Novel borate compound soluble in aliphatic hydrocarbon solvent

Abstract

The purpose of the present invention is to provide a borate compound which is soluble in an aliphatic hydrocarbon solvent, can maintain a homogeneous solution state even at a low temperature, and is useful as a co-catalyst for the solution polymerization of olefins or dienes.　The present invention relates to: a borate compound represented by formula (1) [the definition of each symbol in the formula is as described in the specification]; a method for producing the borate compound; and a use of the borate compound as a co-catalyst for the polymerization of olefins or dienes.

Description

New borate compounds soluble in aliphatic hydrocarbon solvents.

[0001] The present invention relates to a borate compound that is soluble in an aliphatic hydrocarbon solvent and can maintain a homogeneous solution state even at low temperatures, and is useful as a cocatalyst for the polymerization of olefins or dienes, and a method for producing the same.

[0002] Numerous reports have been published on the use of non-metallocene metal complex catalysts such as metallocene compounds, diimine complexes, and phenoxy complexes as catalysts for the polymerization of olefins and dienes. Co-catalysts used to stabilize the cationic active species of these metal complex catalysts include alkylaluminums, aluminoxanes (MAO) such as methylaluminoxane, Bronsted acid salts such as ammonium borate, and Lewis acid salts such as triphenylcarbenium borate (Non-Patent Document 1).

[0003] In the catalytic activation reaction by the Bronsted acid salt, a leaving group on the metal complex catalyst is protonated and eliminated from the metal complex catalyst, generating a cationic active species of the metal complex catalyst, whereby the non-coordinating anion derived from the Bronsted acid salt stabilizes the active species. As the Bronsted base constituting the Bronsted acid salt, various borate compounds such as tetrakis(pentafluorophenyl)borate, which is a non-coordinating anion, have been reported (Non-Patent Document 1), and as the Bronsted acid, a Bronsted acid containing nitrogen, phosphorus, oxygen, and / or sulfur is known (Patent Document 1).

[0004] Known examples of the Bronsted acid salt include nitrogen-containing Bronsted acid salts (ammonium borates), such as dimethylanilinium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, and methylpyrrolidinium tetrakis(pentafluorophenyl)borate (Patent Document 2). In the catalytic activation reaction using these ammonium borates, an amine compound is produced by losing a proton during the protonation step. Such amine compounds may interact with the cationic active species of the metal complex catalyst, which may adversely affect the polymerization reaction.

[0005] In addition, non-polar hydrocarbon solvents are used as solvents for polymerization. In particular, from the viewpoint of odor and toxicity, aromatic hydrocarbon solvents such as toluene are being replaced by aliphatic hydrocarbon solvents such as n-hexane.

[0006] However, it is known that ordinary tetrakis(pentafluorophenyl)borate compounds are poorly soluble in aromatic hydrocarbon solvents such as toluene, or even if they are dissolved, they separate into two liquid-liquid phases: a concentrated phase in which the borate compound is dissolved and a dilute phase in which the borate compound is not dissolved (Patent Document 3).

[0007] Because tetrakis(pentafluorophenyl)borate compounds are poorly soluble in aliphatic hydrocarbon solvents such as n-hexane and n-heptane, compounds that are soluble in aliphatic hydrocarbon solvents are desired and have been proposed (Patent Document 4). Di(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate and bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate, as described in Patent Document 4, are useful as compounds soluble in hydrocarbon solvents.

[0008] However, when di(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate or bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate described in Patent Document 4 is used, the trialkylamine produced after the catalyst activation reaction has nucleophilicity, and therefore there is concern that it may act as a catalyst poison in the polymerization reaction of olefins or dienes.

[0009] Patent Document 5 also describes a compound represented by the following formula (AI):

[0010]

[0011] (The definitions of each symbol in the formula are as described in Patent Document 5.) is described as an activator for olefin polymerization (referred to as a co-catalyst in this specification), and it is described that the solubility of the compound in an aliphatic hydrocarbon solvent at 25°C increases with the number of aliphatic carbon atoms in the cationic group (i.e., ammonium or phosphonium). However, Patent Document 5 does not disclose the solubility of the compound in an aliphatic hydrocarbon solvent at low temperatures.

[0012] US Patent No. 5,132,380 Specification International Publication No. 2010 / 014344 JP 2018-104335 A JP 2000-507157 A JP 2021-522243 A

[0013] Chem. Rev. 2000, 100, 1391-1434

[0014] Generally, borate compounds, which are used as cocatalysts for solution polymerization of olefins or dienes, are obtained in an oily form, making them difficult to handle and measure as a single substance. Therefore, borate compounds are typically dissolved in a solvent used for solution polymerization and stored as a homogeneous solution, which must be diluted and measured before use. However, as mentioned above, borate compounds are generally known to have extremely low solubility in aliphatic hydrocarbon solvents. Furthermore, the present inventors encountered difficulties, such as separation into two phases or solid precipitation, when the borate compound described in Patent Document 5, which is soluble in aliphatic hydrocarbon solvents at 25°C, was stored as a solution in an aliphatic hydrocarbon solvent in winter or at low temperatures. In view of these prior art, the present invention aims to provide a borate compound useful as a cocatalyst for solution polymerization of olefins or dienes, which is soluble in aliphatic hydrocarbon solvents and can maintain a homogeneous solution state even at low temperatures, and an industrial production method thereof.

[0015] As a result of extensive investigation, the present inventors have found that the compound represented by the following formula (1):

[0016]

[0017] [In the formula, R １ and R ２ are each independently a linear C １６－２０ represents an alkyl group; R ３ is a linear C ３－８ represents an alkyl group; and R ４ , R ５ , R ６ and R ７ are each independently one or more fluorine atoms or fluoro C １－４ C substituted with alkyl group ６－１４ represents an aryl group.] (hereinafter also referred to as "the compound of the present invention") is soluble in aliphatic hydrocarbon solvents such as n-hexane and methylcyclohexane, can be stably stored in the form of a homogeneous solution even at low temperatures, and can be used as is when needed. It has been found that the compound is useful as a co-catalyst for the solution polymerization reaction of olefins or dienes, and has led to the completion of the present invention.

[0018] One embodiment of the present invention is, for example, as follows: [1] Formula (1):

[0019]

[0020] [In the formula, R １ and R ２ are each independently a linear C １６－２０ represents an alkyl group; R ３ is a linear C ３－８ represents an alkyl group; and R ４ , R ５ , R ６ and R ７ are each independently one or more fluorine atoms or fluoro C １－４ C substituted with alkyl group ６－１４ [2] R represents an aryl group. １ and R ２ are each independently a linear C １６－１８ is an alkyl group, and R ３ But linear C ４－６ The compound according to the above [1], wherein R is an alkyl group. ４ , R ５ , R ６ and R ７ are each independently a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, each substituted with one or more fluorine atoms or trifluoromethyl groups. ４ , R ５ , R ６ and R ７are all pentafluorophenyl groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups. [5] The compound according to any one of [1] to [4] above, which exhibits a solubility of 3 mM or more in n-hexane at temperatures ranging from -15°C to 25°C and a solubility of 300 mM or more in methylcyclohexane at temperatures ranging from -15°C to 25°C. [6] An n-hexane solution of the compound according to any one of [1] to [4] above, containing 3 mM or more of the compound according to any one of [1] to [4] above, at temperatures ranging from -15°C to 25°C. [7] A methylcyclohexane solution of the compound according to any one of [1] to [4] above, containing 300 mM or more of the compound according to any one of [1] to [4] above, at temperatures ranging from -15°C to 25°C. [8] A co-catalyst for solution polymerization of at least one monomer selected from the group consisting of olefins and dienes, comprising the compound according to any one of [1] to [4] above. [9] A method for producing a polymer, comprising solution polymerizing at least one monomer selected from the group consisting of olefins and dienes, using the compound according to any one of [1] to [4] above as a co-catalyst.

