MAO), and generally participate in metallocene-catalyzed olefin polymerization processes in small molar ratios.

[0004] However, both traditional cocatalysts have their shortcomings: 1. Fluorinated aryl borate compounds have good activation effects and are easy to store and transport, but due to their poor solubility (due to the large amount of fluorine), their application in gas-phase and slurry processes is limited, and they are currently used more in solution polymerization; 2. Traditional catalysts such as trimethylaluminum are more reactive, which places higher demands on storage, transfer and the equipment itself, and their safety is not as good as that of fluorinated aryl borate compounds.

[0005] Therefore, overcoming the shortcomings of the two traditional cocatalysts mentioned above is an important research topic worldwide. This invention is based on this premise. Summary of the Invention

[0006] The purpose of this invention is to provide a fluorinated aryl borate compound containing an alkyl metal group unit, its preparation and application, which, when used as a cocatalyst, can improve the stability of the catalyst system and, to a certain extent, enhance the solubility of the fluorinated aryl borate compound in organic solvents.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] In a first aspect, the present invention provides a fluorinated arylborate compound containing an alkyl metal group unit, the chemical structural formula of which is {(F m Ar 1 ) 4-n [F x Ar 2 -QZM(R) j ] n B} - N + ,in,

[0009] B represents the boron atom at the center of the borate salt, which carries a negative charge; F represents a fluorine atom; Q represents Ar. 2 Direct connection with Z without carbon, or connection to Ar. 2 and Z's C1-C 20 aliphatic linker; F m Ar 1 C6-C connected to the B bond 30 Substituted aryl group; F x Ar 2 C6-C connected to the B bond 18 Substituted aryl groups; Ar 1 Ar 2 Indicates an independently selected aryl group; m is an integer from 0 to 9, preferably not 0; x is an integer from 0 to 12, preferably not 0, representing different numbered aryl groups Ar (i.e., Ar). 1 and Ar 2 The number of fluorine atoms on the ); n is an integer from 1 to 4, which can be 1, 2, 3, or 4; Z is a nonmetallic atom in Group 15 or 16 of the IUPAC periodic table, connected to Q and M, and when Z is in Group 15, it is connected through hydrogen or C1-C. 12 The hydrocarbon group adjusts the number of bonding sites for Z to ensure that the fluorinated aryl borate compound is bonded to saturation and achieves charge balance; M is a metal atom in Group 2 or Group 3 of the IUPAC periodic table; R is C1-C. 20 The alkyl group, j represents the number of alkyl groups R attached to the M atom. When M is a Group 2 metal, j=1; when M is a Group 3 metal, j=2; N + It is an organic cation or a group IA metal cation with a carbon number of 3 to 90.

[0010] Furthermore, Q represents Ar 2 Direct connection with Z without carbon, or connection to Ar. 2 aliphatic linker of C1-C6 with Z; F m Ar 1 C6-C connected to the B bond 12(More preferably C6-C) 10 ) substituted aryl group; F x Ar 2 C6-C connected to the B bond 10 The substituted aryl group; m is an integer from 0 to 7, x is an integer from 0 to 6; Z is an oxygen or sulfur atom, bonded to Q and M; R is C1-C 10 Alkyl groups.

[0011] Furthermore, N + It is an organic cation containing 10 to 40 carbon atoms, selected from trimethylammonium ion, triethylammonium ion, tributylammonium ion, trioctylammonium ion, triethylmethylammonium ion, tributylmethylammonium ion, trioctylmethylammonium ion, tridecylmethylammonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, tetraoctylammonium ion, N,N-dimethylphenylammonium ion, N,N-dimethylphenylacetium ion, N,N-diethylphenylammon ... Any one of the following: methylbenzylammonium ion, N,N-diethylphenylacetate ion, di(tetradecyl)methylammonium ion, di(hexadecyl)methylammonium ion, di(octadecyl)methylammonium ion, triphenylmethyl cation, tri(p-methylphenyl)methyl cation, tri(p-methoxyphenyl)methyl cation, tri(p-trimethylsilylphenyl)methyl cation, tri(p-fluorophenyl)methyl cation, tri(p-trifluoromethylphenyl)methyl cation, or a mixed saturated alkylammonium ion with a total carbon number of 30-40.

[0012] Furthermore, N ＋ It is a group IA metal cation, which can be selected from metal ions such as lithium, sodium, potassium, and rubidium, with sodium ions being preferred.

[0013] Furthermore, M is magnesium or aluminum; and alkyl group R is at least one of methyl, ethyl, butyl, isobutyl, hexyl, isohexyl, and octyl.

[0014] In a second aspect, the present invention provides a method for preparing a fluorinated arylborate compound containing an alkyl metal group unit, wherein the fluorinated arylborate and an alkyl metal compound are reacted in an organic solvent to obtain the compound, wherein the chemical structural formula of the fluorinated arylborate is {(F m Ar 1 ) 4-n [F x Ar 2 -QZH] n B} - N + Wherein, H is a hydrogen atom; the alkyl metal compound is a compound in which M is saturatedly bonded to alkyl R.

[0015] Furthermore, the amount of fluorinated arylborate and alkyl metal compound added satisfies the following: the molar ratio of M atoms to B atoms is not less than n:1, and not more than 20:1, preferably n~5:1.

[0016] Furthermore, the reaction temperature is -100℃ to 100℃, preferably -10℃ to 50℃, and the mass ratio of the total mass of the fluorinated aryl boronic acid salt and the alkyl metal compound to the organic solvent is 0.01~100:1, preferably 0.1~10:1.

