KR100843613B1 - Method for Preparing the phosphonium compound for cyclic olefin polymerization - Google Patents

Abstract

The present invention relates to a method for preparing a phosphonium compound promoter, and in detail, _a protic phosphonium compound represented by [(R ₁ ) -P (R ₂ ) _a (R ₂ ) _b ] HX and [C] ] It is related with the method of manufacturing the promoter which consists of a salt compound which has a phosphonium by reaction with the salt compound represented by [Ani].

The method for producing a phosphonium cocatalyst compound according to the present invention can produce a phosphonium salt compound, which is a promoter for polar cyclic olefin polymerization, in high yield.

Norbornene, phosphonium compounds

Description

Method for preparing the phosphonium compound for cyclic olefin polymer production

The present invention relates to a method for preparing a phosphonium compound, and more particularly, to a phosphonium which is a promoter of a catalyst system for polymerizing a cyclic olefin monomer including a polar functional group to produce a cyclic olefin polymer including the polar functional group. The present invention relates to a method for preparing a compound.

Cyclic olefin polymer is a polymer composed of cyclic monomers such as norbornene, and has excellent transparency, heat resistance, and chemical resistance, and has very low birefringence and water absorption rate compared to existing olefinic polymers. It can be applied to various medical materials such as optical materials, capacitor films, information electronic materials such as low dielectrics, low absorbing syringes, blister packaging, and the like.

However, in order to use polymers for information electronic materials, in general, polymers have adhesion to metal surfaces such as silicon, silicon oxide, silicon nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, nickel, tantalum, and chromium. Because of this demand, attempts have been made to introduce polar functional groups into norbornene-based monomers in order to control the metal adhesion and various electrical, optical and chemical physical properties of these norbornene-based polymers. However, when the polar functional group is introduced into the norbornene-based monomer, the catalyst activity is degraded or an excessive catalyst is required.

For example, US Pat. No. 5,705,503 discloses a method of polymerizing norbornene-based monomers with polar functional groups using ((Allyl) PdCl) ₂ / AgSbF ₆ as catalyst complex, but the ratio of catalyst to monomer is 1 Since the amount of the catalyst used is excessively large as 1: 100 to 1: 250, the catalyst residue remains in a large amount in the finally obtained polymer, and the polymer may be degraded by thermal oxidation in the future, and the light transmittance may also be poor.

In addition, when the ester norbornene monomer was polymerized by the cationic [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ catalyst, the polymerization yield was low, and only exo isomers were selectively polymerized (Sen, A .; Lai, T.-WJ Am. Chem. Soc. 1981, Vol. 103, 4627-4629) When polymerizing norbornene comprising an ester group or an acetyl group, the catalyst is about 1/100 to 1/100 of the monomer. Since it should be used in excess of 400, there was a problem that it is difficult to remove the catalyst residue after the polymerization.

However, it has been found that the catalytic activity is further improved when the promoter is used in the catalyst for the cyclic olefin polymerization. As such a promoter, a neutral phosphine compound, an ammonium compound, or the like has been used as a compound capable of strong sigma bonding with a metal.

For example, in Lipian et al. (Sen, et al., Organometallics 2001, Vol. 20, 2802-2812), [(1,5-Cyclooctadiene) (CH ₃ ) Pd (Cl)] is substituted with PPh _3. In the reaction of polymerization of ester norbornene by activating a phosphine and a promoter such as [Na] ⁺ [B (3,5- (CF ₃ ) ₂ C ₆ H ₃ ) ₄ ] ^- , It is reported that an excess of catalyst is used to obtain a polymer having a molecular weight of about 6500 with a polymerization yield of 40% or less.

U.S. Patent No. 6,455,650 uses [(R ') _z M (L') _x (L '') _y ] _b [WCA] _d and the like as a catalyst complex, and the ligands used herein include phosphine and allyl groups. Although a method of polymerizing a norbornene-based monomer having a functional group by using a hydrocarbon containing a hydrocarbyl group such as is disclosed, when polymerizing a norbornene-based monomer having a polar functional group such as a carbonyl group, the yield is 5%. Since it is low, there existed a problem that it was unsuitable for manufacture of polymer which has polar functional groups, such as a carbonyl group. This low yield was the same for US Pat. Nos. 5,468,819, 5,569,730, 5,912,313, 6,031,058, and the like.

As can be seen from the above, in the case of a catalyst system for cyclic olefin polymerization having a polar functional group, a catalyst system was prepared using various cocatalysts, but there was still a problem in that the catalyst reacted sensitively to the monomer and thus the reactivity was lowered. .

As an alternative to the cocatalysts, a method of using a phosphonium compound as a cocatalyst has been newly proposed (WO 2005/019277, Korean Patent Application No. 2004-0052612, 2004-0074307). There was no description about it.

Therefore, there is a need for a method of simply producing a phosphonium compound used as a promoter of a catalyst system for polymerizing the cyclic olefin monomer including the polar functional group to produce a cyclic olefin including the polar functional group.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a method for preparing a phosphonium compound which is a promoter of a catalyst system for preparing a cyclic olefin in order to solve the problems of the prior art.

The present invention to achieve the above technical problem,

As a method for producing a phosphonium cocatalyst compound represented by the following <Formula 1>

Contacting a phosphonium compound represented by <Formula 2> and a salt compound represented by <Formula 3>;

It provides a manufacturing method comprising a.