[10] A method for storing the compound according to any one of [1] to [4] above, comprising dissolving the compound according to any one of [1] to [4] above in n-hexane or methylcyclohexane, and storing the compound at -15°C to 0°C while maintaining the compound in a homogeneous solution state.

[11] A compound represented by the formula (2):

[0021]

[0022] [In the formula, R １ and R ２ are each independently a linear C １６－２０ represents an alkyl group; R ３ is a linear C ３－８ represents an alkyl group; and X represents a halogen atom.] and a compound represented by formula (3):

[0023]

[0024] [In the formula, R ４ , R ５ , R ６ and R ７are each independently one or more fluorine atoms or fluoro C １－４ C substituted with alkyl group ６－１４ and M represents an alkali metal.] in a mixed solvent of methylcyclohexane and water.

[0025] Generally, in the technical field of solution polymerization of olefins or dienes, aromatic hydrocarbon solvents such as toluene are frequently used as solvents or co-solvents in consideration of the solubility of catalysts and the like. However, it is desirable to reduce the amount of aromatic hydrocarbon solvents or to eliminate their use altogether, not only from the viewpoint of odor and toxicity but also from the viewpoint of removal costs. According to the present invention, a novel borate compound can be provided that can maintain a homogeneous solution state even at low temperatures in an aliphatic hydrocarbon solvent, particularly n-hexane, methylcyclohexane, or a mixture thereof, without using any aromatic hydrocarbon solvent. Because the compound of the present invention can maintain a homogeneous solution state even at low temperatures in an aliphatic hydrocarbon solvent, the compound of the present invention can be stably stored in the form of a diluted solution that is easy to handle and measure, and has the advantage that it can be used as is as a co-catalyst for the solution polymerization reaction of olefins or dienes. Furthermore, the present invention can also provide a simple method for producing the compound of the present invention.

[0026] The definitions of the terms and symbols used in this specification are explained below.

[0027] In this specification, the term "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0028] In the present specification, "linear C １６－２０ The term "alkyl (group)" refers to a linear alkyl group having 16 to 20 carbon atoms, and examples thereof include hexadecyl, octadecyl, nonadecyl, and eicosyl. １６－１８ Alkyl groups are preferred.

[0029] In the present specification, "linear C ３－８The term "alkyl (group)" refers to a linear alkyl group having 3 to 8 carbon atoms, and examples thereof include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. ４－６ Alkyl groups are preferred.

[0030] In this specification, "C １－４ The term "alkyl (group)" refers to a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0031] As used herein, "fluoro C １－４ The "C alkyl (group)" is １－４ "Alkyl" means a group in which one or more hydrogen atoms in the "alkyl" group are substituted with a fluorine atom. Specific examples include difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, and 4,4,4-trifluorobutyl.

[0032] In this specification, the term "alkali metal" refers to a metal element belonging to Group I (Group IA) of the periodic table, and examples thereof include lithium, sodium, potassium, rubidium, cesium, etc. Among these, lithium or sodium is preferred.

[0033] As used herein, the term "hydrocarbon solvent" refers to solvents including aromatic hydrocarbon solvents and / or aliphatic hydrocarbon solvents.

[0034] In the present specification, examples of the "aromatic hydrocarbon solvent" include benzene, toluene, xylene, etc.

[0035] In this specification, examples of the "aliphatic hydrocarbon solvent" include n-hexane, isohexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, mixed solvents thereof, etc. Among these, n-hexane, methylcyclohexane, or mixed solvents thereof are preferred.

[0036] As used herein, the term "soluble in an aliphatic hydrocarbon solvent" means that the compound of the present invention dissolves in an aliphatic hydrocarbon solvent such as n-hexane or methylcyclohexane at a specific concentration at a specific temperature to form a transparent, homogeneous solution. Specific preferred embodiments include, for example, that the compound of the present invention dissolves in n-hexane at a concentration of at least 3 mM, preferably 5 mM or more, in a temperature range of -15°C to 25°C (at any temperature within this range) to form a transparent, homogeneous solution, and that the compound of the present invention dissolves in methylcyclohexane at a concentration of at least 300 mM, preferably 350 mM or more, more preferably 400 mM or more, in a temperature range of -15°C to 25°C (at any temperature within this range) to form a transparent, homogeneous solution.

[0037] In this specification, "low temperature" means a temperature lower than room temperature, and the upper limit is not particularly limited as long as it is lower than 15°C, but is usually 10°C or lower, preferably 5°C or lower, and more preferably 0°C or lower. The lower limit is usually -20°C or higher, and preferably -15°C or higher.

[0038] In this specification, "room temperature" refers to room temperature (15°C to 25°C) as defined in the General Rules of the Japanese Pharmacopoeia, 18th Edition.

[0039] As used herein, the term "solubility in the range of -15°C to 25°C" refers to the molar concentration of the compound of the present invention that can maintain a transparent, homogeneous solution when a solution of the compound of the present invention dissolved in an aliphatic hydrocarbon solvent at 25°C is cooled to any temperature within the range of -15°C to 25°C, i.e., the concentration (mM) of a saturated solution of the compound of the present invention in an aliphatic hydrocarbon solvent at any temperature within the range of -15°C to 25°C.

[0040] In this specification, when the expression "Y°C to Z°C" is used (Y and Z are arbitrary numbers), it means "Y°C or higher and Z°C or lower" unless otherwise specified.

[0041] As used herein, the term "homogeneous solution state" means a transparent state in which the compound of the present invention is homogeneously dissolved in an aliphatic hydrocarbon solvent without precipitating as a solid and without undergoing phase separation (e.g., separation into two phases).

[0042] In this specification, storage in the "storage method" includes keeping the product in a stationary state for a certain period of time, and also includes moving the product without being limited to keeping the product in a stationary state.

[0043] In this specification, the term "solution polymerization" means that a polymerization reaction is carried out in a solvent such as an organic solvent. Therefore, solution polymerization is carried out in such a manner that a mixture of a monomer and a solvent is constantly kept in a solution state, i.e., a homogeneous solution state, during and after the polymerization reaction.

[0044] (Compound of the Present Invention) The compound of the present invention will be described below.

[0045] The compound of the present invention is represented by the following formula (1):

[0046]

[0047] [In the formula, R １ and R ２ are each independently a linear C １６－２０ represents an alkyl group; R ３ is a linear C ３－８ represents an alkyl group; and R ４ , R ５ , R ６ and R ７ are each independently one or more fluorine atoms or fluoro C １－４ C substituted with alkyl group ６－１４ represents an aryl group.] (hereinafter, also referred to as "compound (1)").

[0048] Preferred embodiments of compound (1) are described below.

[0049] Each group in compound (1) will be explained below.

[0050] R １ and R ２ are preferably each independently a linear C １６－１８ is an alkyl group, and R ３ But linear C ４－６ It is an alkyl group.

[0051] R ４ , R ５ , R ６and R ７ are preferably each independently one or more fluorine atoms or fluoro C １－４ R is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 3-phenanthryl group, or 9-phenanthryl group, each of which is independently substituted with one or more fluorine atoms or trifluoromethyl groups, and particularly preferably R ４ , R ５ , R ６ and R ７ are all the same, a pentafluorophenyl group, a 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group, or a 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group.