[0017] Furthermore, the alkyl metal compound is dibutylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, etc.;

[0018] The fluorinated aryl borate is tris(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, tris(pentafluorophenyl)(hydroxytetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, di(pentafluorophenyl)di(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, (pentafluorophenyl)tris(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, tetra(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, tris(pentafluorophenyl)(hydroxymethylphenyl)borate dimethylphenylammonium salt, tris(pentafluorophenyl)(hydroxyphenyl)borate dimethylphenylammonium salt, tris(pentafluorophenyl)(hydroxyethylphenyl)borate dimethylphenylammonium salt, di(pentafluorophenyl)di(hydroxytetrafluoro-substituted ... The following is a list of dimethylphenylammonium tri(pentafluorophenyl)borate, tri(pentafluorophenyl)(hydroxyethyltetrafluoro-substituted phenyl)borate, tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate, tri(pentafluorophenyl)(hydroxyethyltetrafluoro-substituted phenyl)borate, di(pentafluorophenyl)di(hydroxymethyltetrafluoro-substituted phenyl)borate, tri(pentafluorophenyl)tri(hydroxymethyltetrafluoro-substituted phenyl)borate, tetra(hydroxymethyltetrafluoro-substituted phenyl)borate, tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate, and tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate, tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate, and tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate, tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate, tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate, tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate, triethylammonium tri(pentafluorophenyl)borate.

[0019] Furthermore, the organic solvent is an aprotic solvent, for example, it can be n-hexane, etc.

[0020] In a third aspect, the present invention provides the application of a fluorinated aryl borate compound containing an alkyl metal group unit as a cocatalyst in the catalytic polymerization of olefins in conjunction with metallocene compounds.

[0021] In a fourth aspect, the present invention provides a method for catalyzing C2-C 40The catalyst system for olefin polymerization includes a main catalyst, a co-catalyst, and conventional auxiliaries. The main catalyst is a metallocene compound containing a five-membered metal ring coordination bond structure. The co-catalyst is a fluorinated arylborate compound containing an alkyl metal group unit as described in the first aspect above. Here, conventional auxiliaries are generally trimethylaluminum or dibutylmagnesium, etc.

[0022] Furthermore, the chemical structural formula of the metallocene compound is as follows:

[0023] ,

[0024] Where E represents titanium, zirconium, or hafnium;

[0025] X 1 X 2 Each is independently selected from halogens, C1-C 10 Alkyl, C6-C 10 Aryl, C1-C 10 Substituted alkyl, C6-C 10 Substituted aryl, where substituted alkyl or substituted aryl refers to one or more carbon atoms being replaced by heteroatoms;

[0026] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 Each is independently selected from H, C1-C 20 Alkyl, C6-C 20 Aryl, C1-C 20 Substituted alkyl, C6-C 20 Substitution of aryl groups;

[0027] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 Adjacent groups in the ring may optionally bond to each other and form cyclopentadienyl aryl groups with the five-membered ring to which they are attached;

[0028] Y represents silicon or carbon that has achieved valence saturation through substituents, wherein the substituents are C1-C. 20 Alkyl or substituted alkyl, C6-C 20 Aryl.

[0029] Furthermore, the metallocene compound may be dimethylsilylbis(n-propyl)cyclopentadienyl hafnium dichloride, dimethylsilylbis(n-propyl)cyclopentadienyl zirconium dichloride, dimethylsilylbis(n-propyl)cyclopentadienyl zirconium dichloride, dimethylsilylbis(n-propyl)cyclopentadienyl zirconium dichloride, dimethylsilylbis(n-propyl)cyclopentadienyl zirconium dichloride, diethylmethylenecyclopentadienyl(3,5-dimethylphenylindenyl) zirconium dichloride, etc.

[0030] Furthermore, the amounts of the main catalyst and the co-catalyst added satisfy the following condition: the B atom and the X atom... 1 X 2 The molar ratio of the sum is 0.1 to 100:1.

[0031] Compared with the prior art, this invention has made a breakthrough by introducing alkyl metal group units into the basis of fluorinated phenyl borate. The resulting novel catalyst not only improves the stability of the catalyst system, but also improves the solubility of fluorinated aryl borate compounds in organic solvents to a certain extent (the solubility of commonly used fluorinated aryl borates is about 1‰). Moreover, the introduction of the dual action site of the main catalyst metal is beneficial to broadening the molecular weight distribution of polyolefins, improving processing performance, and also facilitating the insertion of comonomers. Attached Figure Description

[0032] Figure 1 The molecular weight distribution diagram of the polymer product prepared in Example 41 is shown.

[0033] Figure 2 The molecular weight distribution diagram is shown for the polymer product prepared in Comparative Example 3. Detailed Implementation

[0034] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0036] As used herein, the terms "and / or," "or / and," and "and / or" encompass any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that, in this application, the technical solution undoubtedly includes solutions connected by "logical AND," and also undoubtedly includes solutions connected by "logical OR."

[0037] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0038] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0039] This document only specifically discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0040] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows temperature fluctuations within the precision range controlled by the instrument, such as ±5°C, ±4°C, ±3°C, ±2°C, or ±1°C.

[0041] In this document, the term "suitable" as used in phrases such as "suitable combination," "suitable method," and "any suitable method" refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0042] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0043] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0044] In the description of the application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0045] Unless otherwise specified, all preparations and tests described herein took place at 25°C.

[0046] The terms “comprising,” “including,” “containing,” “having,” “comprising,” or other variations thereof are intended to cover non-closed inclusion, and no distinction is made between these terms. The term “comprising” means that other steps and ingredients may be added without affecting the final result. The compositions and methods / processes of the present invention comprise, consist of, and substantially consist of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein. No distinction is made between the terms “efficacy,” “performance,” “effect,” and “potency” herein.

[0047] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions. Unless otherwise specified, all technical features and optional technical features of this application can be combined to form new technical solutions.

[0048] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, but sequentially is preferred.

[0049] In the following embodiments, the fluorinated phenyl borate salts such as tris(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt are conventional raw materials in the art and are not part of the innovative protection points of this invention. They can be synthesized by referring to the method of Example 12 in patent CN101863913A, except that equimolar amounts of raw materials such as 4-hydroxytetrafluorophenyl borate ester are used to replace diheptyl 4-hydroxyphenyl borate ester in Example 12 of patent CN101863913A.

