JP2001019723A - Synthetic method for norbornene copolymer and trifluorostyrene (co)polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject norbornene copolymer and trifluorostyrene (co)polymer excellent in heat resistance useful as a polyelectrolyte membrane for fuel cell by polymerizing norbornene, etc., and a monomer having doable bond which is inducible of an ion dissociating group using a specific transition metal catalyst and then inducing an ion dissociating group to the monomer including the above-mentioned double bond. SOLUTION: The objective polymer is obtained by polymerizing norbornene, etc., and a monomer having double bond which is inducible of an ion dissociating group using a catalyst comprising a compound of formula [LnMXm]a+[A]a- M is a transition metal of an eighth-tenth group of the periodic system; L is a ligand having 1-3 π-bonds; X is a ligand having at least one σ-bond and 0-3 π-bonds; n is 0-2, m is 0 or 1 and m and n are not 0 at the same time; a=2 while m is 0, a=1 while m is 1; A is a counter anion of group [LnMXm]a+}, or a multi-components type catalyst including a transition metal compound of a transition metal of an eighth-tenth group of the periodic system and an organic aluminum compound, etc., and then inducing an ion dissociating group to the monomer including the double bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a norbornene-based copolymer using a transition metal catalyst, a method for synthesizing the same, and a method for synthesizing a trifluorostyrene (co) polymer.

[0002]

2. Description of the Related Art OFION, which is currently most frequently used as a polymer solid electrolyte membrane, has a glass transition temperature of about 130.
It is difficult to use in a higher temperature range because of the low temperature. Therefore, a polymer having excellent heat resistance is desired.

[0003] Trifluorostyrene (co) polymer is expected to be used as an electrolyte. The trifluorostyrene polymer can easily introduce an ion dissociating group and a substituent into an aromatic ring, and is excellent in durability. However, trifluorostyrene does not increase in molecular weight when synthesized by a radical polymerization method. That is, in the radical polymerization mechanism, the polymerization growth reaction and the dimerization reaction compete with each other, so that a large amount of a trifluorostyrene monomer dimer is generated, and a high molecular weight polymer cannot be obtained.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a norbornene-based copolymer excellent in heat resistance, a method for synthesizing the same, and a method for synthesizing a trifluorostyrene (co) polymer having a high synthesis efficiency and a high molecular weight by a polymerization reaction. It seeks to provide a way.

[0005]

According to a first aspect of the present invention, as described in claim 1, norbornene or a derivative thereof and a double bond-containing monomer into which an ion dissociating group can be introduced are used by using a transition metal catalyst. A step of polymerizing and a step of introducing an ion-dissociating group into the double bond-containing monomer, wherein the transition metal catalyst is a compound represented by the following formula (IV):

Embedded image {Where, M represents a transition metal element belonging to Groups 8, 9 and 10 of the periodic table, L represents a ligand having 1 to 3 π bonds, X represents at least one σ bond and 0 to 3 Represents a ligand having π bonds, n is 0, 1 or 2, m is 0 or 1, when n and m are not both 0 at the same time, and when m is 0 a is 2, m is a is 1 when 1, a _denotes an anion for ^{_{[L n MX m] a +}} . Or (a) a transition metal compound of a transition metal element belonging to Groups 8, 9 and 10 of the periodic table;
There is a method for synthesizing a norbornene-based copolymer, which is a multi-component catalyst containing (b) an organoaluminum compound and / or (c) an electron-donating component.

According to the synthesis method of the present invention, a norbornene-based copolymer having a high glass transition point, excellent heat resistance, and soluble in an organic solvent can be synthesized. The reason is considered as follows. Norbornene or a derivative thereof has a bulky cyclic structure. Therefore, the molecular mobility of the main chain is hindered, and the polymer has a high glass transition temperature. On the other hand, since the tacticity of the norbornene unit has a random, ie, diheterotactic structure, it is expected that the norbornene unit has no crystallinity and is soluble in an organic solvent. The diheterotactic structure refers to a structure in which diisotactic and disyndiotactic are mixed. On the other hand, when diisotactic and / or disyndiotactic dominates, the norbornene-based copolymer becomes insoluble and infusible.

In the present synthesis method, since the polymerization reaction is carried out using the above-mentioned metal transition catalyst, the polymerization activity is high, and a norbornene polymer having a high molecular weight can be obtained in a short time at room temperature. Some of the metal catalysts used in the present synthesis method (specifically, Pd, Co, Fe-based)
Is stable even in air, so that the polymerization reaction can be performed in air. Therefore, no special device is required.

Next, the details of the synthesis method will be described.
In the copolymerization step in the present synthesis method, a transition metal catalyst is used. The transition metal catalyst comprises a single-component catalyst or a multi-component catalyst.

(Single-component catalyst) The single-component catalyst in the present invention is represented by the following general formula (IV).

Embedded image {Where, M represents a transition metal element belonging to Groups 8, 9 and 10 of the periodic table, L represents a ligand for metal M having 1 to 3 π bonds, X represents at least one σ bond and 0
Represents a ligand for a metal M having three π bonds, n is 0, 1 or 2, m is 0 or 1, and both n and m are not 0 at the same time, m
When a is 0, a is 2; when m is 1, a is 1;
A represents an anion to [LnMXm] ^{a +} . ｝

In the present single-component catalyst, M is a metal element belonging to Groups 8, 9 and 10 of the periodic table. For example, nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iron (Fe), ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (I
r) and the like. Preferably, nickel (Ni), palladium (Pd), cobalt (Co), and iron (Fe) are used. This catalyst contains one or more transition metal elements. The transition metal element is
One kind may be used, or two or more kinds may be used in combination as needed.