[0052] Suitable compounds (1) include the following compounds:

[0053] [Compound (1A)] R in the formula (1) １ and R ２ are each independently a linear C １６－２０ is an alkyl group, R ３ is a linear C ３－８ is an alkyl group, and R ４ , R ５ , R ６ and R ７ each independently represents one or more fluorine atoms or fluoro C １－４ Compound (1) is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 3-phenanthryl group, or 9-phenanthryl group, substituted with an alkyl group (e.g., a trifluoromethyl group).

[0054] [Compound (1B)] R in the formula (1) １ and R２ are each independently a linear C １６－２０ is an alkyl group, R ３ is a linear C ３－８ is an alkyl group, and R ４ , R ５ , R ６ and R ７ are each independently a phenyl group, a 1-naphthyl group or a 2-naphthyl group substituted with one or more fluorine atoms or trifluoromethyl groups.

[0055] [Compound (1C)] R in the formula (1) １ and R ２ are each independently a linear C １６－２０ is an alkyl group, R ３ is a linear C ３－８ is an alkyl group, and R ４ , R ５ , R ６ and R ７ are all the same, a pentafluorophenyl group, a 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group, or a 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group (preferably a pentafluorophenyl group).

[0056] [Compound (1D)] R in the formula (1) １ and R ２ are each independently a linear C １６－１８ is an alkyl group, R ３ But linear C ４－６ is an alkyl group, and R ４ , R ５ , R ６ and R ７ each independently represents one or more fluorine atoms or fluoro C １－４Compound (1) is a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 3-phenanthryl group, or 9-phenanthryl group, substituted with an alkyl group (e.g., a trifluoromethyl group).

[0057] [Compound (1E)] R in the formula (1) １ and R ２ are each independently a linear C １６－１８ is an alkyl group, R ３ But linear C ４－６ is an alkyl group, and R ４ , R ５ , R ６ and R ７ are each independently a phenyl group, a 1-naphthyl group or a 2-naphthyl group substituted with one or more fluorine atoms or trifluoromethyl groups.

[0058] [Compound (1F)] R in the formula (1) １ and R ２ are each independently a linear C １６－１８ is an alkyl group, R ３ But linear C ４－６ is an alkyl group, and R ４ , R ５ , R ６ and R ７ are all the same, a pentafluorophenyl group, a 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group, or a 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group (preferably a pentafluorophenyl group).

[0059] Specific preferred examples of compound (1) include N,N-dihexadecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate (compound (1-1)), N,N-dioctadecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate (compound (1-2)), and the like.

[0060] The compound of the present invention is soluble in aliphatic hydrocarbon solvents, particularly n-hexane, methylcyclohexane, or a mixture thereof, and can maintain a homogeneous solution state even at low temperatures, which has the advantage that the compound of the present invention can be stably stored in a solution state that is easy to handle and measure. Therefore, the compound of the present invention is useful as a cocatalyst for the homogeneous solution polymerization of olefins or dienes.

[0061] (Storage Method of the Compound of the Present Invention) Hereinafter, the storage method of the compound of the present invention (hereinafter also referred to as "storage method of the present invention") will be described.

[0062] The storage method of the present invention is characterized in that the compound of the present invention (compound (1)) is dissolved in an aliphatic hydrocarbon solvent (e.g., n-hexane, methylcyclohexane, or a mixed solvent thereof) and stored at low temperature for a certain period of time while maintaining a homogeneous solution state. The fact that the mixture of the compound of the present invention and the aliphatic hydrocarbon solvent is in a homogeneous solution state can be confirmed visually.

[0063] The lower limit of the concentration of compound (1) during storage, i.e., the solubility, can be set based on the concentration (mM) of a saturated solution of compound (1) in an aliphatic hydrocarbon solvent at the lowest storage temperature, specifically, −20° C. or −15° C.

[0064] A preferred embodiment of the storage method of the present invention is a storage method characterized by dissolving compound (1) in n-hexane to a concentration of at least 3 mM and storing the solution at −15° C. to 0° C. for a certain period of time while maintaining the solution in a homogeneous state.

[0065] Another preferred embodiment of the storage method of the present invention is a storage method comprising dissolving compound (1) in methylcyclohexane at a concentration of at least 300 mM and storing the solution at −15° C. to 0° C. for a certain period of time while maintaining the solution in a homogeneous state.

[0066] (Method for Producing the Compound of the Present Invention) Hereinafter, a method for producing the compound of the present invention (compound (1)) (hereinafter also referred to as "the production method of the present invention") will be described.

[0067] The production method of the present invention is a production method of compound (1), which comprises reacting a compound represented by the following formula (2):

[0068]

[0069] [wherein each symbol has the same meaning as defined above] (hereinafter also referred to as "compound (2)"), and a compound represented by formula (3):

[0070]

[0071] [wherein each symbol has the same meaning as defined above] (hereinafter also referred to as "compound (3)") in a mixed solvent of methylcyclohexane and water (hereinafter also referred to as "step A"). Specific examples of the production method include the production methods described in the Production Examples below.

[0072] In the present production method, examples of compound (2) used as a raw material include N,N-dihexadecylaniline hydrochloride, N,N-diheptadecylaniline hydrochloride, N,N-dioctadecylaniline hydrochloride, N,N-dinonadecylaniline hydrochloride, and N,N-dieicosylaniline hydrochloride.

[0073] The method for producing compound (2) is not particularly limited, but for example, a method for producing a compound represented by the following formula (4):

[0074]

[0075] [The symbols in the formula are as defined above.] (hereinafter also referred to as "compound (4)") is reacted with an alkyl halide (R １ X' and R ２ X′) (wherein X′ represents a halogen atom, and the other symbols are as defined above), to obtain a compound represented by the following formula (5):

[0076]

[0077] wherein each symbol has the same meaning as defined above. (hereinafter also referred to as "Step 1"), and a step of converting compound (5) into compound (2) by reacting compound (5) with hydrogen chloride in a solvent (hereinafter also referred to as "Step 2").

[0078] (Step 1) This step can be carried out in a solvent that does not affect the reaction. The reaction solvent is not particularly limited, but examples include ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetonitrile; and amides such as N,N-dimethylformamide and N,N-dimethylacetamide, among which tetrahydrofuran is preferred.

[0079] Examples of the base include inorganic bases such as sodium hydride, potassium carbonate, sodium hydroxide, and potassium hydroxide; and organic bases such as triethylamine, pyridine, and N,N-diisopropylethylamine, with sodium hydride being preferred. The amount of the base used is usually 2 to 5 mol, preferably 2.2 to 3 mol, per 1 mol of compound (4).

[0080] The amount of alkyl halide used is 1 mole of R １ X' and R ２ Each of X' is usually 1 to 1.5 mol, preferably 1.1 to 1.3 mol. １ and R ２ are identical, R １ X' and R ２ The total amount of X' used is usually 2 to 3 moles, preferably 2.2 to 2.6 moles.

[0081] The reaction temperature is usually 60° C. to 130° C., preferably 70° C. to 90° C., more preferably the reflux temperature of the reaction solvent, and the reaction time is usually 3 to 24 hours.

[0082] (Step 2) This step can be carried out in a solvent that does not affect the reaction. The reaction solvent is not particularly limited, but examples thereof include aliphatic hydrocarbon solvents such as n-hexane and n-heptane, and of these, n-hexane is preferred.

[0083] The hydrogen chloride is not particularly limited, but for example, a hydrogen chloride / diethyl ether solution or a hydrogen chloride / ethyl acetate solution, both of which are readily available commercially, can be used. The amount of hydrogen chloride used is usually 1 to 2 moles, preferably 1.1 to 1.5 moles, per mole of compound (5).