[0050] The dimethylsilyl dicyclopentadienyl zirconium dichloride (CAS: 86050-32-0) used was purchased from Bailingwei Company. The metallocene compounds such as dimethylsilyl di-n-propylcyclopentadienyl hafnium dichloride and dimethylsilyl di-n-propylcyclopentadienyl zirconium dichloride are also conventional raw materials in the field and are not part of the innovative protection of this invention. They can be synthesized with reference to the patent (Example A10 in US10968290B2), except that the final step of chloromethylation was not performed.

[0051] The chemical structural formula of tri(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)borate triethylammonium salt is:

[0052] .

[0053] The chemical structural formula of hafnium dimethylsilylbis(n-propyl)cyclopentadienyl dichloride is:

[0054] .

[0055] Catalyst Synthesis

[0056] Example 1:

[0057] 8.13 g of tris(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane, which means that the concentration of dibutylmagnesium in n-hexane is 1 mol / L, the same below) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the solvent was removed under reduced pressure and crystallized at low temperature (-15 °C) to obtain 8.01 g of tris(pentafluorophenyl)(butylmagnesium oxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, with a yield of 89.8%.

[0058] 1 H NMR (500MHz, CDCl3) δ7.34 (d,2H,Ph-H), 6.51 (d,2H,Ph-H), 4.61 (m,2H,-OCH2-), 3.45 (t,2H,-CH2Mg), 2.68 (s,6H,CH3N-), 1.69 (m,4H,-CH2-), 1.20 (m,3H,-CH3).

[0059] Testing showed that the borate product obtained above had a solubility of 5.1 wt% in toluene at 25°C. However, the solubility of tris(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)borate dimethylaniline salt in toluene, tested under the same conditions as in Example 1, was approximately 0.1%. This demonstrates that the borate product obtained in Example 1, by introducing an alkyl metal group unit, exhibits significantly improved solubility in organic solvents such as toluene, thus making it suitable for gas-phase and slurry-phase processes.

[0060] Example 2

[0061] 8.13 g of tris(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of trimethylaluminum (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered, and the solvent was removed under reduced pressure. Crystallization was carried out at -15 °C to obtain 8.11 g of tris(pentafluorophenyl)(dimethylaluminoxomethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, with a yield of 93.2%.

[0062] 1 H NMR (500MHz, CDCl3) δ7.56 (d,2H,Ph-H), 6.42 (d,2H,Ph-H), 4.43 (m,2H,-OCH2-), 3.54 (t,6H,CH3Al), 2.86 (s,6H,CH3N-).

[0063] The solubility of the obtained borate in toluene was tested to be 3.2 wt% at 25°C.

[0064] Example 3

[0065] 8.13 g of tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of triethylaluminum (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 8.30 g of tri(pentafluorophenyl)(diethylaluminoxomethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, with a yield of 92.5%.

[0066] 1 H NMR (500MHz, CDCl3) δ7.45 (d,2H,Ph-H), 6.67 (d,2H,Ph-H), 4.45 (m,2H,-OCH2-), 3.45 (t,4H,-CH2Al), 2.68 (s,6H,CH3N-), 1.69 (m,6H,-CH3).

[0067] The test showed that the solubility of the obtained borate in toluene was 4.5 wt% at 25°C.

[0068] Example 4

[0069] 8.13 g of tris(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of triisobutylaluminum (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 8.55 g of tris(pentafluorophenyl)(diisobutylaluminumoxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, with a yield of 89.7%.

[0070] 1 H NMR (500MHz, CDCl3) δ7.32 (d,2H,Ph-H), 6.76 (d,2H,Ph-H), 4.48 (m,2H,-OCH2-), 3.78 (m,2 H, -CHAl), 2.78 (s, 6H, CH3N-), 1.64 (m, 6H, -CH3), 1.48 (m, 4H, -CH2CH3), 1.23 (m, 6H, -CH3).

[0071] Tests showed that the borate obtained at 25°C had a solubility of 7.9 wt% in toluene and 3.5% in cyclohexane.

[0072] Example 5

[0073] 8.13 g of tris(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of tri-n-butylaluminum (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 8.65 g of tris(pentafluorophenyl)(di-n-butylaluminoxytetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, with a yield of 90.7%.

[0074] H NMR (500MHz, CDCl3) δ7.38 (d,2H,Ph-H), 6.96 (d,2H,Ph-H), 4.44 (m,2H,-OCH2-), 3.45 (m,2 H, -CHAl), 2.78 (s, 6H, CH3N-), 1.65 (m, 4H, -CH2), 1.24 (m, 4H, -CH2CH3), 1.18 (m, 6H, -CH3).

[0075] Tests showed that the borate obtained at 25°C had a solubility of 7.3 wt% in toluene and 3.3% in cyclohexane.

[0076] Example 6

[0077] 8.13 g of tris(pentafluorophenyl)(hydroxytetrafluorosubstituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 14.64 g of tri-n-octyl aluminum (25 wt% n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 9.1 g of tris(pentafluorophenyl)(dioctyl aluminum oxytetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, with a yield of 85.4%.

[0078] H NMR (500MHz, CDCl3) δ7.36 (d,2H,Ph-H), 6.92 (d,2H,Ph-H), 4.45 (m,2H,-OCH2-), 3.43 (m,2H,- CHAl), 2.78 (s, 6H, CH3N-), 1.65 (m, 4H, -CH3), 1.24-1.48 (m, 12H, -CH2CH3), 1.09 (m, 6H, -CH3).

[0079] Tests showed that the borate obtained at 25°C had a solubility of 10.9 wt% in toluene and 6.9 wt% in cyclohexane.

[0080] Example 7

[0081] 8.21 g of di(pentafluorophenyl)di(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 3 hours, the solvent was removed under reduced pressure and crystallized at -15 °C to obtain 8.0 g of di(pentafluorophenyl)di(butylmagnesium oxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, with a yield of 81.5%.