X is a linear or branched C 1 -C 1
10 alkyl groups, linear or branched C 1 -C 1
It is preferably an alkoxyl group having 20 carbon atoms, an allyloxyl group having 6 to 15 carbon atoms, or an acyclic, monocyclic or polycyclic alkenyl having 3 to 20 carbon atoms which is not substituted or substituted by a halogen atom.

L is a monoolefin having 2 to 12 carbon atoms,
It is preferably selected from linear or cyclic diolefins having 4 to 12 carbon atoms and aromatic compounds having 6 to 20 carbon atoms. L is 2,3-dimethyl-2-
More preferably, it is selected from butyne, cyclooctadiene, norbornadiene and dibenzocyclooctadiene. It is also preferable that L is selected from cycloalkadienes having 6 to 12 carbon atoms, norbornadiene, and cyclotrienes having 10 to 20 carbon atoms.

A is preferably non-coordinating or weakly coordinating to the cation complex. A is BF ₄ ⁻ ,
PF ₆ ⁻ , ALF ₃ O ₃ SCF ₃ ⁻ , SBF ₅ SO
^{_{3 F -, ASF 6 -,}} SBF 6 -, SBF 5 SO
₃ F ^-, AsF ₆ ^-, perfluoro acid _(CF 3 CO ₂
^- ), Perfluoropropionic acid (C ₂ F ₅ C
O ₂ ⁻ ), perfluorobutyric acid (CF ₃ CF ₂ CF ₂ CO)
₂ ^-), perchlorate ^{_{(ClO 4 - · H 2 O}} ), p-
Toluenesulfonic acid _{(p-CH 3 C 6 H} 4 SO 3 -) , and is preferably a tetraphenylborate represented by the following formula 4 formula.

Embedded image ｛Wherein, R ′ is each independently a hydrogen atom,
Represents a fluorine atom or a trifluoromethyl group, n
Is an integer of 1 to 5. ｝

These single-component catalysts are synthesized in advance during polymerization. The single-component catalyst may be used singly or in combination of two or more as needed. Specific examples of the single-component catalyst include the following compounds.

Embedded image

Embedded image

(The present multi-component catalyst) The multi-component catalyst in the present invention is a catalyst containing (a) a transition metal compound, (b) an organoaluminum compound and / or (c) an electron-donating component. That is, the multi-component catalyst includes (a)
And (b), (a) and (c), and (a), (b) and (c).

The present multi-component catalyst forms a transition metal ion in a multi-component mixed system. The transition metal elements that constitute the transition metal compound include iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co),
Rhodium (Rh), iridium (Ir), nickel (N
i), palladium (Pd) and platinum (Pt) are preferred. More preferably, it is nickel, palladium, cobalt, or iron. One transition metal element may be used, or two or more transition metal elements may be used in combination as needed.

In transition metal compounds, one or more ligands are bonded to these metal elements (monodentate, bidentate, multi-coordinate, and the coordination is ionic). But may be neutral). The transition metal compound is 1
Seeds may be used, and two or more kinds may be used in combination as needed.

As the transition metal compound, nickel acetylacetonate, nickel carboxylate, nickel dimethylglyoxime, nickel ethyl hexanoate, cobalt neodecanoate, iron naphthanoate, palladium ethyl hexanoate, NiCl ₂ (PPh ₃ )
₂ , NiCl ₂ (PPh ₂ CH ₂ ) ₂ , nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, bis Allyl nickel bromide, bis allyl nickel chloride, bis allyl nickel iodide, trans PdCl ₂ (PPh ₃ ) ₂ , palladium (II) bis (trifluoroacetate), palladium (II) bis (acetylacetonate), palladium (II) ₂ -ethylhexanoate, Pd (acetate) ₂ (PPh ₃ ) ₂ , palladium (II) bromide, palladium (II) chloride, palladium (I
I) iodide, palladium (II) oxide, monoacetonitrile tris (triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis (acetonitrile) palladium (II) tetrafluoroborate, dichlorobis (acetonitrile) palladium (II), dichlorobis (tri Phenylphosphine) palladium (II), dichlorobis (benzonitrile) palladium (II), iron (II) chloride, iron (II)
I) chloride, iron (II) bromide, iron (III)
Bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (II)
I) acetylacetone, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexylcobalt acetate, cobalt (II) stearate, cobalt (II) tetrafluoroborate,
Bis (allyl) nickel, bis (cyclopentadienyl) nickel, palladium acetylacetonate, palladium bis (acetonitrile) dichloride, palladium bis (dimethylsulfoxide) dichloride, platinum bistriethylphosphine hydrobromide, ruthenium tris (triphenylphosphine) dichloride ,
Ruthenium tris (triphenylphosphine) hydride chloride, ruthenium trichloride, ruthenium trichloride, ruthenium tetrakis (acetonitrile) dichloride, ruthenium tetrakis (dimethylsulfoxide) dichloride, rhodium chloride, rhodium tris (triphenylphosphine) trichloride, bis-2, 6-diisopropylphenyliminoacenaphthalene nickel dichloride, bis-2,6-diisopropylphenyliminoacenaphthalene nickel dibromide, bis-2,6-dimethylphenyliminoacenaphthalene nickel dibromide, bis-2,6-dimethylphenyliminoace Naphthalene nickel dichloride, bis-2,6-diphenyliminoacenaphthalene nickel dibromide, bis 2,6-diphenyl-imino acenaphthalene nickel dichloride, 1,4-bis-diisopropylphenyl 2,3-dimethyl-diaza-butadiene nickel dibromide, 1,4-bis-diisopropylphenyl 2,
3-dimethyldiazabutadiene nickel dichloride,
1,4-bisdimethylphenyl 2,3-dimethyldiazabutadiene nickel dibromide, 1,4-bisdimethylphenyl 2,3-dimethyldiazabutadiene nickel dichloride, 1,4-bisphenyl2,3-dimethyldiaza Butadiene nickel dibromide, 1,4-bisphenyl 2,3-dimethyldiazabutadiene nickel dichloride, 1,4-bisdiisopropylphenyldiazabutadiene nickel dibromide, 1,4-bisdiisopropylphenyldiazabutadiene nickel dichloride, , 4
-Bisdimethylphenyldiazabutadienenickel dibromide, 1,4-bisdimethylphenyldiazabutadienenickel dichloride, 1,4-bisphenyldiazabutadienenickel dibromide, 1,4-bisphenyldiazabutadienenickel dichloride, bipyridyl Nickel dibromide, bipyridyl nickel dichloride, phenanthrolyl nickel dibromide, phenanthrolyl nickel dichloride, 2,6-bis [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron chloride, 2,6- Bis [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron bromide,
2,6-bis [1- (phenylimino) ethyl] pyridine iron chloride, 2,6-bis [1- (phenylimino) ethyl] pyridine iron bromide, 2,6-bis [1- (2,6-diisopropyl) Phenylimino) ethyl] pyridine cobalt chloride, 2,6-bis [1-
(2,6-diisopropylphenylimino) ethyl] pyridine cobalt bromide, 2,6-bis [1- (phenylimino) ethyl] pyridine cobalt chloride, or 2,6-bis [1- (phenylimino) ethyl] pyridine cobalt It is preferably bromide.