[0084] The reaction temperature is usually normal temperature (15° C. to 25° C.), preferably room temperature (20° C. to 25° C.), and the reaction time is usually 1 to 4 hours.

[0085] In the present production method, examples of compound (3) used as a raw material include lithium tetrakis(pentafluorophenyl)borate, sodium tetrakis(pentafluorophenyl)borate, lithium tetrakis(nonafluoro[1,1'-biphenyl]-4-yl)borate, sodium tetrakis(nonafluoro[1,1'-biphenyl]-4-yl)borate, lithium tetrakis(heptafluoro-2-naphthyl)borate, sodium tetrakis(heptafluoro-2-naphthyl)borate, lithium [3,5-bis(trifluoromethyl)phenyl]borate, sodium [3,5-bis(trifluoromethyl)phenyl]borate, and diethyl ether complexes thereof.

[0086] Compound (3) may be a commercially available product or a purified product, or may be prepared by a method known per se (see, for example, Angew. Chem. Int. Ed., 2009, 48(40), 7444-7447).

[0087] (Process A)

[0088]

[0089] This step can be carried out in a mixed solvent of hydrocarbon solvent and water (two-phase system). The hydrocarbon solvent used is not particularly limited, but examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane. Among these, aliphatic hydrocarbon solvents such as methylcyclohexane are preferred because the solution after post-treatment can be used directly in a solution polymerization reaction. The mixing ratio (v / v) of hydrocarbon solvent to water can be appropriately set depending on the type of hydrocarbon solvent used, but the hydrocarbon solvent:water ratio is usually 1:1 to 10:1, and preferably 1:1 to 5:1.

[0090] The reaction temperature is usually normal temperature (15° C. to 25° C.), preferably room temperature (20° C. to 25° C.), and the reaction time is usually 1 to 4 hours.

[0091] In this step, after the reaction is completed, the organic phase is washed with water, the hydrocarbon solvent is distilled off under reduced pressure, and then the hydrocarbon solvent is added to the residue and distilled off again under reduced pressure. This step is repeated three times, and the resulting residue is then post-treated by dissolving it in an aliphatic hydrocarbon solvent, thereby obtaining a solution of the compound of the present invention in an aliphatic hydrocarbon solvent. By quantifying the concentration of the compound of the present invention contained in the solution, the solution can be stored at low temperatures in the form of a homogeneous, transparent solution, and can be easily used as is as a cocatalyst for the solution polymerization of olefins or dienes.

[0092] The method for quantifying the concentration (solubility) of the compound of the present invention contained in an aliphatic hydrocarbon solvent solution of the compound of the present invention is not particularly limited, and for example, the quantification can be carried out by quantitative analysis by NMR using an internal standard.

[0093] The compound of the present invention is soluble in an aliphatic hydrocarbon solvent and can be stably stored while maintaining a homogeneous solution state even at low temperatures. Therefore, the compound of the present invention and / or a solution of the compound of the present invention in an aliphatic hydrocarbon solvent (e.g., an n-hexane solution, a methylcyclohexane solution) is useful as a cocatalyst for the solution polymerization of olefins or dienes, which is easy to quantify and handle.

[0094] The present invention encompasses a method for producing a polymer, which comprises solution polymerizing at least one monomer selected from the group consisting of olefins and dienes using the compound of the present invention as a cocatalyst.

[0095] Specifically, the production of a polymer using the compound of the present invention as a co-catalyst can be carried out, for example, in accordance with the method described in Test Example 2 below.

[0096] The present invention will be specifically explained by the following Production Examples, Examples, and Test Examples, but the present invention is not limited to these Production Examples and Examples. % indicates mol / mol% for yield, and % by weight for other values ​​unless otherwise specified. Room temperature indicates 20°C to 25°C.

[0097] The following instruments were used for the analysis: １ H-NMR and １９ F-NMR: ECZ400S FT-NMR manufactured by JEOL Ltd. Solvents and reagents used in the following Production Examples and Examples were purchased from distributors such as Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., Fujifilm Wako Pure Chemical Industries, Ltd., Junsei Chemical Co., Ltd., Kanto Chemical Co., Ltd., and Combi-Blocks, unless otherwise specified. Deuterated solvents used in NMR measurements were purchased from Cambridge Isotope Laboratory.

[0098] [Production Example 1] Synthesis of N,N-dihexadecyl-4-butylaniline hydrochloride (1) Tetrahydrofuran (10.7 g) was added to sodium hydride (content 66.4 wt%, 1.26 g, 33.8 mmol), and the mixture was heated to reflux at 75°C in an oil bath, while a solution of 4-butylaniline (2.0 g, 13.4 mmol) in tetrahydrofuran (5.6 g) was added dropwise. Subsequently, a solution of 1-bromohexadecane (8.2 g, 26.9 mmol) in tetrahydrofuran (17.8 g) was added dropwise to the reaction mixture, and the mixture was heated and refluxed for 20 hours. After cooling the reaction mixture, a mixed solution of water (0.4 g) and tetrahydrofuran (1.9 g) was added. After the evolution of hydrogen gas subsided, water (10.0 g) was added, and the mixture was separated. The organic phase was concentrated under reduced pressure, and n-hexane (53.6 g) was added to the residue to dissolve it. After washing with water, the solution was concentrated under reduced pressure and dried to obtain N,N-dihexadecyl-4-butylaniline (8.2 g). 1 H NMR (CDCl) δ: 7.01 (d, J=8.7 Hz, 2H), 6.57 (d, J=8.7 Hz, 2H), 3.20 (t, J=7.5 Hz, 4H), 2.49 (t, J=7.8 Hz, 2H), 1.48-1.64 (m, 4H), 1.09-1.45 (m, 56H), 0.78-0.97 (m, 9H). (2) N,N-Dihexadecyl-4-butylaniline (8.2 g, 13.7 mmol) obtained in (1) above was dissolved in n-hexane (27.2 g), and a 4 mol / L hydrogen chloride / ethyl acetate solution (3.4 g, 15.4 mmol) was added dropwise with stirring. Then, n-hexane (19.6 g) was added, and the mixture was stirred at room temperature for 1 hour. The resulting solid was filtered off, washed with n-hexane (11.0 g), and then dried under reduced pressure to obtain the title compound (7.2 g, 11.3 mmol). 1H NMR(CDCl3) δ: 13.70 (s, 1H), 7.60 (d, J=7.9Hz, 2H), 7.30 (d, J=8.6Hz, 2H), 3.35-3.53 (m, 2H), 3.03-3.24 (m, 2H), 2.65 (t, J=7.6Hz, 2H), 1.90-2.12 (m, 2H), 1.53-1.68 (m, 2H), 0.99-1.46 (m, 56H), 0.94 (t, J=7.3Hz, 3H), 0.88 (t, J=7.0Hz, 6H).