[0082] 1 H NMR (500MHz, CDCl3) δ7.38 (d,2H,Ph-H), 6.54 (d,2H,Ph-H), 4.53 (m,2H,-OCH2-), 3.45 (t,4H,-CH2Mg), 2.68 (s,6H,CH3N-), 1.64 (m,8H,-CH2-), 1.25 (m,6H,-CH3).

[0083] Tests showed that the borate obtained at 25°C had a solubility of 5.3 wt% in toluene and 2.7% in cyclohexane.

[0084] Example 8

[0085] 8.33 g of (pentafluorophenyl)tris(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 3 hours, the solvent was removed under reduced pressure and crystallized at -15 °C to obtain 8.67 g of (pentafluorophenyl)tris(butylmagnesium oxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, with a yield of 80.8%.

[0086] 1 H NMR (500MHz, CDCl3) δ7.45 (d,2H,Ph-H), 6.65 (d,2H,Ph-H), 4.43 (m,2H,-OCH2-), 3.54 (t,4H,-CH2Mg), 2.56 (s,6H,CH3N-), 1.68 (m,12H,-CH2-), 1.20 (m,9H,-CH3).

[0087] Tests showed that the borate obtained at 25°C had a solubility of 5.8 wt% in toluene and 2.7% in cyclohexane.

[0088] Example 9

[0089] 8.45 g of tetra(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 3 hours, the solvent was removed under reduced pressure and crystallized at -15 °C to obtain 8.9 g of tetra(butylmagnesium oxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, with a yield of 76.3%.

[0090] 1 H NMR (500MHz, CDCl3) δ7.23 (d,2H,Ph-H),6.45 (d,2H,Ph-H),4.45 (m,2H,-OCH2-),3 .56 (t,4H,-CH2Mg), 2.67 (s,6H,CH3N-), 1.63 (m,16H,-CH2-), 1.23 (m,12H,-CH3).

[0091] Tests showed that the borate obtained at 25°C had a solubility of 7.8 wt% in toluene and 3.9% in cyclohexane.

[0092] Example 10

[0093] 7.41 g of tris(pentafluorophenyl)(hydroxymethylphenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of trimethylaluminum (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 7.1 g of tris(pentafluorophenyl)(dimethylaluminoxomethylphenyl)borate dimethylphenylammonium salt, with a yield of 89.0%.

[0094] 1 H NMR (500MHz, CDCl3) δ7.56 (d,2H,Ph-H),7.24 (d,2H,Ph-H),6.87 (d,2H,Ph-H),6 .40 (d,2H,Ph-H), 4.41 (m,2H,-OCH2-), 3.51 (t,6H,CH3Al), 2.82 (s,6H,CH3N-).

[0095] Example 11

[0096] 7.27 g of tris(pentafluorophenyl)(hydroxyphenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of trimethylaluminum (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 7.0 g of tris(pentafluorophenyl)(dimethylaluminoxyphenyl)borate dimethylphenylammonium salt, with a yield of 89.3%.

[0097] 1 H NMR (500MHz, CDCl3) δ7.44 (d,2H,Ph-H), 7.39 (d,2H,Ph-H), 6.86 (d,2H,Ph-H), 6.44 (d,2H,Ph-H), 3.45 (t,6H,CH3Al), 2.82 (s,6H,CH3N-).

[0098] Example 12

[0099] 7.55 g of tri(pentafluorophenyl)(hydroxyethylphenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of trimethylaluminum (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 7.2 g of tri(pentafluorophenyl)(dimethylaluminoxoethylphenyl)borate dimethylphenylammonium salt, with a yield of 88.7%.

[0100] 1H NMR (500MHz, CDCl3) δ7.67 (d, 2H, Ph-H), 7.34 (d, 2H, Ph-H), 6.90 (d, 2H, Ph-H), 6.32 (d, 2H, Ph-H), 4.33 (m,2H,-OCH2-), 3.65 (m,2H,-PhCH2-), 3.45 (t,6H,CH3Al), 2.67 (s,6H,CH3N-).

[0101] Example 13

[0102] 7.97 g of di(pentafluorophenyl)bis(hydroxytetrafluoro-substituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the solvent was removed under reduced pressure and crystallized at -15 °C to obtain 7.86 g of di(pentafluorophenyl)bis(butylmagnesiumoxytetrafluoro-substituted phenyl)borate dimethylphenylammonium salt, with a yield of 86.5%.

[0103] 1 H NMR (500MHz, CDCl3) δ7.48 (d,2H,Ph-H), 6.65 (d,2H,Ph-H), 3.67 (t,4H,-CH2Mg), 2.86 (s,6H,CH3N-), 1.46 (m,8H,-CH2-), 1.27 (m,6H,-CH3).

[0104] Example 14

[0105] 8.27 g of tris(pentafluorophenyl)(hydroxyethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 8.1 g of tris(pentafluorophenyl)(butylmagnesium oxyethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, with a yield of 89.3%.

[0106] 1 H NMR (500MHz, CDCl3) δ7.38 (d,2H,Ph-H), 6.54 (d,2H,Ph-H), 4.66 (m,2H,-OCH2-), 3.67 (m,2H ,-CH2Ph), 3.44 (t,2H,-CH2Mg), 2.65 (s,6H,CH3N-), 1.63 (m,4H,-CH2-), 1.25 (m,3H,-CH3).

[0107] Example 15

[0108] 9.37 g of tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate triphenylmethane salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 8.69 g of tri(pentafluorophenyl)(butylmagnesium oxymethyltetrafluoro-substituted phenyl)borate triphenylmethane salt, with a yield of 85.4%.

[0109] Tests showed that the solubility of the borate product obtained above in toluene was 8.2 wt% at 25°C.

[0110] 1 H NMR (500MHz, CDCl3) δ7.23-6.95 (m,15H,Ph-H), 4.55 (m,2H,-OCH2-), 3.43 (t,2H,-CH2Mg), 1.62 (m,4H,-CH2-), 1.24 (m,3H,-CH3).