<Formula 1>

[(R ₁ ) -P (R ₂ ) _a (R _{2 '} ) _b [Z (R ₃ ) _d ] _c ] [Ani]

(Wherein

a, b and c are each an integer of 0 to 3 and a + b + c = 3;

Z is oxygen, sulfur, silicon, or nitrogen;

d is 1 when Z is oxygen or sulfur, 2 when Z is nitrogen, and 3 when Z is silicon;

R ₁ is hydrogen, alkyl or aryl;

R ₂ , R _{2 '} and R ₃ Are each independently hydrogen; Hydrocarbon, halogen or C _{1 -20} alkyl, halo-substituted or unsubstituted C 1 -C 20 linear or branched alkyl, alkoxy, allyl, the alkenyl, or vinyl; Hydrocarbon, a halogen or a C _{1 -20} halo-substituted or unsubstituted, having 3 to 12 carbon atoms in the alkyl cycloalkyl; Hydrocarbon, halogen or C _{1 -20} aryl substituted or unsubstituted by halo alkyl having a carbon number of 6 to 40; Aralkyl (aralkyl) substituted or unsubstituted with hydrocarbon, halogen or haloalkyl of C _{1 -20} 7 to 15 carbon atoms; Alkynyl group (alkynyl) substituted or unsubstituted with hydrocarbon, halogen or haloalkyl of C _{1 -20} 3 to 20 carbon atoms; Tri (linear or branched alkyl) having 1 to 10 carbon atoms, tri (linear or branched alkoxy) silyl having 1 to 10 carbon atoms; Tri (substituted or unsubstituted cycloalkyl) silyl; Tri (substituted or unsubstituted aryl having 6 to 40 carbon atoms) silyl; Tri (substituted or unsubstituted aryloxy having 6 to 40 carbon atoms) silyl; Tri (linear or branched alkyl of 1 to 10 carbon atoms) siloxy; Tri (substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms) siloxy; Or tri (substituted or unsubstituted aryl having 6 to 40 carbon atoms) siloxy, wherein each substituent in the silyl or siloxy is hydrocarbon, halogen or haloalkyl having 1 to 20 carbon atoms;

[Ani] is borate, aluminate, [SbF ₆ ]-, [PF ₆ ]-, [AsF ₆ ]-, perfluoroacetate ([CF ₃ CO ₂ ]-), perfluoropropionate ( perfluoropropionate; [C ₂ F ₅ CO ₂ ]-), perfluorobutyrate; [CF ₃ CF ₂ CF ₂ CO ₂ ]-), perchlorate ([ClO ₄ ]-), para-toluenesulfonate (p-toluenesulfonate; [p-CH ₃ C ₆ H ₄ SO ₃ ]-), [SO ₃ CF ₃ ]-, borabenzene, or halogen substituted or unsubstituted carborane)

<Formula 2>

[(R ₁ ) -P (R ₂ ) _a (R _{2 '} ) _b ] HX

Wherein H is hydrogen, X is a halogen atom, and the rest are as defined in <Formula 1>;

<Formula 3>

[C] [Ani]

In the above formula, C is an alkali metal or MgX, and [Ani] is as defined in <Formula 1>.

According to an embodiment of the present invention, as a method for preparing a phosphonium compound represented by the formula (2),

Contacting a phosphine compound and an acid represented by the following <Formula 4>;

It is preferable to further include.

<Formula 4>

[(R ₁ ) -P (R ₂ ) _a (R _{2 '} ) _b ]

Wherein each symbol is as defined above.

The method for producing a phosphonium cocatalyst compound according to the present invention can produce a phosphonium salt compound, which is a promoter for polar cyclic olefin polymerization, in high yield.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention provides a method for preparing a phosphonium cocatalyst compound represented by the following <Formula 1>, comprising contacting a phosphonium compound represented by the following <Formula 2> and a salt compound represented by the following <Formula 3> It provides a manufacturing method.

<Formula 1>

[(R ₁ ) -P (R ₂ ) _a (R _{2 '} ) _b [Z (R ₃ ) _d ] _c ] [Ani]

In Formula 1, a, b and c are each an integer of 0 to 3, and a + b + c = 3; Z is oxygen, sulfur, silicon, or nitrogen; d is 1 when Z is oxygen or sulfur, 2 when Z is nitrogen, and 3 when Z is silicon; R ₁ is hydrogen, alkyl or aryl; R ₂ , R _{2 '} And R ₃ Are each independently hydrogen; Hydrocarbon, halogen or C _{1 -20} alkyl, halo-substituted or unsubstituted C 1 -C 20 linear or branched alkyl, alkoxy, allyl, the alkenyl, or vinyl; Hydrocarbon, a halogen or a C _{1 -20} halo-substituted or unsubstituted, having 3 to 12 carbon atoms in the alkyl cycloalkyl; Hydrocarbon, halogen or C _{1 -20} aryl substituted or unsubstituted by halo alkyl having a carbon number of 6 to 40; Aralkyl (aralkyl) substituted or unsubstituted with hydrocarbon, halogen or haloalkyl of C _{1 -20} 7 to 15 carbon atoms; Alkynyl group (alkynyl) substituted or unsubstituted with hydrocarbon, halogen or haloalkyl of C _{1 -20} 3 to 20 carbon atoms; Tri (linear or branched alkyl) having 1 to 10 carbon atoms, tri (linear or branched alkoxy) silyl having 1 to 10 carbon atoms; Tri (substituted or unsubstituted cycloalkyl) silyl; Tri (substituted or unsubstituted aryl having 6 to 40 carbon atoms) silyl; Tri (substituted or unsubstituted aryloxy having 6 to 40 carbon atoms) silyl; Tri (linear or branched alkyl of 1 to 10 carbon atoms) siloxy; Tri (substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms) siloxy; Or tri (substituted or unsubstituted aryl having 6 to 40 carbon atoms) siloxy, wherein each substituent in the silyl or siloxy is hydrocarbon, halogen or haloalkyl having 1 to 20 carbon atoms;

[Ani] is borate, aluminate, [SbF ₆ ]-, [PF ₆ ]-, [AsF ₆ ]-, perfluoroacetate ([CF ₃ CO ₂ ]-), perfluoropropionate ( perfluoropropionate; [C ₂ F ₅ CO ₂ ]-), perfluorobutyrate; [CF ₃ CF ₂ CF ₂ CO ₂ ]-), perchlorate ([ClO ₄ ]-), para-toluenesulfonate (p-toluenesulfonate; [p-CH ₃ C ₆ H ₄ SO ₃ ]-), [SO ₃ CF ₃ ]-, boratabenzene, or carbolane unsubstituted or substituted with halogen;

<Formula 2>

[(R ₁ ) -P (R ₂ ) _a (R _{2 '} ) _b ] HX

In Formula 2, H is hydrogen, X is a halogen atom, and the rest are as defined in <Formula 1>;

<Formula 3>

[C] [Ani]

In Chemical Formula 3, C is an alkali metal or MgX, and [Ani] is as defined in <Formula 1>.