[0099] Preparation Example 2 Synthesis of N,N-dioctadecyl-4-butylaniline hydrochloride (1) Tetrahydrofuran (10.7 g) was added to sodium hydride (content 66.4 wt %, 1.26 g, 33.8 mmol), and the mixture was heated to reflux at 75°C in an oil bath, while a solution of 4-butylaniline (2.0 g, 13.4 mmol) in tetrahydrofuran (5.6 g) was added dropwise. Subsequently, a solution of 1-bromooctadecane (9.8 g, 29.4 mmol) in tetrahydrofuran (17.8 g) was added dropwise to the reaction mixture, and the mixture was heated and refluxed for 21 hours. After cooling the reaction mixture, a mixed solution of water (0.5 g) and tetrahydrofuran (1.8 g) was added. After the evolution of hydrogen gas subsided, water (10.0 g) was added, and the mixture was separated. The organic phase was concentrated under reduced pressure, and n-hexane (53.6 g) was added to the residue to dissolve it. After washing with water, the solution was concentrated under reduced pressure and dried to obtain N,N-dioctadecyl-4-butylaniline (9.7 g). 1H NMR (CDCl) δ: 7.01 (d, J = 8.7 Hz, 2H), 6.57 (d, J = 8.7 Hz, 2H), 3.21 (t, J = 7.5 Hz, 4H), 2.49 (t, J = 7.5 Hz, 2H), 1.47-1.65 (m, 4H), 1.01-1.46 (m, 64H), 0.79-0.98 (m, 9H). (2) N,N-Dioctadecyl-4-butylaniline (9.3 g, 14.2 mmol) obtained in (1) above was dissolved in n-heptane (64.9 g), and a 4 mol / L hydrogen chloride / ethyl acetate solution (3.5 g, 15.8 mmol) was added dropwise with stirring, followed by stirring at room temperature for 2 hours. The resulting solid was filtered off, washed with n-heptane (12.8 g), and then dried under reduced pressure to obtain the title compound (8.4 g, 12.2 mmol). 1 H NMR(CDCl3) δ: 13.71 (bs, 1H), 7.59 (d, J=8.6Hz, 2H), 7.29 (d, J=8.6hz, 2H), 3.32-3.54 (m, 2H), 3.02-3.22 (m, 2H), 2.65 (t, J=7.9Hz, 2H), 1.87-2.12 (m, 2H), 1.54-1.67 (m, 2H), 1.05-1.45 (m, 64H), 0.94 (t, J=7.3Hz, 3H), 0.87 (t, J=7.0Hz, 6H).

[0100] Preparation Example 3 Synthesis of N,N-dihexadecylaniline Tetrahydrofuran (10.72 g) was added to sodium hydride (content 66.4 wt %, 2.07 g, 55.5 mmol), and the mixture was heated to reflux at 75°C in an oil bath, while a solution of aniline (2.0 g, 21.9 mmol) in tetrahydrofuran (5.5 g) was added dropwise. Subsequently, a solution of 1-bromohexadecane (13.1 g, 42.9 mmol) in tetrahydrofuran (17.8 g) was added dropwise to the reaction mixture, and the mixture was heated and refluxed for 5 hours. After cooling the reaction mixture, a mixed solution of water (0.4 g) and tetrahydrofuran (1.8 g) was added. After the evolution of hydrogen gas subsided, water (10.1 g) and tetrahydrofuran (6.3 g) were added, and the mixture was separated. The organic phase was heated to 45° C., ethanol (111 g) was added, the mixture was cooled to 20° C., and stirred at 20 to 25° C. for 15 hours. The resulting solid was collected by filtration, washed with ethanol, and dried under reduced pressure to obtain the title compound (10.4 g). 1 H NMR(CDCl3) δ: 7.12-7.23 (m, 3H), 6.55-6.69 (m, 2H), 3.24 (m, 4H), 1.58-1.49 (m, 4H), 1.30-1.11 (m, 52H), 0.88 (t, J=6.9 Hz, 6H).

[0101] Preparation Example 4 Synthesis of N,N-dioctadecylaniline hydrochloride Tetrahydrofuran (53.6 g) was added to sodium hydride (content 66.4 wt %, 10.09 g, 270.7 mmol), and the mixture was heated to reflux at 75°C in an oil bath, while a solution of aniline (10.01 g, 107.5 mmol) in tetrahydrofuran (26.81 g) was added dropwise. Subsequently, a solution of 1-bromooctadecane (78.9 g, 236.7 mmol) in tetrahydrofuran (89.1 g) was added dropwise to the reaction mixture, and the mixture was heated and refluxed for 5 hours. After cooling the reaction mixture, a mixed solution of water (2.0 g) and tetrahydrofuran (8.9 g) was added. After the evolution of hydrogen gas subsided, water (50.0 g) was added, and the mixture was separated. The organic phase was concentrated under reduced pressure, and n-hexane (425 g) and water (50.7 g) were added to the residue and stirred. After that, n-hexane (43 g) and water (49.7 g) were added to the organic phase and stirred again, followed by separation, yielding a hexane solution of N,N-dioctadecylaniline (531.6 g). To the resulting hexane solution of N,N-dioctadecylaniline (528.1 g) was added n-hexane (170.7 g), and a 1 mol / L hydrogen chloride / diethyl ether solution (77.3 g, 118.7 mmol) was added dropwise under stirring, followed by stirring at room temperature for 1.5 hours. The resulting solid was filtered and washed with n-hexane (213 g). The solid was then dispersed in n-hexane (637.3 g), stirred at 50°C for 2 hours, and then cooled to room temperature. The solid was filtered off, washed with n-hexane (213 g), and dried under reduced pressure to obtain the title compound (65.9 g, 103.9 mmol). 1 H NMR(CDCl3) δ: 7.19 (m, 2H), 6.64-6.59 (m, 3H), 3.40-3.05 (m, 4H), 1.57 (m, 4H), 1.02-1.46 (m, 60H), 0.88 (t, J=7.0Hz, 6H).

[0102] Preparation Example 5 Synthesis of N,N-dioctadecyl-4-methylaniline Tetrahydrofuran (10.7 g) was added to sodium hydride (content 66.4 wt %, 1.75 g, 47.0 mmol), and the mixture was heated to reflux at 75°C in an oil bath, while a solution of 4-methylaniline (2.0 g, 18.7 mmol) in tetrahydrofuran (5.4 g) was added dropwise. Subsequently, a solution of 1-bromooctadecane (12.4 g, 37.2 mmol) in tetrahydrofuran (17.85 g) was added dropwise to the reaction mixture, and the mixture was heated and refluxed for 5 hours. After cooling the reaction mixture, a mixed solution of water (0.4 g) and tetrahydrofuran (1.9 g) was added. After the evolution of hydrogen gas subsided, water (10.0 g) was added, and the mixture was separated. Tetrahydrofuran (5.4 g) was added to the organic phase, and ethanol (81 g) was added while heating and stirring at 45° C., and then the mixture was cooled to 25° C. and stirred continuously for 20 hours. The resulting solid was filtered off, washed with ethanol, and dried under reduced pressure to obtain the title compound (10.2 g). 1 H NMR(CDCl3) δ: 7.01 (d, J=8.2Hz, 2H), 6.56 (d, J=8.7Hz, 2H), 3.20 (t, J=7.8Hz, 4H), 2.23 (s, 3H), 1.47-1.65 (4H), 1.06-1.46 (m, 60H), 0.88 (t, J=6.9Hz, 6H).