[0111] Comparative Example 1

[0112] Using the solubility test conditions in Example 15, the solubility of tri(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)boronic acid triphenylmethane alkyl salt in toluene was measured to be 0.4%. This demonstrates that even with different types of borates using different cations, the solubility in organic solvents such as toluene is still significantly improved by introducing alkyl metal groups.

[0113] Example 16

[0114] 9.51 g of tri(pentafluorophenyl)(hydroxyethyltetrafluorosubstituted phenyl)boronic acid triphenylmethane salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 3 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 8.5 g of tri(pentafluorophenyl)(butylmagnesium oxymethyltetrafluorosubstituted phenyl)boronic acid triphenylmethane salt, with a yield of 82.4%.

[0115] 1 H NMR (500MHz, CDCl3) δ7.35-6.75 (m,15H,Ph-H), 4.56 (m,2H,-OCH2-), 3.93 (m,2H,-PhCH2-) 3.44 (t,2H,-CH2Mg), 1.65 (m,4H,-CH2-), 1.24 (m,3H,-CH3).

[0116] Example 17

[0117] 9.49 g of triphenylmethane di(pentafluorophenyl)di(hydroxymethyltetrafluoro-substituted phenyl)borate was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 80 mL of toluene were added sequentially at room temperature. After stirring for 3 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 8.89 g of triphenylmethane di(pentafluorophenyl)di(butylmagnesium oxymethyltetrafluoro-substituted phenyl)borate, with a yield of 80.1%.

[0118] 1 H NMR (500MHz, CDCl3) δ7.38-6.72 (m,15H,Ph-H), 4.53 (m,2H,-OCH2-), 3.44 (t,2H,-CH2Mg), 1.65 (m,8H,-CH2-), 1.24 (m,6H,-CH3).

[0119] Example 18

[0120] 9.37 g of tri(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)boronic acid triphenylmethane salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of trimethylaluminum (1.0 M n-hexane) and 80 mL of toluene were added sequentially at room temperature. After stirring for 3 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 8.89 g of tri(pentafluorophenyl)(dimethylaluminoxomethyltetrafluorosubstituted phenyl)triphenylmethane salt, with a yield of 89.5%.

[0121] 1 H NMR (500MHz, CDCl3) δ7.39-6.70 (m,15H,Ph-H), 4.58 (m,2H,-OCH2-), 3.49 (s,6H,-CH3Al).

[0122] Example 19

[0123] 9.37 g of tri(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)boronic acid triphenylmethane salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of triethylaluminum (1.0 M n-hexane) and 80 mL of toluene were added sequentially at room temperature. After stirring for 3 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 8.97 g of tri(pentafluorophenyl)(diethylaluminum methyltetrafluorosubstituted phenyl)triphenylmethane salt, with a yield of 87.8%.

[0124] 1 H NMR (500MHz, CDCl3) δ7.29-6.71 (m,15H,Ph-H), 4.56 (m,2H,-OCH2-), 3.48 (q,4H,-CH2Al), 1.89 (t,6H,CH3).

[0125] Example 20

[0126] 9.37 g of tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)boronic acid triphenylmethane salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of tri-n-butylaluminum (1.0 M n-hexane) and 80 mL of toluene were added sequentially at room temperature. After stirring for 3 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 9.21 g of tri(pentafluorophenyl)(di-n-butylaluminoxomethyltetrafluoro-substituted phenyl)triphenylmethane salt, with a yield of 83.8%.

[0127] 1 H NMR (500MHz, CDCl3) δ7.39-6.70 (m,15H,Ph-H), 4.57 (m,2H,-OCH2-), 3.65 (m,6H,-CH2Al), 1.89 (m,8H,-CH2CH3), 1.23 (t,6H,-CH3).

[0128] Example 21

[0129] 9.35 g of tri(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)borate triphenylmethane salt was added to a 250 mL flask filled with nitrogen. Then, 14.64 g of tri-n-octylaluminum (25 wt% n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 9.6 g of tri(pentafluorophenyl)(dioctylaluminoxomethyltetrafluorosubstituted phenyl)borate triphenylmethane salt, with a yield of 83.0%.

[0130] 1 H NMR (500MHz, CDCl3) δ7.39-6.70 (m,15H,Ph-H), 4.56 (m,2H,-OCH2-), 3.60 (m,6H,-CH2Al), 1.87-1.56 (m,24H,-CH2CH3), 1.23 (t,6H,-CH3).

[0131] Example 22

[0132] 9.59 g of triphenylmethane (pentafluorophenyl)tris(hydroxymethyltetrafluoro-substituted phenyl)borate was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 9.8 g of triphenylmethane (pentafluorophenyl)tris(butylmagnesium oxymethyltetrafluoro-substituted phenyl)borate, with a yield of 81.7%.

[0133] 1H NMR (500MHz, CDCl3) δ7.38-6.72 (m,15H,Ph-H), 4.52 (m,2H,-OCH2-), 3.44 (t,6H,-CH2Mg), 1.65 (m,12H,-CH2-), 1.26 (m,9H,-CH3).

[0134] Example 23

[0135] 9.71 g of tetra(hydroxymethyltetrafluoro-substituted phenyl)borate triphenylmethane salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 10.5 g of tetra(butylmagnesium oxymethyltetrafluoro-substituted phenyl)borate triphenylmethane salt, with a yield of 81.3%.

[0136] 1 H NMR (500MHz, CDCl3) δ7.39-6.71 (m,15H,Ph-H), 4.52 (m,2H,-OCH2-), 3.47 (t,8H,-CH2Mg), 1.67 (m,16H,-CH2-), 1.26 (m,12H,-CH3).

[0137] Example 24

[0138] 8.63 g of tri(pentafluorophenyl)(hydroxymethylphenyl)borate triphenylmethane salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to give 8.11 g of tri(pentafluorophenyl)(butylmagnesiumoxymethylphenyl)borate triphenylmethane salt, with a yield of 86.0%.