More specifically, as a method for producing the phosphonium promoter catalyst represented by the formula (1), by reacting the protic phosphonium compound represented by the formula (2) and the salt compound represented by the formula (3), [ C] [X] is a method of preparing a phosphonium compound represented by Chemical Formula 1 through a reaction in which a by-product is formed as a precipitate. The salt compound represented by Chemical Formula 3 is a salt compound for [Ani], which is an anionic form containing mainly alkali metal or halo magnesium (MgX).

As the reaction solvent of the two salt compounds represented by Formula 2 and Formula 3, it is possible to use a general organic solvent such as hydrocarbon, such as hexane, dichloromethane, chloroform, THF, diethyl ether, benzene, toluene chlorobenzene, etc. And preferably halogen solvents such as dichloromethane, chloroform, and chlorobenzene. Depending on the reaction solvent selection, the two salt compounds may be reacted in the form of a solution dissolved in an organic solvent or in the form of a slurry in which one salt compound is not dissolved. After the reaction of the two salt compounds, a byproduct of [C] [X] is produced which should be easy to remove. In the present invention, a by-product of [C] [X] may be formed as a precipitate through a reaction solvent, and a phosphonium promoter compound represented by Chemical Formula 1 may be obtained without further purification. The reaction temperature is preferably 0-100 ^o C, more preferably room temperature.

In addition, in the production method of the present invention, as a method for producing a phosphonium compound represented by the above <Formula 2>, further comprising the step of contacting the phosphine compound and acid (acid) represented by the following <Formula 4> desirable.

<Formula 4>

[(R ₁ ) -P (R ₂ ) _a (R _{2 '} ) _b ]

In Chemical Formula 4, each symbol is as defined above.

More specifically, the phosphonium compound represented by Chemical Formula 2 may be prepared through a reaction between a phosphine compound represented by Chemical Formula 4 and a protic acid. Here, the protic acid is an acid capable of providing H ⁺ , such as HCl, HBr, HI, HF, and HPF _6, and the range thereof is not particularly limited, and includes all acids generally used in the art. In the preparation method, a protic phosphonium compound is formed as a precipitate in a reaction between a phosphine compound and a protic acid using a hydrocarbon and an ether such as hexane as a solvent, and the reaction proceeds. As a result, protic phosphonium compounds can be obtained without further purification. The reaction temperature is preferably 0 to 100 ^° C., more preferably room temperature.

In the present invention, the borate or aluminate of Chemical Formula 1 is preferably an anion represented by the following Chemical Formula 1a or Chemical Formula 1b.

<Formula 1a>

[M '(R ₄ ) ₄ ]

<Formula 1b>

[M '(OR ₄ ) ₄ ]

In Formulas 2a and 2b, M 'is boron or aluminum; Each R ₄ is independently halogen; Hydrocarbon, halogen or a linear or branched unsubstituted or substituted by haloalkyl of _{1 -20} C 1 -C 20 branched alkyl, alkenyl; Hydrocarbon, a halogen or a C _{1 -20} halo-substituted or unsubstituted, having 3 to 12 carbon atoms in the alkyl cycloalkyl; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with hydrocarbon, halogen, haloalkyl having 1 to 20 carbon atoms; Aryl having 6 to 40 carbon atoms substituted with linear or branched trialkylsiloxy having 3 to 20 carbon atoms or linear or branched triarylsiloxy having 18 to 48 carbon atoms; A substituted or unsubstituted with hydrocarbon, halogen or haloalkyl of C _{1 -20} 7 to 15 carbon atoms it is an aralkyl group (aralkyl).

The polymer may be prepared by addition polymerization of the cyclic olefin monomer using the cocatalyst compound prepared by the production method of the present invention.

The catalyst system including the cocatalyst compound prepared by the production method of the present invention can suppress the deactivation of the catalyst by the polar functional group of the monomer due to the excellent thermal chemical stability, and thus, the polymer having a high molecular weight with high yield. It can be prepared, it is possible to reduce the amount of catalyst used relative to the monomer, there is no need to separately remove the catalyst residue.

The catalyst system including the cocatalyst compound prepared by the production method of the present invention is preferably made of a Group 10 organometallic compound procatalyst represented by the following Formula 5 and a phosphonium compound promoter represented by the formula The procatalyst has a high stability against a monomer having a polar reactor, and the cocatalyst serves to prevent catalyst stabilization by phosphonium and deactivation of the catalyst by polar groups of the polar monomer, as compared with the conventional cocatalyst ammonium borate. can do.

<Formula 5>

(R ₅ ) _x (R ₆ ) _y M

In Formula 5, M is a Group 10 metal; x and y are 0 to 2; R ₅ and R ₆ are hydrogen; halogen; Linear or branched alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms; Or linear, cyclic or branched alkyl having 1 to 20 carbon atoms, including atoms or functional groups selected from the group consisting of heteroatoms such as halogen, Si, Ge, S, O, N, alkyl alkenyl, and alkynyl; Aryl of 20 to 20, alkoxy of 1 to 20 carbon atoms, carboxyl group, amine, aralkyl of 7 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms; Linear or branched haloalkyl having 1 to 20 carbon atoms; Haloalkenyl having 1 to 20 carbon atoms; Haloalkynyl having 3 to 20 carbon atoms; Or haloaryl of 6 to 40 carbon atoms, substituted or unsubstituted with a hydrocarbon.

More specifically, the method for producing a cyclic olefin-based polymer using a catalyst system comprising a cocatalyst compound prepared by the production method of the present invention is a Group 10 metal-containing procatalyst represented by the following general formula (1) and the following general formula (2). Preparing a catalyst mixture comprising a cocatalyst comprising a phosphonium-containing salt compound and a cyclic olefin monomer comprising a polar functional group at a temperature of 80 ° C. to 150 ° C. in the presence of the catalyst mixture. It comprises the step of addition polymerization of the monomer solution containing.