[0103] Preparation Example 6 Synthesis of N,N-didodecyl-4-butylaniline hydrochloride (1) Tetrahydrofuran (10.8 g) was added to sodium hydride (content 66.4 wt %, 1.26 g, 33.8 mmol), and the mixture was heated to reflux at 75°C in an oil bath, while a solution of 4-butylaniline (2.0 g, 13.4 mmol) in tetrahydrofuran (5.5 g) was added dropwise. Subsequently, a solution of 1-bromododecane (6.7 g, 26.9 mmol) in tetrahydrofuran (17.9 g) was added dropwise to the reaction mixture, and the mixture was heated and refluxed for 19 hours. After cooling the reaction mixture, a mixed solution of water (0.4 g) and tetrahydrofuran (1.8 g) was added. After the evolution of hydrogen gas subsided, water (10.0 g) was added, and the mixture was separated. The organic phase was concentrated under reduced pressure, and n-hexane (43.6 g) was added to the residue to dissolve it. After washing with water, the solution was concentrated under reduced pressure and dried to obtain N,N-didodecyl-4-butylaniline (6.7 g). 1 H NMR (CDCl) δ: 7.01 (d, J=8.7 Hz, 2H), 6.57 (d, J=8.7 Hz, 2H), 3.21 (t, J=7.8 Hz, 4H), 2.49 (t, J=7.5 Hz, 2H), 1.47-1.65 (m, 4H), 1.15-1.47 (m, 40H), 0.94-0.87 (m, 2H). (2) N,N-didodecyl-4-butylaniline (6.5 g, 13.4 mmol) obtained in (1) above was dissolved in n-hexane (21.6 g), and a 4 mol / L hydrogen chloride / ethyl acetate solution (3.3 g, 15.0 mmol) was added dropwise with stirring. Then, n-hexane (6.4 g) was added, and the mixture was stirred at room temperature for 2 hours. The resulting solid was filtered off, washed with n-hexane (8.7 g), and then dried under reduced pressure to obtain the title compound (5.8 g, 11.1 mmol). 1H NMR(CDCl3) δ: 13.70 (s, 1H), 7.59 (d, J=8.6Hz, 2H), 7.29 (d, J=8.6Hz,2H), 3.31-3.58 (m, 2H), 2.87-3.28 (m, 2H), 2.65 (t, J=7.6Hz, 2H), 1.85-2.15 (m, 2H), 1.52-1.69 (m, 2H), 1.05-1.46 (m, 40H), 0.94 (t, J=7.3Hz, 3H), 0.87 (t, J=6.7Hz, 6H).

[0104] Preparation Example 7 Synthesis of N,N-ditetradecyl-4-butylaniline hydrochloride (1) Tetrahydrofuran (10.7 g, mmol) was added to sodium hydride (content 66.4 wt %, 1.26 g, 33.8 mmol), and the mixture was heated to reflux at 75°C in an oil bath, while a solution of 4-butylaniline (2.0 g, 13.4 mmol) in tetrahydrofuran (5.4 g) was added dropwise. Subsequently, a solution of 1-bromotetradecane (7.4 g, 26.7 mmol) in tetrahydrofuran (18.0 g) was added dropwise to the reaction mixture, and the mixture was heated and refluxed for 12 hours. After cooling the reaction mixture, a mixed solution of water (0.4 g) and tetrahydrofuran (1.9 g) was added. After the evolution of hydrogen gas subsided, water (10.0 g) was added, and the mixture was separated. The organic phase was concentrated under reduced pressure, and n-hexane (53.6 g) was added to the residue to dissolve it. After washing with water, the solution was concentrated under reduced pressure and dried to obtain N,N-ditetradecyl-4-butylaniline (7.5 g). 1H NMR (CDCl) δ: 7.01 (d, J = 8.6 Hz, 2H), 6.57 (d, J = 9.2 Hz, 2H), 3.20 (t, J = 7.6 Hz, 4H), 2.49 (t, J = 7.9 Hz, 2H), 1.46-1.65 (m, 4H), 1.00-1.46 (m, 48H), 0.78-0.98 (m, 9H). (2) N,N-Ditetradecyl-4-butylaniline (7.0 g, 12.9 mmol) obtained in (1) above was dissolved in n-hexane (46 g), and a 4 mol / L hydrogen chloride / ethyl acetate solution (3.1 g, 14.1 mmol) was added dropwise with stirring, followed by stirring at room temperature for 1 hour. The resulting solid was filtered off, washed with n-hexane (23.3 g), and then dried under reduced pressure to obtain the title compound (5.7 g, 9.9 mmol). 1 H NMR(CDCl3) δ: 13.41-13.99 (bs, 1H), 7.59 (d, J=8.6Hz, 2H), 7.29 (d, J=7.9Hz,2H), 3.29-3.55 (m, 2H), 3.01-3.28 (m, 2H), 2.65 (t, J=7.6Hz, 2H), 1.85-2.12 (m, 2H), 1.49-1.71 (m, 2H), 1.00-1.49 (m, 48H), 0.94 (t, J=7.3Hz, 3H), 0.87 (t, J=7.0Hz, 6H).

[0105] Example 1 N,N-Dihexadecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate (Compound (1-1))

[0106]

[0107] N,N-Dihexadecyl-4-butylaniline hydrochloride (5.0 g, 7.9 mmol) obtained in Production Example 1 was dissolved in methylcyclohexane (19.3 g), and water (10.0 g) and lithium tetrakis(pentafluorophenyl)borate 3-diethyl ether complex (8.2 g, 7.9 mmol) were added with stirring, followed by stirring at room temperature for 2 hours. The reaction mixture was separated, and the organic phase was washed with water. After distilling off methylcyclohexane (18 g) under reduced pressure, methylcyclohexane (18 g) was added to the residue, and methylcyclohexane (16 g) was again distilled off under reduced pressure. Methylcyclohexane (18 g) was again added to the residue, and methylcyclohexane (16 g) was again distilled off under reduced pressure. Methylcyclohexane (16 g) was added to the residue again, and the methylcyclohexane (16 g) was distilled off under reduced pressure to obtain a methylcyclohexane solution of N,N-dihexadecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate. Quantitative analysis by NMR using an internal standard revealed that the concentration of N,N-dihexadecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate was 50.0 wt % (351 mM). 1 H NMR(CDCl3) δ: 7.39 (d, J=8.2Hz, 2H), 7.02 (d, J=8.7Hz, 2H), 3.19-3.72 (m, 4H), 2.71 (t, J=7.8Hz, 2H), 1.55-1.74 (m, 2H), 1.00-1.55 (m, 58H), 0.96 (t, J=7.3Hz, 3H), 0.87 (t, J=6.9Hz, 6H); 19 F NMR(CDCl3) δ: -132.5 (d, J=10.1Hz, 8F), -161.8 (t, J=21.0Hz, 4F), -166.0 (t, J=18.1Hz, 8F).

[0108] Example 2 N,N-Dioctadecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate (Compound (1-2))

[0109]

[0110] N,N-Dioctadecylaniline hydrochloride (5.0 g, 7.2 mmol) obtained in Preparation Example 2 was dissolved in methylcyclohexane (19.3 g), and water (10.0 g) and lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (8.2 g, 7.2 mmol) were added with stirring, followed by stirring at room temperature for 2 hours. The reaction mixture was separated, and the organic phase was washed with water. After distilling off methylcyclohexane (18 g) under reduced pressure, methylcyclohexane (18 g) was added to the residue, and methylcyclohexane (16 g) was again distilled off under reduced pressure. Methylcyclohexane (18 g) was added to the residue again, and methylcyclohexane (16 g) was again distilled off under reduced pressure. Methylcyclohexane (16 g) was again added to the residue, and methylcyclohexane (16 g) was again distilled off under reduced pressure, yielding a methylcyclohexane solution of the title compound. As a result of quantitative analysis by NMR using an internal standard, the concentration of N,N-dihexadecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate was 50.9% by weight (333 mM). 1 H NMR(CDCl3) δ: 0.87 (d, J=6.9Hz, 6H), 0.96 (t, J=7.3Hz, 3H), 1.01-1.53 ​​(m, 66H), 1.57-1.73 (m, 2H), 2.71 (t, J=7.8Hz, 2H), 3.22-3.73 (m, 4H), 7.02 (d, J=8.7Hz, 2H), 7.39 (d, J=8.7Hz, 2H); 19 F NMR(CDCl3) δ: -132.5 (d, J=10.1Hz, 8F), -161.8 (t, J=21.0Hz, 4F), -166.0 (t, J= 18.1Hz, 8F).