[0139] 1 H NMR (500MHz, CDCl3) δ7.23-6.95 (m, 15H, Ph-H), 6.92-6.65 (m, 5H, Ph-H), 4.45 (m,2H,-OCH2-), 3.23 (t,2H,-CH2Mg), 1.72 (m,4H,-CH2-), 1.29 (m,3H,-CH3).

[0140] Example 25

[0141] 7.81 g of tri(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate triethylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of dibutylmagnesium (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The mixture was then crystallized at -15 °C to obtain 8.01 g of tri(pentafluorophenyl)(butylmagnesium oxymethyltetrafluoro-substituted phenyl)borate triethylammonium salt, with a yield of 93.0%.

[0142] 1 H NMR (500MHz, CDCl3) δ4.45 (m,2H,-OCH2-), 4.02 (m,6H,-CH2N), 3.26 (t,2H,-CH2Mg), 1.98 (m,9H,-CH2CH3), 1.75 (m,4H,-CH2-), 1.25 (m,3H,-CH3).

[0143] Example 26

[0144] 7.81 g of tri(pentafluorophenyl)(hydroxymethyltetrafluorosubstituted phenyl)borate triethylammonium salt was added to a 250 mL flask filled with nitrogen. Then, 10 mL of trimethylaluminum (1.0 M n-hexane) and 60 mL of toluene were added sequentially at room temperature. After stirring for 2 hours, the mixture was filtered and the solvent was removed under reduced pressure. The solution was then crystallized at -15 °C to give 7.65 g of tri(pentafluorophenyl)(dimethylaluminoxomethyltetrafluorosubstituted phenyl)borate triethylammonium salt, with a yield of 91.3%.

[0145] 1 H NMR (500MHz, CDCl3) δ4.54 (m,2H,-OCH2-), 4.07 (m,6H,-CH2N), 3.29 (s,6H,CH3Al).

[0146] The polymerization reaction of the fluorinated aryl borate compounds prepared in the above examples was further tested, as follows.

[0147] Example 27

[0148] 100 g of 1-hexene was added to a 250 mL flask filled with nitrogen and heated at 80 °C for 30 minutes. Then, 30 mg of tris(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, 38 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)hafnium dichloride prepared in Example 1 were added sequentially. After reacting for 1 hour, a small amount of isopropanol was added to terminate the reaction. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure to obtain 75.89 g of polyolefin product, with a yield of 75%. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 98,700, a number-average molecular weight (Mn) of 21,900, and a molecular weight distribution (PDI) of 4.5.

[0149] Comparative Example 2

[0150] Using the same polymerization conditions as in Example 27, but replacing tris(pentafluorophenyl)(methylmagnesiumoxytetrafluorophenyl)borate dimethylphenylammonium salt with an equimolar amount of tris(pentafluorophenyl)(hydroxymethyltetrafluorophenyl)borate, 70.35 g of product was obtained, with a yield of 70%. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 87,600, a number-average molecular weight (Mn) of 29,200, and a molecular weight distribution (PDI) of 3.

[0151] Comparing Example 27 with Comparative Example 2, it can be seen that the molecular weight distribution (PDI) of the polymerization product obtained by using the catalytic system provided in Example 27 is significantly greater than that in Comparative Example 2. This indicates that fluoroaryl boronic acid compounds containing alkyl metal groups can effectively broaden the molecular weight distribution of the polymerization product catalyzed by the reaction, thereby improving its processing performance, compared to fluoroaryl boronic acid compounds without alkyl metals.

[0152] Example 28

[0153] 100 g of 1-octene was added to a 250 mL flask filled with nitrogen and heated at 120 °C for 30 minutes. Then, 32 mg of tris(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, 38 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)zirconium dichloride were added sequentially. After reacting for 1 hour, a small amount of isopropanol was added to terminate the reaction. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure to obtain 95.25 g of product, with a yield of 95%. High-temperature GPC analysis showed a weight-average molecular weight (Mw) of 97,800, a number-average molecular weight (Mn) of 20,200, and a molecular weight distribution (PDI) of 4.84.

[0154] Example 29

[0155] 100 g of 1-octene was added to a 250 mL flask filled with nitrogen and heated at 100 °C for 30 minutes. Then, 32 mg of tris(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, 38 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)hafnium dichloride were added sequentially. After reacting for 1 hour, a small amount of isopropanol was added to terminate the reaction. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure to obtain 96.72 g of product, with a yield of 96%. High-temperature GPC analysis showed a weight-average molecular weight (Mw) of 97,000, a number-average molecular weight (Mn) of 20,600, and a molecular weight distribution (PDI) of 4.71.

[0156] Example 30

[0157] 100 g of 1-decene was added to a 250 mL flask filled with nitrogen and heated at 120 °C for 30 minutes. Then, 41 mg of di(pentafluorophenyl)bis(butylmagnesiumoxytetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, 38 mg of trimethylaluminum, and 3 μmol of dimethylsilyldicyclopentadienylzirconium dichloride were added sequentially. After reacting for 1 hour, a small amount of isopropanol was added to terminate the reaction. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure to obtain 87.92 g of the product, with a yield of 88%. High-temperature GPC analysis showed a weight-average molecular weight (Mw) of 96,900, a number-average molecular weight (Mn) of 21,500, and a molecular weight distribution (PDI) of 4.5.

[0158] Example 31

[0159] 100 g of 1-decene was added to a 250 mL flask filled with nitrogen and heated at 120 °C for 30 minutes. Then, 45 mg of triphenylmethane di(pentafluorophenyl)bis(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate prepared in Example 17, 52 mg of triethylaluminum, and 4 μmol of dimethylsilyldicyclopentadienylzirconium dichloride were added sequentially. After reacting for 1 hour, a small amount of isopropanol was added to terminate the reaction. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure to obtain 93.02 g of the product, with a yield of 93%. High-temperature GPC analysis showed a weight-average molecular weight (Mw) of 98,600, a number-average molecular weight (Mn) of 21,100, and a molecular weight distribution (PDI) of 4.67.