In the case of a catalyst system comprising a promoter prepared by the process of the present invention, it is thermally stable so as not to decompose at a temperature of 80 ° C. or higher, thereby interfering with the interaction of the polar functional group of the norbornene monomer with the cationic catalyst at a high temperature, Because of the ability to form or recover catalytically active sites, cyclic olefinic polymers containing high molecular weight polar functional groups can be prepared in high yield. On the other hand, when the polymerization temperature exceeds 150 ℃, the catalyst component is pyrolyzed to lower the activity, it is difficult to produce a cyclic olefin polymer containing a high molecular weight polar functional group.

The monomer used in the manufacturing method of the cyclic olefin polymer containing a polar functional group is a norbornene-type monomer containing a polar functional group. Cyclic norbornene-based monomers or norbornene derivatives are monomers containing at least one norbornene (bicyclo [2.2.1] hept-2-ene) unit. It means.

The cyclic olefin-based addition polymer having a polar functional group is prepared by addition polymerization of a norbornene-based monomer including at least one polar functional group in the presence of the above-described catalyst system, to prepare a homo polymer, or a novo including different polar functional groups. The addition-polymerization of the nene-based monomers to prepare a binary or tertiary copolymer consisting of norbornene-based monomers containing a polar functional group, or by addition-polymerization of norbornene-based monomers containing a polar functional group and norbornene containing a polar functional group by addition polymerization. Binary or terpolymers can be prepared.

Norbornene-based monomer having a polar functional group as described above is a compound represented by the formula (6).

<Formula 6>

In Chemical Formula 6, m is an integer of 0 to 4, at least one of R ₇ , R ₇ ^′ , R ₇ ^″, and R ₇ ^{′ ″} represents a polar functional group, and the rest are nonpolar functional groups; R ₇ , R ₇ ^′ , R ₇ ^'' and R ₇ ^'' may be linked together to form a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or an aromatic ring having 6 to 24 carbon atoms; The nonpolar functional group is hydrogen; halogen; Linear or branched alkyl of 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; Linear or branched alkynyl, haloalkynyl having 3 to 20 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Or aralkyl having 7 to 15 carbon atoms, unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; The polar functional group is a non-hydrocarbonaceous polar group including at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron, -R ⁸ OR ⁹ , -OR ⁹ , -C (O) OR ⁹ , -R ⁸ C (O) OR ⁹ , -OC (O) OR ⁹ , -R ⁸ OC (O) OR ⁹ , -C (O) R ⁹ , -R ⁸ C (O) R ⁹ , -OC (O) R ⁹ , -R ⁸ OC (O) R ⁹ ,-(R ⁸ O) _k -OR ⁹ ,-(OR ⁸ ) _k -OR ⁹ , -C (O) -OC (O) R ⁹ , -R ⁸ C (O) -OC (O) R ⁹ , -SR ⁹ , -R ⁸ SR ⁹ , -SSR ⁸ , -R ⁸ SSR ⁹ , -S (= O) R ⁹ , -R ⁸ S (= O) R ⁹ , -R ⁸ C (= S) R ⁹ , -R ⁸ C (= S) SR ⁹ , -R ⁸ SO ₃ R ⁹ , -SO ₃ R ⁹ , -R ⁸ N = C = S, -N = C = S, -NCO, R ⁸ -NCO, -CN, -R ⁸ CN, -NNC (= S) R ⁹ , -R ⁸ NNC (= S) R ⁹ , -NO ₂ , -R ⁸ NO ₂ , -P (R ⁹ ) ₂ , -R ⁸ P (R ⁹ ) ₂ , -P (= O) (R ⁹ ) ₂ , -R ⁸ P (= O) (R ⁹ ) ₂ ,

At least one functional group selected from the group consisting of;

Each of R ⁸ and R ¹¹ in the polar functional group is linear or branched alkylene, haloalkylene, alkenylene, haloalkenylene having 1 to 20 carbon atoms; Linear or branched alkynylene, haloalkynylene having 3 to 20 carbon atoms; Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl; Arylene having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl; Or aralkylene having 7 to 15 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl,

Each of R ⁹ , R ¹² , R ¹³ and R ¹⁴ in the polar functional group is hydrogen; halogen; Linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl having 1 to 20 carbon atoms; Linear or branched alkynyl, haloalkynyl having 3 to 20 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Or an alkoxy, haloalkoxy, carboxyl group, halocarboxyl group,

k is an integer between 0 and 10.

In the method for preparing the addition polymer of the cyclic olefin including the polar functional group, the ratio of the cocatalyst to the procatalyst containing the transition metal of the Group 10 may be 0.5 to 10 moles with respect to 1 mole of the procatalyst, When the mole number of the cocatalyst is less than 0.5 mole, the activation effect of the procatalyst is weak. When the molar number is more than 10 mole, the excess phosphonium coordinates to the metal to prevent the norbornene monomer coordination in three dimensions. It is not preferable because there is a problem that stabilization weakens the double bond and interaction of the norbornene monomer, and as a result, both the polymerization yield and the molecular weight decrease.

In the process for preparing the addition polymer of the cyclic olefin containing the polar functional group, the catalyst mixture may be used on a particulate support, and the particulate support may be silica, titania, silica / chromia, silica / chromia / Titania, silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. Thus, when used by being supported on the particulate support, there is an advantage that the molecular weight distribution can be adjusted according to the use, and the apparent density of the obtained polymer can be improved.

The catalyst mixture may be added directly into a solid phase without using a solvent, but may be added after mixing the solvents to prepare an activated catalyst solution, and dissolving the procatalyst and the cocatalyst in a separate solution to polymerize the catalyst. You can also put it in. Solvents that can be used when dissolving the catalyst mixture in a solvent include dichloromethane, dichloroethane, toluene, chlorobenzene or mixtures thereof.

The total amount of the organic solvent in the reaction system may be 50% to 800% with respect to the total monomer weight in the monomer solution, preferably 50% to 400%, when less than 50%, the viscosity of the solution is too high during the polymerization reaction, it is difficult to stir There is a problem for commercialization because the unreacted monomers are left and the polymerization yield is lowered, and the viscosity is too high to add the excess solvent to dilute the solution, and when it exceeds 800%, the polymerization reaction rate is slowed and the polymerization yield and molecular weight are exceeded. All of these tend to decrease.