The organic aluminum compound is preferably a trialkylaluminum, a dialkylaluminum halide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, an aluminoxamine, or a mixture thereof.

Specifically, trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trit-butylaluminum, triisopropylaluminum, tripentylaluminum,
Trinormal hexyl aluminum, tri (2-methylpentyl) aluminum, trinormal octyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, methyl aluminum sesquichloride, isobutyl aluminum sesquichloride, di-t-butyl aluminum chloride, diisopropyl aluminum chloride, dipentyl aluminum Chloride, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, t-butylaluminum dichloride,
Isopropylaluminum dichloride and pentylaluminum dichloride are preferred.

The aluminoxane is obtained by the condensation of one type of trialkylaluminum with water, and is obtained by the condensation of two or more types of trialkylaluminum with water. Or a cage-like condensate. Specific examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Particularly, methylaluminoxane and methylisobutylaluminoxane are preferable.

The electron donating component is specifically a Lewis acid, a Bronsted acid, a halogenated compound, or a mixture thereof. In particular, the electron donating component is nickel, ruthenium, iron, palladium as a transition metal element,
It is preferably used when a transition metal compound having a metal element selected from cobalt and platinum is used.

As the Lewis acid, BF ₃ .ethylate,
TiCl ₄ , SbF ₅ , BCl ₃ , B (OCH ₂ C
H ₃ ), SiCl ₄ , tris (perfluorophenyl)
Boron, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ , LiB
(C ₆ F ₅ ) ₄ and NH (CH ₂ ) ₂ C ₆ H ₄ B (C
₆ F ₅ ) ₄ .
HSbF ₆ , HPF ₆ , C
F ₃ CO ₂ H, FSO ₃ H · SbF ₅ , H ₂ C (SO ₂ C
It is preferably selected from the group consisting of F ₃ ) ₂ , CF ₃ SO ₃ H and paratoluenesulfonic acid.

The halogenated compounds include hexachloroacetone, hexafluoroacetone, 3-butenic acid-2,2,3,4,4-pentachlorobutyl ester, hexachloroglutaric acid, hexafluoroisopropanol and chloranil. And a mixture thereof.

Using each of these types of catalysts, the above-mentioned norbornene monomer or derivative thereof is combined with:
It can be copolymerized with a monomer having a double bond into which an ion dissociating group can be introduced.

For the polymerization reaction, any method such as slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization and suspension polymerization may be used in the presence of the catalyst of the present invention. In the polymerization method, as a polymerization solvent that can be used in the case of solution polymerization, butane,
n-pentane, n-hexane, n-octane, iso-
Octane, n-nonane, aliphatic hydrocarbons such as n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, alicyclic hydrocarbons such as norbornane, benzene, Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene,
Ethers such as diethyl ether and tetrahydrofuran; chlorobenzene; o-dichlorobenzene;
Aromatic halogens such as 4-trichlorobenzene, freon,
Fluorine compounds such as alternative fluorocarbons can be exemplified. One of these polymerization solvents may be used alone,
A mixture of two or more species may be used.

The amount of the catalyst used in the present polymerization method is not particularly limited.
The metal element is in a range of 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ^−2.
mol range. In the present polymerization method, the polymerization temperature is:
It is set as required, but is generally in the range of -80 to 120C, preferably in the range of -30 to 110C, and more preferably in the range of 0 to 100C. As the atmosphere of the polymerization system, an inert atmosphere formed with an inert gas such as nitrogen, argon, or helium may be used, or an inert atmosphere may not be required.