[0160] Example 32

[0161] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 32 mg of tris(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, 50 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)zirconia dichloride were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain the pressure at 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 850 g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 135,000, a number-average molecular weight (Mn) of 30,600, a molecular weight distribution (PDI) of 4.4, and an SCB / 1000TC ratio of 34.3.

[0162] Example 33

[0163] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 33mg of tris(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, 50mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)zirconia were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain the pressure at 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 756g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 123,000, a number-average molecular weight (Mn) of 27,300, a molecular weight distribution (PDI) of 4.5, and an SCB / 1000TC ratio of 37.5.

[0164] Example 34

[0165] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 32 mg of di(pentafluorophenyl)bis(butylmagnesiumoxytetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, 50 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propyl)cyclopentadienylzirconium dichloride were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain the pressure at 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 634 g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 145,000, a number-average molecular weight (Mn) of 34,500, a molecular weight distribution (PDI) of 4.2, and an SCB / 1000TC ratio of 39.3.

[0166] Example 35

[0167] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 32 mg of di(pentafluorophenyl)bis(butylmagnesium oxymethyltetrafluorophenyl)borate dimethylphenylammonium salt, 50 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propyl)cyclopentadienylzirconium dichloride were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain the pressure at 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 458 g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 149,000, a number-average molecular weight (Mn) of 34,600, a molecular weight distribution (PDI) of 4.3, and an SCB / 1000TC ratio of 41.7.

[0168] Example 36

[0169] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 36mg of tri(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate triphenylmethane salt, 50mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)zirconia dichloride prepared in Example 15 were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain a pressure of 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 789g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 127,000, a number-average molecular weight (Mn) of 27,000, a molecular weight distribution (PDI) of 4.7, and an SCB / 1000TC ratio of 35.3.

[0170] Example 37

[0171] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 32 mg of tri(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)boronic acid triphenylmethane salt, 50 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)zirconia dichloride were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain a pressure of 3MPa. After reacting for 0.5 hours, the liquid was poured off and dried in a vacuum oven. 678 g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 138,000, a number-average molecular weight (Mn) of 33,000, a molecular weight distribution (PDI) of 4.0, and an SCB / 1000TC of 36.5.

[0172] Example 38

[0173] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 32 mg of tri(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate triethylamine salt, 50 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)zirconia dichloride prepared in Example 25 were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain a pressure of 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 435g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 142,000, a number-average molecular weight (Mn) of 35,000, a molecular weight distribution (PDI) of 4.1, and an SCB / 1000TC ratio of 38.8.

[0174] Example 39

[0175] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 32 mg of tri(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate triethylamine salt, 50 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)hafnium dichloride prepared in Example 25 were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain a pressure of 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 467g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 136,000, a number-average molecular weight (Mn) of 31,000, a molecular weight distribution (PDI) of 4.4, and an SCB / 1000TC ratio of 41.3.

[0176] Example 40

[0177] A 5L reactor filled with nitrogen was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 32 mg of tri(pentafluorophenyl)(dimethylaluminoxomethyltetrafluorosubstituted phenyl)borate triethylamine salt, 50 mg of trimethylaluminum, and 3 μmol of dimethylsilylbis(n-propylcyclopentadienyl)zirconia prepared in Example 26 were added sequentially to prepare a catalyst composition. This composition was added to the reactor through a bypass pipe, and ethylene was added to maintain a pressure of 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 678g of product was obtained. High-temperature GPC testing showed a weight-average molecular weight (Mw) of 145,000, a number-average molecular weight (Mn) of 33,000, a molecular weight distribution (PDI) of 4.4, and an SCB / 1000TC ratio of 42.2.

[0178] Example 41

[0179] A 5L nitrogen-filled reactor was injected with 3L of n-hexane, 900g of 1-octene, and 5mmol of H2. The mixture was heated at 80°C for 30 minutes, then saturated with ethylene and maintained at a pressure of 3MPa. In a glove box, 32 mg of tris(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluorosubstituted phenyl)borate dimethylphenylammonium salt, 50 mg of trimethylaluminum, and 3 μmol of diethylmethylenecyclopentadienyl(3,5-dimethylphenylindenyl)zirconia dichloride were added sequentially to prepare a catalyst composition. This composition was then added to the reactor via a bypass pipe. Ethylene was added to maintain the pressure at 3MPa. After reacting for 1 hour, the liquid was poured off and dried in a vacuum oven. 467g of product was obtained. Analysis showed that its weight-average molecular weight was 130,600, its molecular weight distribution index (PDI) was 4.3, and its SCB / 1000TC ratio was 43.3 (see Appendix). Figure 1 ).

[0180] Comparative Example 3

[0181] The process was largely the same as in Example 41, except that an equimolar amount of dimethylamine tris(pentafluorophenyl)borate was used instead of dimethylphenyl tris(butylmagnesiumoxymethyltetrafluoro)borate for polymerization, yielding 447g of product with a weight-average molecular weight of 120,600, a molecular weight distribution index (PDI) of 2.4, and an SCB / 1000TC ratio of 13.4 (see Appendix). Figure 2 ).

[0182] Comparing Example 41 with Comparative Example 3, it can be seen that the polymerization product obtained using the catalytic system of Example 41 (due to the further introduction of alkyl metal group units) has a higher molecular weight distribution index (PDI), a wider molecular weight distribution, and a higher SCB / 1000TC index, which indicates that more comonomers are incorporated.