The catalyst mixture may be a metal catalyst complex comprising the procatalyst and the cocatalyst, and the amount of the catalyst mixture may be in the range of 1 / 2,500 to 1 / 200,000 relative to the total molar amount of the monomer in the monomer solution based on the procatalyst component. have. That is, it is possible to polymerize norbornene-based monomers having polar functional groups in a high yield while using a much smaller amount of catalyst than conventional catalyst systems. The amount used is more preferably 1/5000 to 1/20000.

The norbornene addition polymer comprising a polar functional group prepared according to the method for preparing the addition polymer of the cyclic olefin including the polar functional group includes at least 0.1 to 99.9 mol% of the norbornene-based monomer including the polar functional group, wherein the polar group Norbornene comprising a endo, exo isomer mixture consists of, the mixture composition ratio is irrelevant.

The method for preparing an addition polymer of the cyclic olefin containing the polar functional group is polymerized by dissolving and mixing a norbornene-based monomer and a catalyst in a solvent as in the conventional method for producing a norbornene-based polymer. When the cyclic olefin-based addition polymer including a polar functional group is prepared by the production method of the present invention, at least 40% or more may be produced in a high yield, and the weight average molecular weight (M _w ) of the prepared additive polymer may be 100,000 or more Can have In addition, the molecular weight is preferably adjusted to 100,000 to 1,000,000 if the optical film is prepared using the addition polymer.

The norbornene-based polymer having a polar functional group prepared according to the above production method is transparent, has excellent adhesion to metals and polymers having other polar functional groups, has a low dielectric constant that can be used as an insulating electronic material, thermal stability and strength. Is an excellent cyclic olefin polymer. In addition, the polymer can be attached to a substrate of an electronic material without a coupling agent, can be attached to a metal substrate such as copper, silver, or gold, and can be used as a protective film of a polarizing plate. It has excellent characteristics and can be used in electronic materials such as integrated circuits, printed circuit boards or multichip modules.

On the other hand, the conformational unit of the general cyclic olefin has one or two stable rotation states, and thus may have an extended form such as a polyimide having a rigid phenyl ring as a main chain. When a polar group is introduced into a norbornene-based polymer having such an extended form, the interaction between molecules is increased by introducing a polar group than a polymer having a compact form, and thus a directional order for packing between molecules. ) And may be optically and electrically anisotropic.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments, but the present invention is not limited thereto.

In the examples and comparative examples below, all operations dealing with air or water sensitive compounds were performed using standard Schlenk techniques or dry box techniques. Nuclear magnetic resonance spectra were obtained using a Bruker 600 spectrometer. The molecular weight and molecular weight distribution of the polymer were measured using a water permeation gel permeation chromatography (GPC) apparatus, wherein polystyrene samples were used as standard. Toluene and diethyl ether were purified by distillation in potassium / benzophenone and dichloromethane was used by distillation purification in CaH ₂ .

Example 1

( Cy ) ₃ PHCl  Manufacture

(Cy) ₃ P (2.02 g, 7.2 mmol, Cy is cyclohexyl) was added to a 250 mL Schlenk flask, and diethyl ether (150 mL) was added to dissolve it. Next, anhydrous HCl (14.4 mL, 1.0M in ether) was added at room temperature, and a white precipitate was formed during the reaction. The reaction was performed for about 20 minutes, and the white precipitate was filtered through a glass filter, followed by diethyl ether (80 mL), and then the solvent was removed by vacuum in a residual solvent at room temperature (Cy) ₃ PHCl (86%, 1.95 g) was obtained.

¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ 7.02 -6.23 (d, 1H, J _{H -P} = 470 Hz), 2.56-1.30 (m, 33H); ¹³ C-NMR (600 MHz, CD ₂ Cl ₂ ): δ 28.9 (d), 28.5 (d), 26.8 (d), 25.6 (s). ³¹ P-NMR (600 MHz, CD ₂ Cl ₂ ): δ 22.98 (d, J _{P -H} = 470 Hz).

Example 2

(n- Bu ) ₃ PHCl  Manufacture

(n-Bu) ₃ P (2.0 g, 10.0 mmol) was added to a 250 mL Schlenk flask, and diethyl ether (100 mL) was added to dissolve it. Next, anhydrous HCl (20.0 mL, 1.0M in ether) was added at room temperature, and a white precipitate was formed during the reaction. The reaction was performed for about 20 minutes, and the white precipitate was filtered through a glass filter, followed by diethyl ether (80 mL), and then the solvent was removed in vacuo at room temperature to obtain a solvent (n-Bu) ₃ PHCl (90%, 2.15g).

Example 3

[( Cy ) ₃ PH ] [B ( C ₆ F ₅ ) ₄ Manufacture of

In a glove box, (Cy) ₃ PHCl (0.56 g, 1.75 mmol) and [Li] [B (C ₆ F ₅ ) ₄ ] (1.0 g, 1.46 mmol) obtained in Preparation Example 3 were each 100 mL Schlenk. ) Was added to the flask and dissolved in dichloromethane (20 mL). Next, (Cy) ₃ PHCl solution was slowly added dropwise to the [Li] [B (C ₆ F ₅ ) ₄ ] solution at room temperature. After the reaction for about 1 hour unreacted material was filtered through a glass filter and the solvent was removed in vacuo to give [(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (90%, 1.26g).

¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ 5.32 -4.65 (d, 1H, J _{H -P} = 440 Hz), 2.43-1.33 (m, 33H); ¹³ C-NMR (600 MHz, CD ₂ Cl ₂ ): δ 149.7, 148.1, 139.7, 139.2, 138.1, 138.0, 137.8, 136.2, 125.1, 124.9, 29.0, 28.8, 26.7 (d), 25.4 (s). ³¹ P-NMR (600 MHz, CD ₂ Cl ₂ ): 31.14 (d, J _{P −H} = 440 Hz). ¹⁹ F-NMR (600 MHz, CD ₂ Cl ₂ ): -130.90, -161.51, -163.37.

Crystals suitable for X-ray diffraction analysis were obtained from dichloromethane solution. The results of the X-ray crystal structure analysis are shown in FIG. 1. Specifically, the structure shows that there is a nonbonding interaction between the P atom of the [(Cy) ₃ PH] moiety and the F atom of the [B (C ₆ F ₅ ) ₄ ] moiety.