[0111] Comparative Example 1 N,N-Dihexadecylanilinium tetrakis(pentafluorophenyl)borate (Compound of Comparative Example 1)

[0112]

[0113] N,N-Dihexadecylaniline (6.0 g, 11.1 mmol) obtained in Preparation Example 3 was dissolved in methylcyclohexane (24.6 g), and water (7.2 g) and 2 mol / L hydrochloric acid (5.8 g, 11.3 mmol) were added with stirring. Lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (11.5 g, 11.1 mmol) was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. The resulting reaction mixture was separated, and the organic phase was washed with water. After distilling off methylcyclohexane (23 g) under reduced pressure, methylcyclohexane (24 g) was added to the residue, and methylcyclohexane (24 g) was again distilled off under reduced pressure. The same addition and distillation of methylcyclohexane was repeated two more times to obtain a methylcyclohexane solution of the title compound (52.7 wt % (401 mM)). 1 H NMR(CDCl3) δ: 7.54-7.71 (m, 3H), 7.07-7.21 (m, 2H), 3.51 (t, J=8.0Hz, 4H), 0.99-1.52 (56H), 0.87 (t, J=6.9hz, 6H); 19 F NMR(CDCl3) δ: -132.5 (d, J=10.1Hz, 8F), -161.7 (t, J=21.0Hz, 4F), -166.0 (t, J=18.1Hz, 8F).

[0114] [Comparative Example 2] N,N-Dioctadecylanilinium tetrakis(pentafluorophenyl)borate (Comparative Example 2 Compound)

[0115]

[0116] N,N-Dioctadecylaniline hydrochloride (7.02 g, 11.1 mmol) obtained in Preparation Example 4 and methylcyclohexane (27.1 g) were mixed, and while stirring, lithium tetrakis(pentafluorophenyl)borate 3-diethyl ether complex (11.4 g, 11.0 mmol) and water (14.0 g) were added, and the mixture was stirred at room temperature for 2 hours. The resulting reaction mixture was separated, and the organic phase was washed with water. After distilling off methylcyclohexane (26 g) under reduced pressure, methylcyclohexane (27 g) was added, and methylcyclohexane (22 g) was again distilled off under reduced pressure. The same addition and distillation of methylcyclohexane was repeated two more times to obtain a methylcyclohexane solution of the title compound. Quantitative analysis by NMR using an internal standard revealed that the concentration of N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate in the solution was 49.0 wt % (338 mM). 1 H NMR(CDCl3) δ: 7.54-7.70 (m, 3H), 7.15 (d, J=6.7Hz, 2H), 3.51 (t, J=7.9Hz, 4H), 1.35-1.59 (m, 4H), 0.94-1.35 (60H), 0.87 (t, J=6.7Hz, 6H); 19 F NMR(CDCl3) δ: -132.6 (d, J=10.1Hz, 8F), -161.8 (t, J=21.0Hz, 4F), -166.0 (t, J=18.1Hz, 8F).

[0117] Comparative Example 3 N,N-Dioctadecyl-4-methylanilinium tetrakis(pentafluorophenyl)borate (Compound of Comparative Example 3)

[0118]

[0119] N,N-Dioctadecyl-4-methylaniline (5.0 g, 8.2 mmol) obtained in Preparation Example 5 was dissolved in methylcyclohexane (20.5 g), and water (6.5 g) and 2 mol / L hydrochloric acid (4.3 g, 8.3 mmol) were added with stirring. Lithium tetrakis(pentafluorophenyl)borate tri-diethyl ether complex (8.5 g, 8.2 mmol) was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. The resulting reaction mixture was separated, and the organic phase was washed with water. After distilling off methylcyclohexane (17 g) under reduced pressure, methylcyclohexane (17 g) was added to the residue, and methylcyclohexane (14 g) was again distilled off under reduced pressure. Methylcyclohexane (15 g) was again added to the residue, and methylcyclohexane (16 g) was distilled off under reduced pressure to obtain a methylcyclohexane solution of the title compound. As a result of quantitative analysis by NMR using an internal standard, the concentration of N,N-dihexadecyl-4-methylanilinium tetrakis(pentafluorophenyl)borate in the solution was 51.3% by weight (366 mM). 1 H NMR(CDCl3) δ: 7.38 (d, J=8.2Hz, 2H), 7.00 (d, J=8.7Hz, 2H), 3.47 (t, J=8.0Hz, 4H), 2.46 (s, 3H), 0.95-1.54 (64H), 0.87 (t, J=6.9Hz, 6H); 19 F NMR(CDCl3) δ: -132.5 (d, J=10.1Hz, 8F), -161.8 (t, J=20.2Hz, 4F), -166.0 (t, J=18.1Hz, 8F).

[0120] Comparative Example 4 N,N-didodecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate (Compound of Comparative Example 4)

[0121]

[0122] N,N-didodecyl-4-butylaniline hydrochloride (5.0 g, 9.6 mmol) obtained in Production Example 6 was dissolved in methylcyclohexane (19.3 g), and water (10.0 g) and lithium tetrakis(pentafluorophenyl)borate 3-diethyl ether complex (9.9 g, 9.6 mmol) were added with stirring, followed by stirring at room temperature for 2 hours. The resulting reaction mixture was separated, and the organic phase was washed with water. After distilling off methylcyclohexane (12 g) under reduced pressure, methylcyclohexane (12 g) was added to the residue, and methylcyclohexane (10 g) was again distilled off under reduced pressure. Methylcyclohexane (21 g) was again added to the residue, and methylcyclohexane (9 g) was again distilled off under reduced pressure to obtain a methylcyclohexane solution of the title compound. As a result of quantitative analysis by NMR using an internal standard, the concentration of N,N-didodecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate in the solution was 58.6% by weight (472 mM). 1 H NMR(CDCl3) δ: 7.39 (d, J=8.7Hz, 2H), 7.02 (d, J=8.7Hz, 2H), 3.48 (bs, 4H), 2.71 (t, J=8.0Hz, 2H), 1.54-1.75 (m, 2H), 0.99-1.54 (m, 42H), 0.96 (t, J=7.3Hz, 3H), 0.88-0.84 (t, J=6.9Hz, 6H); 19 F NMR(CDCl3) δ: -132.5 (d, J=10.1Hz, 8F), -161.8 (t, J=20.2Hz, 4F), -166.0 (t, J=18.8Hz, 8F).