The pressure of the polymerization system is not particularly limited. In the case of copolymerization with a vinyl monomer, gaseous monomers such as ethylene, propylene, butadiene, and allene can be added at 1 atm or more. In the present polymerization method, the time required for the polymerization reaction varies depending on the purpose or the polymerization conditions, and thus it is not particularly limited.However, in many cases, the time is within 24 hours, and is within 1 to 3 hours. There can be.

In carrying out the present polymerization method, various forms of polymers and copolymers can be obtained by a conventionally known method. Generally, the random copolymer, the alternating copolymer and the tapered block copolymer can be produced by charging two or more monomers into a polymerization system in the same manner as the homopolymer. The block copolymer can be produced by adding one monomer to the catalyst solution and, after complete consumption, adding the other monomer.

When various copolymers such as a random copolymer, an alternating copolymer and a block copolymer are to be obtained by the present polymerization method, the above-mentioned catalysts of each type can be used. Depending on the type, there is an effective type of catalyst.

According to the third aspect of the present invention, the transition metal in the transition metal catalyst is nickel, palladium, cobalt,
Preferably, it is at least one of iron. These transition metals have high polymerization activity and give a soluble norbornene-based copolymer. Also, palladium, cobalt,
When iron is used, a polymer is often obtained even in an inert atmosphere.

In the present polymerization method, after achieving a predetermined polymerization rate, a known terminal modifier, terminal branching agent, and further a polymerization terminator, a polymerization stabilizer and an oxidation stabilizer may be added as necessary. Can be. Further, after the polymerization reaction, it is possible to further derivatize the molecular structural unit with hydrogen, a halogen atom, an organic functional group or the like. The polymer can be recovered by a conventionally known solvent removing operation, drying operation and the like.

In the present polymerization method, norbornene or a derivative thereof is copolymerized with a double bond-containing monomer into which an ion dissociating group can be introduced, using the above transition metal catalyst.
The norbornene derivative has a norbornene cyclic skeleton having one double bond, and has a substituent bonded to the skeleton excluding the double bond.

The double bond-containing monomer may be cyclic, chain-like, or branched. When the double bond-containing monomer is classified, it becomes as in the invention of claim 2, but is not limited thereto. Those having an aromatic ring such as styrene. An ion dissociating group can be introduced into this aromatic ring later. A compound having a plurality of double bonds and involving only one of the double bonds in polymerization. For example, there are dicyclopentadiene, 5-ethylidene-2-norbornene, and the like. Reactive groups (such as double bonds) are formed at new positions after polymerization. For example, there is 1,3-cyclohexadiene.

The above norbornene or its derivative (i)
And a double bond-containing monomer (i
The mixing ratio (i / ii) with i) is 98/2 to 10/90.
It is preferable that If it exceeds 98/2, the amount of ion-dissociating groups introduced may decrease, and ionic conductivity may not be easily exhibited. If it is less than 10/90, the heat resistance may be reduced. More preferable mixing ratio (i / i
i) is from 95/5 to 30/70. Thereby, in-conductivity is high and heat resistance is further improved.

Next, a step of introducing an ion-dissociating group into the norbornene-based copolymer is performed. Examples of the ion dissociating group to be introduced include a sulfone group and a phosphon group. Examples of the method for introducing an ion dissociating group include immersion in a strong acid (such as sulfuric acid), a reaction with a halogenated sulfonic acid or a halogenated phosphonic acid, a reaction with a sulfur trioxide solution,
Subsequent SO ₃ H introduction by hydrolysis with NaOH or the like can be used, and all other known methods can be used.

The norbornene-based copolymer obtained by the above synthesis method is, as described in claim 4, a norbornene-based copolymer comprising norbornene or a derivative thereof and a double bond-containing monomer into which an ion dissociating group can be introduced. There is a norbornene-based copolymer in which an ion-dissociating group is introduced into the double bond-containing monomer.

The norbornene-based copolymer has an extremely high glass transition point of 350 ° C. or higher, and is excellent in heat resistance.
It is soluble in organic solvents. Therefore, a cast film, that is, a film obtained by dissolving a polymer in an organic solvent, applying a viscous liquid on a glass plate or a petri dish and gradually evaporating the solvent can be produced. It is considered that such conflicting properties are caused by the following.

The norbornene copolymer has a bulky cyclic structure of norbornene or a derivative thereof. Therefore, the molecular mobility of the main chain is hindered, and a high glass transition point is exhibited. On the other hand, since the tacticity (arrangement) of the norbornene unit has a random, ie, diheterotactic structure, it is expected that the norbornene unit is soluble in an organic solvent without crystallinity. Further, since an ion dissociating group is introduced into the double bond-containing monomer, ionic conductivity can be imparted to the norbornene-based polymer.

The norbornene-based copolymer is obtained by copolymerizing norbornene or a derivative thereof and a monomer having a double bond having an ion-dissociating group, and details thereof are the same as those described in the above synthesis method. It is.

An ion-dissociating group is introduced into the double bond-containing monomer. The kind of the ion dissociating group is the same as that in the above synthesis method. The ion dissociation amount (EW) bound to the double bond-containing monomer is 100 to 1000.
It is preferable that If it is less than 100, the number of ion-dissociating groups increases, and the heat resistance may decrease. 1100
When it exceeds, the number of ion dissociation groups decreases, and the ion conductivity may decrease.