Example 4

[( Cy ) ₃ PH ] [B ( C ₆ F ₅ ) ₄ Manufacture of

_{[Li] [B (C 6} F 5) 4] instead of the _{[Na] [B (C 6} F 5) 4] or _{[MgBr] [B (C 6} F 5) 4] used and the same as in Example 3, the [(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] was prepared by the method. Synthetic yield was about 90%, almost the same as in Example 3.

Example 5

[(n- Bu ) ₃ PH ] [B ( C ₆ F ₅ ) ₄ Manufacture of

In a glove box, (n-Bu) ₃ PHCl (0.42 g, 1.75 mmol) and [Li] [B (C ₆ F ₅ ) ₄ ] (1.0 g, 1.46 mmol) obtained in Preparation Example 4 were each 100 mL Schlenk. (schlenk) was added to the flask and dichloromethane (20 mL) was added to dissolve. Next, slowly add dropwise (n-Bu) ₃ PHCl solution to [Li] [B (C ₆ F ₅ ) ₄ ] solution at room temperature, and after 1 hour, unreacted material was filtered through a glass filter and the solvent was evacuated. The solvent was removed through to give [(n-Bu) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (87%, 1.12 g).

Example 6

[(t- Bu ) ₃ PH ] [B ( C ₆ F ₅ ) ₄ Manufacture of

(t-Bu) ₃ P (0.35 g, 1.73 mmol) was added to a 250 mL Schlenk flask, and diethyl ether (30 mL) was added to dissolve it. Next, anhydrous HCl (1.9 mL, 1.0M in ether) was added at room temperature, and a white precipitate was formed during the reaction. The reaction was performed for about 20 minutes, and the white precipitate was filtered through a glass filter, followed by diethyl ether (30 mL), and the residual solvent was removed in vacuo at room temperature by (t-Bu) ₃ PHCl as a white solid.

(t-Bu) ₃ PHCl was dissolved in dichloromethane (10 mL), and 100 mL Schlenk flask of [Li] [B (C ₆ F ₅ ) ₄ ] (1.07 g, 1.56 mmol) was added to the glovebox. In dichloromethane (20 mL) to dissolve. Next, (t-Bu) ₃ PHCl solution was slowly added dropwise to the [Li] [B (C ₆ F ₅ ) ₄ ] solution at room temperature. After 1 hour of reaction, the side reactant, LiCl, was filtered through a glass filter, and the solvent was removed in vacuo, followed by [(t-Bu) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (67%, 1.05g). Got it.

¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ 5.34 -4.63 (d, 1H, J _{H -P} = 440 Hz), 1.61 (d, 27H); ¹³ C-NMR (600 MHz, CD ₂ Cl ₂ ): δ 149.5, 147.9, 139.6, 138.0, 137.7, 136.0, 124.4, 38.3, 30.4. ³¹ P-NMR (600 MHz, CD ₂ Cl ₂ ): 63.0 (d, J _{P −H} = 440 Hz). ¹⁹ F-NMR (600 MHz, CD ₂ Cl ₂ ): -133.3, -163.9, -167.8.

Example 7

[( Et ) ₃ PH ] [B ( C ₆ F ₅ ) ₄ Manufacture of

(Et) ₃ P (0.8 g, 6.77 mmol) was added to a 250 mL Schlenk flask and diethyl ether (50 mL) was added to dissolve it. Next, anhydrous HCl (7.4 mL, 1.0M in ether) was added at room temperature, and a white precipitate was formed during the reaction. The reaction was performed for about 20 minutes, the solvent was removed under vacuum, and washed with hexane (30 mL). Next, the solvent was removed in vacuo at room temperature to obtain (Et) ₃ PHCl as a white solid.

(Et) ₃ PHCl was dissolved in dichloromethane (10 mL) and [Li] [B (C ₆ F ₅ ) ₄ ] (4.41 g, 6.43 mmol) was added to a 100 mL Schlenk flask in a glovebox. Dichloromethane (50 mL) was added to dissolve. Next, (Et) ₃ PHCl solution was slowly added dropwise to the [Li] [B (C ₆ F ₅ ) ₄ ] solution at room temperature. After reacting for about 1 hour, the side reactant LiCl was filtered through a glass filter, and the solvent was removed under vacuum to obtain [(Et) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (54%, 2.91).

¹ H-NMR (600 MHz, CD ₂ Cl ₂ ): δ 6.06 (m, 0.5H), 5.30 (m, 0.5H), 2.28 (m, 6H), 1.40 (m, 9H); ¹³ C-NMR (600 MHz, CD ₂ Cl ₂ ): δ 149.5, 147.9, 139.7, 138.0, 137.9, 137.7, 136.1, 124.6, 10.6 (d), 6.8 (d). ³¹ P-NMR (600 MHz, CD ₂ Cl ₂ ): 26.3 (d). ¹⁹ F-NMR (600 MHz, CD ₂ Cl ₂ ): -133.5, -163.7, -167.8.

Example 8

5- Norborneen -2- Carboxylic acid methyl  Polymerization of esters

5-norbornene-2-carboxylic acid methyl ester (MENB, 10 mL, 55.6 mmol) prepared in Preparation Example 1 was added to a 250 mL Schlenk flask and Pd (OAc) ₂ (OAc = acetate, 2.5 mg, 11 μmol) and [(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (21.1 mg, 22 μmol) were added to a 250 mL Schlenk flask and dissolved in 1 mL of dichloromethane. Next, the catalyst solution was added dropwise to the monomer through a syringe at 90 ° C., reacted at 90 ° C. for 10 hours, and 50 mL of toluene was added to dissolve the polymer, which was added to an excess of ethanol to obtain a white polymer precipitate. . The precipitate was filtered by a glass funnel and the polymer recovered was dried in a vacuum oven at 80 ° C. for 24 hours to obtain 8.4 g of a polymer of 5-norbornene-2-carboxylic acid methyl ester (80.5 wt% based on the total amount of monomer introduced). The molecular weight (Mw) was 200,400 and Mw / Mn was 2.02.