[0183] Comparative Example 4:

[0184] The process was largely the same as in Example 41, except that an equimolar amount of tris(pentafluorophenyl)(hydroxymethyltetrafluoro-substituted phenyl)borate dimethylamine salt + 2 times the molar amount of dibutylmagnesium (1.0M n-hexane) was used instead of tris(pentafluorophenyl)(butylmagnesiumoxymethyltetrafluoro-substituted phenyl)borate dimethylphenylammonium salt for polymerization, yielding 421g of product with a weight-average molecular weight of 111,600, a molecular weight distribution index (PDI) of 2.2, and an SCB / 1000TC of 12.4.

[0185] Comparing Example 42 with Comparative Example 4, it can be seen that the catalyst system using a mixture of alkyl metal and fluorinated aryl borate compound is less effective in broadening the molecular weight distribution of polyolefin products. This demonstrates that alkyl metal groups must be introduced into the structure of the cocatalyst compound in a reactive form.

[0186] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A fluorine-containing arylborate compound containing an alkyl metal-based unit, characterized by, Its chemical structural formula is {(F m Ar 1 ) 4-n [F x Ar 2 -Q-Z-M(R) j ] n B} - N + , wherein B is a borate center boron atom with a negative charge; F is a fluorine atom; Q represents Ar 2 and Z are directly connected without carbon; F m Ar 1 is a fluorine-substituted phenyl group bonded to B; F x Ar 2 is a fluorine-substituted phenyl group bonded to B; m is 5, and x is 4; n is 1, 2, 3, or 4; Z is an oxygen or sulfur atom connected to Q and M; M is a magnesium or aluminum atom; R is a C1-C 20 alkyl group, and j represents the number of alkyl groups R connected to the M atom, with j = 1 when M is a magnesium atom and j = 2 when M is an aluminum atom; N + is an organic cation with a carbon number of 3 to 90 or an IA group metal cation.

2. The fluoroarylborate compound containing an alkyl metal-based unit according to claim 1, characterized in that, Q represents Ar 2 and Z is a direct carbon-free linkage, or is a C1-C6 aliphatic linker; F 2 and Z is a direct carbon-free linkage, or is a C1-C6 aliphatic linker; F m Ar 1 is a substituted aryl group bonded to B; F 10 is a substituted aryl group bonded to B; F x Ar 2 is a substituted aryl group bonded to B; F 10 is a substituted aryl group bonded to B; m is an integer from 0 to 7, x is an integer from 0 to 6; R is a C1-C 10 alkyl group.

3. The fluoroarylborate compound containing an alkyl metal-based unit according to claim 1, wherein N + is an organic cation having a carbon number of 10 to 40 selected from any one of trimethylammonium ion, triethylammonium ion, tributylammonium ion, trioctylammonium ion, triethylmethylammonium ion, tributylmethylammonium ion, trioctylmethylammonium ion, tridecylmethylammonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, tetraoctylammonium ion, N,N-dimethylanilinium ion, N,N-dimethylanilinium ion, N,N-dimethylanilinium ion, N,N-diethylanilinium ion, N,N-diethylanilinium ion, N,N-diethylanilinium ion, di(tetradecyl)methylammonium ion, di(hexadecyl)methylammonium ion, di(octadecyl)methylammonium ion, triphenylmethyl cation, tri(p-methylphenyl)methyl cation, tri(p-methoxyphenyl)methyl cation, tri(p-trimethylsilylphenyl)methyl cation, tri(p-fluorophenyl)methyl cation, tri(p-trifluoromethylphenyl)methyl cation, and mixed saturated alkylammonium ions having a total carbon number of 30-40.

4. The fluoroarylborate compound containing an alkyl metal-based unit according to claim 1, wherein The alkyl R is at least one of methyl, ethyl, butyl, isobutyl, hexyl, isohexyl, and octyl.

5. A process for the preparation of a fluoroarylborate compound containing an alkyl metal-based unit according to any one of claims 1 to 4, characterized in that, A fluorine-containing aryl borate and an alkyl metal compound are used as raw materials to obtain a compound in an organic solvent, wherein the fluorine-containing aryl borate has a chemical structural formula of {(F m Ar 1 ) 4-n [F x Ar 2 -Q-Z-H] n B} - N + wherein H is a hydrogen atom; and the alkyl metal compound is a compound in which M is connected to an alkyl group R by a saturated bond.

6. The fluoroarylborate compound containing an alkyl metal-based unit according to claim 5, wherein The alkyl metal compound and the fluorine-containing aryl borate are added in a molar ratio of n~5:1 of M atoms to B atoms.

7. Use of a fluorine-containing aryl borate compound containing an alkyl metal group unit as a cocatalyst in catalyzing polymerization of olefins in cooperation with a metallocene compound.

8. A catalyst system for the catalytic polymerization of C2-C 40 olefins comprising a procatalyst and a cocatalyst, characterized in that, The main catalyst is a metallocene compound containing a metal penta-ring coordination bond structure, and the cocatalyst is a fluorine-containing aryl borate compound containing an alkyl metal group unit according to any one of claims 1-4.

9. A catalyst system for the catalytic polymerization of C2-C 40 olefins according to claim 8, characterized in that, The chemical structural formula of the metallocene compound is: ， E is titanium, zirconium, or hafnium. X 1 , X 2 each independently is selected from the group consisting of halogen, Ci-C 10 alkyl, C6-C 10 aryl, Ci-C 10 substituted alkyl, C6-C 10 substituted aryl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 each independently is selected from the group consisting of H, C1-C 20 alkyl, C6-C 20 aryl, C1-C 20 substituted alkyl, C6-C 20 substituted aryl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 optionally are mutually bonded between adjacent groups in R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and the five-membered ring to which they are attached to form a cyclopentadienyl aryl group. Y is silicon or carbon valence saturated by substituents which are C1-C 20 alkyl or substituted alkyl, C6-C 20 aryl.

10. A catalyst system for the catalytic polymerization of C2-C 40 olefins according to claim 9, characterized in that, The amount of the procatalyst and the cocatalyst added satisfies the molar ratio of the sum of B atoms and X 1 , X 2 is 0.1 to 100: 1.

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