The ion dissociation amount (EW value) is an index of the amount of ion dissociation groups introduced. The EW value is the reciprocal of the ion dissociating group (mol) per 1 g of the polymer, and a smaller value indicates that more sulfone groups have been introduced. The EW value of Nafion is 1100.

EW (g / eq) = W / ((Qblank−Qsample) /1000×0.5×FHCl) (1)

W: membrane weight (g), Qblank: titer for blank (ml), Qsample: titer for sample (ml), FHCl: titer of 0.5N hydrochloric acid

The norbornene-based copolymers include block copolymers such as random copolymers, alternating copolymers, tapered block copolymers, graft copolymers, diblocks, and radial blocks. The weight average molecular weight of the norbornene-based copolymer is 1,000 to 1,000,000.
It is preferable that If it is less than 1,000, film formation may be difficult. If it exceeds 1,000,000, the viscosity may be high and handling may be difficult.

The glass transition point of the norbornene-based copolymer is preferably from 150 to 400 ° C. 150 ° C
If it is less than 3, heat resistance may be insufficient. 400
When the temperature exceeds ℃, the flexibility of the produced film may be reduced. The norbornene-based copolymer is suitable for use as a polymer electrolyte membrane for a fuel cell because a high-strength, high-heat-resistant membrane can be produced. In addition, the norbornene-based copolymer has other uses such as resin glass, thermoplastic elastomer, and optical material.

Next, a second aspect of the present invention is a method for synthesizing a trifluorostyrene (co) polymer by polymerizing a trifluorostyrene monomer using a transition metal catalyst. The transition metal catalyst is a compound represented by the following formula (IV) (also referred to as a single-component catalyst in the present specification):

Embedded image {Where, M represents a transition metal element belonging to Groups 8, 9 and 10 of the periodic table, L represents a ligand having 1 to 3 π bonds, X represents at least one σ bond and 0 to 3 Represents a ligand having π bonds, n is 0, 1 or 2, m is 0 or 1, when n and m are not both 0 at the same time, and when m is 0 a is 2, m is a is 1 when 1, a _denotes an anion for ^{_{[L n MX m] a +}} . Or (a) a transition metal compound of a transition metal element belonging to Groups 8, 9 and 10 of the periodic table;
There is a method for synthesizing a trifluorostyrene (co) polymer, which comprises a multi-component catalyst containing (b) an organoaluminum compound and / or (c) an electron-donating component.

The second invention is a method for polymerizing a trifluorostyrene monomer. In this polymerization, the same transition metal catalyst as in the synthesis method of the first invention is used. When a polymerization reaction is carried out using a transition metal catalyst, no radical reaction occurs and no monomer dimerization occurs. Therefore, the polymerization reaction of the monomer proceeds efficiently.

The transition metal catalyst can be copolymerized with olefin compounds such as ethylene, α-olefin, and diene, which are difficult to polymerize by radical polymerization. Also,
Since trifluorostyrene has no hydrogen at the double bond site, β-β is a side reaction peculiar to the polymerization of transition metal catalyst.
No hydrogen elimination reaction occurs. Therefore, a single compound can be obtained.

Next, the details of the present invention will be described. The transition metal catalyst used in the second invention is the same as the transition metal catalyst of the first invention. That is, in the polymerization reaction in the present synthesis method, a transition metal catalyst is used. The transition metal catalyst comprises a single-component catalyst or a multi-component catalyst.

(Single-component catalyst) The single-component catalyst in the present invention is represented by the following general formula (IV).

Embedded image {Where, M represents a transition metal element belonging to Groups 8, 9 and 10 of the periodic table, L represents a ligand for metal M having 1 to 3 π bonds, X represents at least one σ bond and 0
Represents a ligand for a metal M having three π bonds, n is 0, 1 or 2, m is 0 or 1, and both n and m are not 0 at the same time, m
When a is 0, a is 2; when m is 1, a is 1;
A represents an anion to [LnMXm] ^{a +} . ｝

M is a metal element belonging to groups 8, 9 and 10 of the periodic table. For example, nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iron (F
e), ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir) and the like. Preferably, nickel (Ni), palladium (Pd), cobalt (Co), and iron (Fe) are used. This catalyst contains one or more transition metal elements. The transition metal element may be one kind,
If necessary, two or more kinds can be used in combination.

X represents a linear or branched C 1 -C 1
10 alkyl groups, linear or branched C 1 -C 1
It is preferably an alkoxyl group having 20 carbon atoms, an allyloxyl group having 6 to 15 carbon atoms, or an acyclic, monocyclic or polycyclic alkenyl having 3 to 20 carbon atoms which is not substituted or substituted by a halogen atom.

L is a monoolefin having 2 to 12 carbon atoms,
It is preferably selected from linear or cyclic diolefins having 4 to 12 carbon atoms and aromatic compounds having 6 to 20 carbon atoms. L is 2,3-dimethyl-2-
More preferably, it is selected from butyne, cyclooctadiene, norbornadiene and dibenzocyclooctadiene. It is also preferable that L is selected from cycloalkadienes having 6 to 12 carbon atoms, norbornadiene, and cyclotrienes having 10 to 20 carbon atoms.