Examples 9-15

5- Norborneen -2- methyl  Polymerization of Acetate

[(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] amount to 2: 1, 1: 1, 2: 3, 1: 2, 1: 4, 1: 8 relative to molar Pd (OAc) 2 Change to polymerize 5-norbornene-2-methyl acetate. 5-norbornene-2-methyl acetate (4 mL, 24.7 mmol) and toluene (12 mL) of Preparation Example 2 were added to a 100 mL Schlenk flask, and Pd (OAc) ₂ (1.1 mg, 4.9 μmol) was used as a catalyst. And [(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ], which were changed at various equivalent ratios, were dissolved in dichloromethane (1 mL), and added to a monomer solution, followed by reaction at 90 ° C. for 4 hours. Polymerization reaction and polymer recovery were carried out in the same manner as in Example 1 to prepare a polymer of 5-norbornene-2-methyl acetate, the results are shown in Table 1.

division Pd (OAc) ₂ (mg) [(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (mg) Pd / B yield Mw Mw / Mn [g] [%] Example 9 1.1 2.4 2/1 1.77 43.2 333,400 2.11 Example 10 1.1 4.7 1/1 3.52 86.0 272,800 2.28 Example 11 1.1 7.1 2/3 3.82 93.2 260,000 2.56 Example 12 1.1 9.5 1/2 3.83 93.4 256,300 2.49 Example 13 1.1 19.0 1/4 3.80 90.5 221,600 2.45 Example 14 1.1 28.4 1/6 3.39 82.7 194,100 2.25 Example 15 1.1 38.0 1/8 3.30 80.5 193,200 2.20

Example 16

Preparation of 5-norbornene-2-carboxylic acid methyl ester / norbornene addition copolymer

In a 250 ml Schlenk flask, 37 ml of norbornene carboxylic acid methyl ester (16.74 g), norbornene (4.44 g) and purified toluene as solvent were added as monomers. Pd (OAc) ₂ (4.79 mg) and [(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (40.4 mg) dissolved in dichloromethane (2 mL) were added to the flask. The reaction was carried out while stirring. After 10 hours, the reaction product was added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 65 ° C. for 24 hours to obtain 14.86 g of norbornene and 5-norbornene-2-carboxylic acid methyl ester copolymer (yield: based on the total amount of monomers charged). 70.2% by weight). The weight average molecular weight (Mw) of this polymer was 184,000, and Mw / Mn was 2.12.

Example 17

Preparation of 5-norbornene-2-carboxylic acid methyl ester / butyl norbornene addition copolymer

In a 250 mL Schlenk flask, 5-norbornene-2-carboxylic acid methyl ester (14.64 g), butyl norbornene (6.14 g) and toluene (37 mL) were added as monomers. To this flask was added Pd (acac) ₂ (4.19 mg, acac = acetylacetonate) and [(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (32.8 mg) dissolved in dichloromethane (2 mL). The reaction was stirred at 90 ° C. for a time. After 10 hours, the reaction product was added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was filtered with a glass funnel and the copolymer was dried in a vacuum oven at 65 ° C. for 24 hours to obtain 13.7 g of butyl norbornene and 5-norbornene-2-carboxylic acid methyl ester copolymer (yield: total amount of monomers charged). 65.9 wt%). The weight average molecular weight (Mw) of this polymer was 157,000, and Mw / Mn was 2.13.

Example 18

Preparation of 5-norbornene-2-methyl acetate / butyl norbornene addition copolymer (catalyst: Pd (acac) ₂ )

5-norbornene-2-methyl acetate (8.2 g), butylnorbornene (3.2 g) and toluene (36 mL) were charged to a 250 mL Schlenk flask. Pd (OAc) ₂ (3.2 mg) and [(Cy) ₃ PH] [B (C ₆ F ₅ ) ₄ ] (27.0 mg) were added to the flask as a catalyst dissolved in dichloromethane (2 mL) for 4 hours. The reaction was stirred at 90 ° C. After 4 hours, the reaction product was added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 65 ° C. for 24 hours to obtain 9.30 g of a copolymer of butyl norbornene and 5-norbornene-2-carboxylic acid methyl acetate (yield: monomer charged). 81.7% by weight). The weight average molecular weight (Mw) of this polymer was 218,300, and Mw / Mn was 3.52.

Comparative Example 1

5- Norborneen -2- Carboxylic acid  polymerization

10 g of 5-norbornene-2-carboxylic acid and 100 mg of [Pd (C ₆ H ₅ CN) Cl ₂ ] ₂ were charged to the reaction flask and reacted at 140 ° C. for 10.5 hours to obtain 5.75 g of a polymer having a weight average molecular weight of 1129. It was.

Comparative Example 2

5- Norborneen -2- methyl - Decanyl  Acetate polymerization

5-norbornene-2-methyl-decanyl acetate (1.03 g, 3.7 mmol) was placed in a Schlenk flask and in another flask [(Allyl) PdCl] ₂ (13.15 mg, 3.60 × 10 ^-2 mmol, Allyl = allyl) And AgSbF ₆ (35 mg, 10.1 × 10 ^-2 mmol), and add 2 mL of chlorobenzene to dissolve it. The AgCl precipitate is filtered off and added dropwise to the monomer at room temperature and reacted for 24 hours. The polymerization yield was 1.01 g (98%) and the weight average molecular weight was 58,848.

Comparative Example 3

5- Norborneen -2- methyl  Acetate polymerization

In a Schlenk flask, add Li [B (C ₆ F ₅ ) ₄ ] to ₅ -norbornene-2-methyl acetate (5.0 g, 30 mmol). [(Allyl) PdCl] ₂ (0.55 mg, 0.0015 mmol) and P (Cy) ₃ (0.84 mg, 0.0030 mmol) are dissolved in 0.1 mL of toluene and added dropwise to the monomer. 0.25g (5%) of polymer was obtained when reacting at 65 degreeC for 4 hours.