[0123] Comparative Example 5 N,N-ditetradecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate (Compound of Comparative Example 5)

[0124]

[0125] N,N-Ditetradecyl-4-butylaniline hydrochloride (5.0 g, 8.6 mmol) obtained in Production Example 7 was dissolved in methylcyclohexane (19.3 g), and water (10.0 g) and lithium tetrakis(pentafluorophenyl)borate 3-diethyl ether complex (9.0 g, 8.7 mmol) were added with stirring, followed by stirring at room temperature for 2 hours. The resulting reaction mixture was separated, and the organic phase was washed with water. After distilling off methylcyclohexane (17 g) under reduced pressure, methylcyclohexane (17 g) was added to the residue, and methylcyclohexane (16 g) was again distilled off under reduced pressure. Methylcyclohexane (18 g) was added to the residue, and methylcyclohexane (16 g) was again distilled off under reduced pressure. Methylcyclohexane (17 g) was then added to the residue, and methylcyclohexane (16 g) was again distilled off under reduced pressure. Furthermore, methylcyclohexane (17 g) was again added to the residue, and methylcyclohexane (17 g) was again distilled off under reduced pressure, yielding a methylcyclohexane solution of the title compound. As a result of quantitative analysis by NMR using an internal standard, the concentration of N,N-ditetradecyl-4-butylanilinium tetrakis(pentafluorophenyl)borate in the solution was found to be 55.5% by weight (423 mM). 1 H NMR(CDCl3) δ: 7.38 (d, J=8.7Hz, 2H), 7.02 (d, J=8.7Hz, 2H), 3.48 (bs, 4H), 2.71 (t, J=7.8Hz, 2H), 1.54-1.74 (m, 2H), 1.01-1.54 (m, 50H), 0.95 (t, J=7.3Hz, 3H), 0.86 (t, J=6.9Hz, 6H); 19 F NMR(CDCl3) δ: -132.5 (d, J=10.1Hz, 8F), -161.8 (t, J=20.2Hz, 4F), -166.0 (t, J=18.1Hz, 8F).

[0126] Test Example 1 (Evaluation of Solubility) A methylcyclohexane solution containing 50% by weight of each of the compounds obtained in Examples 1 and 2 and Comparative Examples 1 to 5, and an n-hexane solution containing 0.6% by weight (≈3 mM) of each of the compounds were prepared, and after storing at room temperature or at -15°C for 3 days, the appearance of each solution was visually inspected. The results are shown in Tables 1 and 2 below. The symbols used to evaluate solubility in the tables mean the following: ◯: Uniform, transparent solution; △: Cloudy; ×: Two-phase separation or crystal precipitation.

[0127]

[0128]

[0129] According to Tables 1 and 2, it was confirmed that Examples 1 and 2 were able to maintain significantly higher solubility in aliphatic hydrocarbon solvents even at low temperatures compared to Comparative Examples 1 to 5.

[0130] Test Example 2 (Evaluation of Polymerization Performance) A typical polymerization method using the compound of the present invention (compound (1-2)) as a cocatalyst is described below. In a glove box, 1-octene, triisobutylaluminum (TIBA, 1.00 M hexane solution), and a solvent (methylcyclohexane (MCH)) were added to a 100 mL autoclave to prepare a comonomer solution. Dimethylsilylene(tert-butylamido)-(tetramethylcyclopentadienyl)-titanium(IV)-dichloride (CGC), which is a polymerization catalyst, triisobutylaluminum (1.00 M hexane solution), and a solvent were added to prepare a catalyst solution of a predetermined concentration, which was then transferred to a Schlenk flask. Compound (1-2) (cocatalyst) was dissolved in a solvent to prepare a cocatalyst solution of a predetermined concentration, which was then transferred to a Schlenk flask. The mixture was transferred to a Lenk flask. After mixing the comonomer solution, catalyst solution, and cocatalyst solution, the total amount of solvent and the total amount of triisobutylaluminum were adjusted to be constant. After purging the autoclave with ethylene gas, the catalyst solution and cocatalyst solution were added sequentially to the autoclave, and the ethylene gas pressure was quickly adjusted to a predetermined pressure, followed by stirring at 50°C for 6 minutes. After ice-cooling the reaction mixture and venting the ethylene gas, the mixture was poured into methanol (100 mL) containing 3 mL of hydrochloric acid and stirred at room temperature for 30 minutes. The precipitate was collected by filtration and dried under reduced pressure at 60°C to obtain an ethylene-octene copolymer (47.3 mg).

[0131] (Reaction conditions) Catalyst: CGC (3 μmol); catalyst:cocatalyst=1:1; TIBA (3000 μmol); total amount of solvent (40 ml); 1-octene (1 mL); ethylene pressure (8 atmospheres); reaction temperature: 50° C.; reaction time: 6 minutes

[0132] (Melting Point Measurement) The melting point of the sample was measured by differential scanning calorimetry (DSC). This was carried out using a DSC7000X (manufactured by Hitachi High-Tech Science Corporation). To remove thermal history, the sample was heated from room temperature to 250°C (heating rate: 20°C / min) and then held at 250°C for 5 minutes. Thereafter, the temperature was lowered to -100°C at 10°C / min, held for 10 minutes, and then heated from -100°C to 250°C at a rate of 10°C / min. The melting point value during the second heating was recorded. The melting point of the polymer obtained under the above conditions was 127.5°C.

[0133] As described above, it has been revealed that the compounds of the present invention function as cocatalysts in metallocene-catalyzed polymerization.

[0134] According to the present invention, it is possible to provide a novel borate compound that can maintain a homogeneous solution state in an aliphatic hydrocarbon solvent, particularly n-hexane, methylcyclohexane, or a mixed solvent thereof, even at low temperatures, without using any aromatic hydrocarbon solvent. Because the compound of the present invention can maintain a homogeneous solution state in an aliphatic hydrocarbon solvent even at low temperatures, the compound of the present invention can be stably stored in the form of a diluted solution that is easy to handle and measure, which has the advantage that it can be used as is as a cocatalyst for the solution polymerization reaction of olefins or dienes. Furthermore, the present invention also provides a simple method for producing the compound of the present invention.

[0135] This application is based on Japanese Patent Application No. 2023-156460 filed on September 21, 2023 in Japan, the contents of which are incorporated in their entirety herein.

Claims

1. Formula (1): [In the formula, R １ and R ２ are each independently a linear C １６－２０ represents an alkyl group; R ３ is a linear C ３－８ represents an alkyl group; and R ４ , R ５ , R ６ and R ７ Each independently represents one or more fluorine atoms or fluoro C １－４ C substituted with alkyl group ６－１４ represents an aryl group.

2. R １ and R ２ each independently represents a linear C １６－１８ is an alkyl group, and R ３ But linear C ４－６ The compound of claim 1 which is an alkyl group.

3. R ４ , R ５ , R ６ and R ７ The compound according to claim 1, wherein each of the is independently a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, each of which is substituted with one or more fluorine atoms or trifluoromethyl groups.

4. R ４ , R ５ , R ６ and R ７ The compound according to claim 1, wherein all of are pentafluorophenyl groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups.

5. The compound according to any one of claims 1 to 4, wherein the compound exhibits a solubility of 3 mM or more in n-hexane at a temperature range of -15°C to 25°C, and a solubility of 300 mM or more in methylcyclohexane at a temperature range of -15°C to 25°C.

6. A solution of the compound according to any one of claims 1 to 4 in n-hexane at a temperature in the range of -15°C to 25°C, the solution containing the compound at a concentration of 3 mM or more.

7. A methylcyclohexane solution of the compound according to any one of claims 1 to 4, containing 300 mM or more of the compound at a temperature in the range of -15°C to 25°C.

8. A cocatalyst for the solution polymerization of at least one monomer selected from the group consisting of olefins and dienes, comprising the compound according to any one of claims 1 to 4.

9. A method for storing the compound according to any one of claims 1 to 4, comprising dissolving the compound in n-hexane or methylcyclohexane and storing the compound at -15°C to 0°C while maintaining the compound in a homogeneous solution state.

10. Formula (2): [In the formula, R １ and R ２ are each independently a linear C １６－２０ represents an alkyl group; R ３ is a linear C ３－８ represents an alkyl group; and X represents a halogen atom.] and a compound represented by formula (3): [In the formula, R ４ , R ５ , R ６ and R ７ Each independently represents one or more fluorine atoms or fluoro C １－４ C substituted with alkyl group ６－１４ and M represents an alkali metal; in a mixed solvent of methylcyclohexane and water.

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