A is preferably non-coordinating or weakly coordinating to the cation complex. A is BF ₄ ⁻ ,
PF ₆ ⁻ , ALF ₃ O ₃ SCF ₃ ⁻ , SBF ₅ SO
^{_{3 F -, ASF 6 -,}} SBF 6 -, SBF 5 SO
₃ F ^-, AsF ₆ ^-, perfluoro acid _(CF 3 CO ₂
^- ), Perfluoropropionic acid (C ₂ F ₅ C
O ₂ ⁻ ), perfluorobutyric acid (CF ₃ CF ₂ CF ₂ CO)
₂ ^-), perchlorate ^{_{(ClO 4 - · H 2 O}} ), p-
It is preferable to use toluene sulfonic acid (p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ) and tetraphenyl boric acid represented by the following formula.

Embedded image ｛Wherein, R ′ is each independently a hydrogen atom,
Represents a fluorine atom or a trifluoromethyl group, n
Is an integer of 1 to 5. ｝

These single-component catalysts are synthesized in advance at the time of polymerization. The single-component catalyst may be used singly or in combination of two or more as needed. Specific examples of the single-component catalyst include the following compounds.

Embedded image

Embedded image

(The present multi-component catalyst) The multi-component catalyst of the present invention is a catalyst containing (a) a transition metal compound, (b) an organoaluminum compound and / or (c) an electron-donating component. That is, (a) and (b), (a) and (c), and (a), (b) and (c)
There is a combination with. The present multi-component catalyst forms a transition metal ion in a multi-component mixed system.

The transition metal elements constituting the transition metal compound include iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), Palladium (P
d), and preferably platinum (Pt). More preferably, it is nickel, palladium, cobalt, or iron. One transition metal element may be used, or two or more transition metal elements may be used in combination as needed. In transition metal compounds, one or two or more ligands are bonded to these metal elements (monodentate, bidentate, multiple coordination, and the coordination is ionic or neutral). May be). One transition metal compound may be used,
If necessary, two or more kinds can be used in combination.

As the transition metal compound, nickel acetylacetonate, nickel carboxylate, nickel dimethylglyoxime, nickel ethyl hexanoate, cobalt neodecanoate, iron naphthanoate, palladium ethyl hexanoate, NiCl ₂ (PPh ₃ )
₂ , NiCl ₂ (PPh ₂ CH ₂ ) ₂ , nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, bis Allyl nickel bromide, bis allyl nickel chloride, bis allyl nickel iodide, trans PdCl ₂ (PPh ₃ ) ₂ , palladium (II) bis (trifluoroacetate), palladium (II) bis (acetylacetonate), palladium (II) ₂ -ethylhexanoate, Pd (acetate) ₂ (PPh ₃ ) ₂ , palladium (II) bromide, palladium (II) chloride, palladium (I
I) iodide, palladium (II) oxide, monoacetonitrile tris (triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis (acetonitrile) palladium (II) tetrafluoroborate, dichlorobis (acetonitrile) palladium (II), dichlorobis (tri Phenylphosphine) palladium (II), dichlorobis (benzonitrile) palladium (II), iron (II) chloride, iron (II)
I) chloride, iron (II) bromide, iron (III)
Bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (II)
I) acetylacetone, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexylcobalt acetate, cobalt (II) stearate, cobalt (II) tetrafluoroborate,
Bis (allyl) nickel, bis (cyclopentadienyl) nickel, palladium acetylacetonate, palladium bis (acetonitrile) dichloride, palladium bis (dimethylsulfoxide) dichloride, platinum bistriethylphosphine hydrobromide, ruthenium tris (triphenylphosphine) dichloride ,
Ruthenium tris (triphenylphosphine) hydride chloride, ruthenium trichloride, ruthenium trichloride, ruthenium tetrakis (acetonitrile) dichloride, ruthenium tetrakis (dimethylsulfoxide) dichloride, rhodium chloride, rhodium tris (triphenylphosphine) trichloride, bis-2, 6-diisopropylphenylimino acenaphthalene nickel dichloride, bis-2,6
-Diisopropylphenyliminoacenaphthalene nickel dibromide, bis-2,6-dimethylphenyliminoacenaphthalenenickel dibromide, bis-2,
6-dimethylphenyliminoacenaphthalene nickel dichloride, bis-2,6-diphenyliminoacenaphthalene nickel dibromide, bis-2,6-diphenyliminoacenaphthalene nickel dichloride, 1,4-bisdiisopropylphenyl 2,3-dimethyldia Zabutadiene nickel dibromide, 1,4-bisdiisopropylphenyl 2,3-dimethyldiazabutadiene nickel dichloride, 1,4-bisdimethylphenyl 2,3-dimethyldiazabutadiene nickel dibromide, 1,4-bisdimethylphenyl 2,3-dimethyldiazabutadiene nickel dichloride, 1,4-bisphenyl 2,3-dimethyldiazabutadiene nickel dibromide, 1,4-
Bisphenyl 2,3-dimethyldiazabutadiene nickel dichloride, 1,4-bisdiisopropylphenyldiazabutadiene nickel dibromide, 1,4-bisdiisopropylphenyldiazabutadiene nickel dichloride, 1,4-bisdimethylphenyldiazabutadiene Nickel dibromide, 1,4-bisdimethylphenyldiazabutadiene nickel dichloride, 1,4-bisphenyldiazabutadiene nickel dibromide, 1,4-bisphenyldiazabutadiene nickel dichloride, bipyridyl nickel dibromide, bipyridyl nickel dichloride Phenanthoryl nickel dibromide, phenanthrolyl nickel dichloride, 2,6-bis [1- (2,
6-diisopropylphenylimino) ethyl] pyridine iron chloride, 2,6-bis [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron bromide, 2,6-bis [1- (phenylimino) ethyl] pyridine Iron chloride, 2,6-bis [1-
(Phenylimino) ethyl] pyridine iron bromide, 2,6-bis [1- (2,6-diisopropylphenylimino) ethyl] pyridine cobalt chloride, 2,
6-bis [1- (2,6-diisopropylphenylimino) ethyl] pyridine cobalt bromide, 2,6-bis [1- (phenylimino) ethyl] pyridine cobalt chloride, or 2,6-bis [1- (phenyl) Imino)
[Ethyl] pyridine cobalt bromide.