Comparative Example 4

Pd ( OAc ) 2 and Dimethylanilinium Tetrakis (pentafluorophenyl) borate Polymerization of 5-norbornene-2-methyl acetate by catalytic system

5-norbornene-2-methyl acetate (5 mL, 30.9 mmol) and toluene (15 mL) were added to a 250 mL Schlenk flask. Pd (OAc) 2 (1.4 mg, 6.2 mol) and dimethylanilinium tetrakis (pentafluorophenyl) borate (10.9 mg, 13.6 mol) were added to the flask with a catalyst dissolved in dichloromethane (1 ml) for 18 hours. Reaction was stirred at 90 ° C. After reacting for 18 hours, the reaction was added to excess ethanol but no polymer precipitate was obtained.

1 is an X-ray crystal structure analysis result showing the molecular structure of tricyclohexylphosphonium (tetrakispentafluorophenyl) borate.

Claims (1)

 A phosphonium compound prepared by the method for preparing a phosphonium compound represented by the following <Formula 1> comprising the step of contacting a phosphonium compound represented by the following <Formula 2> and a salt compound represented by the following <Formula 3> As a polymer produced using  A polymer having a cyclic olefin monomer containing a polar functional group represented by the following formula (6) and having a weight average molecular weight (Mw) of 100,000 to 1000,000: <Formula 1> [(R ₁ ) -P (R ₂ ) _a (R _{2 '} ) _b [Z (R ₃ ) _d ] _c ] [Ani] (Wherein a, b and c are each an integer of 0 to 3 and a + b + c = 3; Z is oxygen, sulfur, silicon, or nitrogen; d is 1 when Z is oxygen or sulfur, 2 when Z is nitrogen, and 3 when Z is silicon; R ₁ is hydrogen, alkyl or aryl; R ₂ , R _{2 '} and R ₃ Are each independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms, unsubstituted or substituted with hydrocarbon, halogen or C _1-20 haloalkyl, alkoxy, allyl, alkenyl, or vinyl; Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with hydrocarbon, halogen or haloalkyl of C _1-20 ; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with hydrocarbon, halogen or haloalkyl of C _1-20 ; _Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with hydrocarbon, halogen or haloalkyl of C _1-20 ; Alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with hydrocarbon, halogen or haloalkyl of C _1-20 ; Tri (linear or branched alkyl) having 1 to 10 carbon atoms, tri (linear or branched alkoxy) silyl having 1 to 10 carbon atoms; Tri (substituted or unsubstituted cycloalkyl) silyl; Tri (substituted or unsubstituted aryl having 6 to 40 carbon atoms) silyl; Tri (substituted or unsubstituted aryloxy having 6 to 40 carbon atoms) silyl; Tri (linear or branched alkyl of 1 to 10 carbon atoms) siloxy; Tri (substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms) siloxy; Or tri (substituted or unsubstituted aryl having 6 to 40 carbon atoms) siloxy, wherein each substituent in the silyl or siloxy is hydrocarbon, halogen or haloalkyl having 1 to 20 carbon atoms; [Ani] is borate, aluminate, [SbF ₆ ]-, [PF ₆ ]-, [AsF ₆ ]-, perfluoroacetate ([CF ₃ CO ₂ ]-), perfluoropropionate ( perfluoropropionate; [C ₂ F ₅ CO ₂ ]-), perfluorobutyrate; [CF ₃ CF ₂ CF ₂ CO ₂ ]-), perchlorate ([ClO ₄ ]-), para-toluenesulfonate (p-toluenesulfonate; [p-CH ₃ C ₆ H ₄ SO ₃ ]-), [SO ₃ CF ₃ ]-, borabenzene, or halogen substituted or unsubstituted carborane) <Formula 2> [(R ₁ ) -P (R ₂ ) _a (R _{2 '} ) _b ] HX Wherein H is hydrogen, X is a halogen atom, and the rest are as defined in <Formula 1>; <Formula 3> [C] [Ani] In the above formula, C is an alkali metal or MgX, [Ani] is as defined in <Formula 1>, <Formula 6>

In Chemical Formula 6, m is an integer of 0 to 4, at least one of R ₇ , R ₇ ^′ , R ₇ ^″, and R ₇ ^{′ ″} represents a polar functional group, and the rest are nonpolar functional groups; R ₇ , R ₇ ^′ , R ₇ ^'' and R ₇ ^'' may be linked together to form a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or an aromatic ring having 6 to 24 carbon atoms; The nonpolar functional group is hydrogen; halogen; Linear or branched alkyl of 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; Linear or branched alkynyl, haloalkynyl having 3 to 20 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Or aralkyl having 7 to 15 carbon atoms, unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; The polar functional group is-(R ⁸ O) _k -OR ⁹ ,-(OR ⁸ ) _k -OR ⁹ , -C (O) -OC (O) R ⁹ , -R ⁸ C (O) -OC (O) R ⁹ , -SR ⁹ , -R ⁸ SR ⁹ , -SSR ⁸ , -R ⁸ SSR ⁹ , -S (= O) R ⁹ , -R ⁸ S (= O) R ⁹ , -R ⁸ C (= S ) R ⁹ , -R ⁸ C (= S) SR ⁹ , -R ⁸ SO ₃ R ⁹ , -SO ₃ R ⁹ , -R ⁸ N = C = S, -N = C = S, -NCO, R ⁸ -NCO, -CN, -R ⁸ CN, -NNC (= S) R ⁹ , -R ⁸ NNC (= S) R ⁹ , -NO ₂ , -R ⁸ NO ₂ , -P (R ⁹ ) ₂ ,- R ⁸ P (R ⁹ ) ₂ , -P (= O) (R ⁹ ) ₂ ,-R ⁸ P (= O) (R ⁹ ) ₂ ,

At least one functional group selected from the group consisting of; Each of R ⁸ and R ¹¹ in the polar functional group is linear or branched alkylene, haloalkylene, alkenylene, haloalkenylene having 1 to 20 carbon atoms; Linear or branched alkynylene, haloalkynylene having 3 to 20 carbon atoms; Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl; Arylene having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl; Or aralkylene having 7 to 15 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, Each of R ⁹ , R ¹² , R ¹³ and R ¹⁴ in the polar functional group is hydrogen; halogen; Linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl having 1 to 20 carbon atoms; Linear or branched alkynyl, haloalkynyl having 3 to 20 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Or an alkoxy, haloalkoxy, carboxyl group, halocarboxyl group, k is an integer between 1 and 10.

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