The organic aluminum compound is preferably a trialkylaluminum, a dialkylaluminum halide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, an aluminoxamine, or a mixture thereof. In particular,
Trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, tri-t-
Butyl aluminum, triisopropyl aluminum,
Tripentyl aluminum, trinormal hexyl aluminum, tri (2-methylpentyl) aluminum,
Trinormal octyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, methyl aluminum sesquichloride, isobutyl aluminum sesquichloride, di-t-butyl aluminum chloride, diisopropyl aluminum chloride, dipentyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, Preferred examples include t-butylaluminum dichloride, isopropylaluminum dichloride, and pentylaluminum dichloride.

The aluminoxane is obtained by the condensation of one kind of trialkylaluminum with water, and is obtained by the condensation of two or more kinds of trialkylaluminum with water. Or a cage-like condensate. Specific examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Particularly, methylaluminoxane and methylisobutylaluminoxane are preferable.

The electron donating component is specifically a Lewis acid, a Bronsted acid, a halogenated compound, or a mixture thereof. In particular, the electron donating component is nickel, ruthenium, iron, palladium as a transition metal element,
It is preferably used when a transition metal compound having a metal element selected from cobalt and platinum is used. Examples of Lewis acids include BF ₃ ethylate, Ti
Cl ₄ , SbF ₅ , BCl ₃ , B (OCH ₂ CH ₃ ),
SiCl ₄ , tris (perfluorophenyl) boron,
(C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ , LiB (C
₆ F _{5) 4,} and _{NH (CH 2) 2 C 6} H 4 B (C 6 F
₅ ) It is preferably selected from the group consisting of ₄ . HSbF ₆ , HPF ₆ , CF ₃
CO ₂ H, FSO ₃ H.SbF ₅ , H ₂ C (SO ₂ CF
₃ ) It is preferably selected from the group consisting of ₂ , CF ₃ SO ₃ H and paratoluenesulfonic acid. The halogenated compound is hexachloroacetone, hexafluoroacetone, 3-butenic acid-2,2,3,4,4.
It is preferably selected from the group consisting of -pentachlorobutyl ester, hexachloroglutaric acid, hexafluoroisopropanol and chloranil, and mixtures thereof.

The trifluorostyrene can be polymerized by using each of these types of catalysts. For the polymerization reaction, any method such as slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization, and suspension polymerization may be used in the presence of the catalyst of the present invention. In the polymerization method of the present invention, a polymerization solvent that can be used in the case of solution polymerization includes aliphatic hydrocarbons such as butane, n-pentane, n-hexane, n-octane, iso-octane, n-nonane, and n-decane. , Cyclopentane, methylcyclopentane, cyclohexane,
Methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, alicyclic hydrocarbons such as norbornane, benzene, toluene, xylene, ethylbenzene, aromatic hydrocarbons such as cumene, diethyl ether, ethers such as tetrahydrofuran, chlorobenzene, Examples thereof include aromatic halogens such as o-dichlorobenzene and 1,2,4-trichlorobenzene, and fluorine compounds such as chlorofluorocarbon and alternative fluorocarbons. These polymerization solvents may be used alone or in combination of two or more.

In the present polymerization method, the amount of the catalyst used is not particularly limited.
The metal element is in a range of 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ^−2.
mol range. In the present polymerization method, the polymerization temperature is:
It is set as required, but is generally in the range of -80 to 120C, preferably in the range of -30 to 110C, and more preferably in the range of 0 to 100C. As the atmosphere of the polymerization system, an inert atmosphere formed with an inert gas such as nitrogen, argon, or helium may be used, or an inert atmosphere may not be required. There is no particular limitation on the pressure of the polymerization system. In the case of copolymerization with a vinyl monomer, gaseous monomers such as ethylene, propylene, butadiene, and allene can be added at 1 atm or more. In the present polymerization method, the time required for the polymerization reaction varies depending on the purpose or the polymerization conditions, and is not particularly limited.
In many cases, it is less than 24 hours, and sometimes less than 1 to 3 hours.

According to the present invention, the transition metal in the transition metal catalyst is nickel, palladium, cobalt,
Preferably, it is at least one of iron. These transition metals have high polymerization activity and give a soluble norbornene-based copolymer. Also, palladium, cobalt,
When iron is used, a polymer is often obtained even in an inert atmosphere.

In the present polymerization method, after achieving a predetermined polymerization rate, if necessary, a known terminal modifier, terminal branching agent, a polymerization terminator, a polymerization stabilizer, and an oxidation stabilizer are added. Can be. Further, after the polymerization reaction, it is possible to further derivatize the molecular structural unit with hydrogen, a halogen atom, an organic functional group or the like. The polymer can be recovered by a conventionally known solvent removing operation, drying operation and the like.

The starting material for this polymerization step is a trifluorostyrene monomer. The trifluorostyrene monomer is C
F ₂ = CF (C ₆ H ₅ ). The concentration of the trifluoroethylene monomer in the polymerization reaction solution is preferably 0.1 mol / l or more from the viewpoint of reaction efficiency. If it is less than 0.1 mol / l, the polymerization reaction may be slow and the efficiency may be reduced.

The trifluorostyrene (co) polymer obtained by the present synthesis method has relatively water repellency. In addition, when there are many copolymer components, there exists a tendency for water repellency to fall. Further, as in the invention of claim 6, the trifluorostyrene monomer and an olefin compound can be copolymerized.

The trifluorostyrene (co) polymer obtained by the present synthesis method has use as a polymer electrolyte for fuel cells or a precursor thereof. The precursor of this electrolyte is formed by introducing an ion-dissociating group such as a sulfone group or a phosphone group into an aromatic ring of a trifluorostyrene (co) polymer and forming a film. Incidentally, an ion dissociating group may be introduced after the film formation.

[0070]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 An embodiment of the first invention will be described with reference to Examples 1 to 9. Example 1 In a glove box, 8.5 mg of bisallylnickel bromide and 40 g of chlorobenzene were mixed at room temperature under an argon atmosphere to prepare a main catalyst solution. On the other hand, as shown in FIG. 1 (a), 20 g of norbornene and 22 g of styrene, which are cyclic olefin monomers, and 0.25 g of methylaluminoxane as a co-catalyst were added to 2.1 g of toluene in a glove box at room temperature under an argon atmosphere. The solution was dissolved, and the entire amount was added to the entire amount of the main catalyst solution with stirring while maintaining the temperature of the solution at room temperature. The polymerization proceeded quickly and the polymerization reaction was completed within 3 hours. Take out the resulting viscous polymer solution from the glove box, add to a large amount of hydrochloric acid acidic methanol,
The polymer was isolated by precipitation. Subsequently, methanol was removed by filtration, followed by vacuum drying at room temperature for 24 hours.
(Yield 100%) was obtained. As a result of IR and NMR measurements, the resulting polymer was found to be a norbornene-styrene copolymer as shown in FIG. 1 (b). Mw calculated from GPC (polystyrene conversion)
(Weight average molecular weight) was 168 × 10 ³ .

Next, in order to introduce a chlorosulfonic acid group into the styrene unit of the copolymer, 0.5 g of the above copolymer was mixed with 10 g of chlorosulfonic acid and 160 g of tetrachloroethane (excess amount). ) At room temperature for 1 hour. After the reaction, the sample was washed with ethanol to remove unreacted components. Subsequently, the sample was immersed in 50 ml of a 1N aqueous solution of potassium hydroxide, and heated under reflux for 1 hour to hydrolyze chlorosulfonic acid groups. In addition, 1
Proton exchange of sulfonic acid groups was performed by heating and refluxing for 1 hour using 50 ml of N hydrochloric acid. After the obtained sample was washed with distilled water, it was dried under reduced pressure at 80 ° C.
As shown in (c), a norbornene / styrene copolymer in which sulfonic acid was introduced into styrene units was obtained.

At this time, the EW value, which is an index of sulfone group introduction, was 537 (* Method for measuring EW is as follows). Thermogravimetric loss measurement of the sulfonated copolymer (T
GA), no thermogravimetric loss was observed up to a temperature range (220 to 250 ° C.) where the sulfone group itself thermally decomposed. Further, a clear glass transition point did not appear in the range of room temperature to 250 ° C., indicating that the obtained copolymer had high heat resistance.

* EW (Equivalent Weight) Measurement A 0.1 g sample into which sulfonic acid was introduced was immersed in 25 ml of a 0.1N aqueous sodium hydroxide solution for 12 hours at room temperature to exchange sulfonic acid groups with sodium. At the same time, a sample to which no sample was added was similarly prepared and used as a blank. After immersion, the membrane of the sample formed from the sodium hydroxide solution was taken out, and the membrane surface was washed with distilled water, and the washing solution was washed with the sodium hydroxide solution to obtain a titration sample. Automatic titrator (Hiranuma Comt
ite T-900), titrate the sample and blank with 0.5 N hydrochloric acid, and determine the end point from the inflection point of the titration curve,
The EW of the film was calculated by the following equation (1). The EW value is the reciprocal of the ion dissociating group (mol) per 1 g of the polymer,
The smaller the value, the more sulfone groups were introduced. The EW value of Nafion is 1100.

EW (g / eq) = W / ((Qblank−Qsample) /1000×0.5×FHCl) (1)

W: membrane weight (g), Qblank: titer for blank (ml), Qsample: titer for sample (ml), FHCl: titer of 0.5N hydrochloric acid

Example 2 The same procedure as in Example 1 was repeated except that dicyclopentadiene was used instead of styrene to obtain a norbornene / dicyclopentadiene copolymer (yield: 95%). . At this time, Mw of the produced polymer was 139 × 10 ³ .

Further, a norbornene / dicyclopentadiene copolymer into which sulfonic acid was introduced was obtained in the same manner as in Example 1 (EW value 1058). What is the sulfonated copolymer? As in the case of Example 1, no thermogravimetric loss and no glass transition point were observed up to around 250 ° C., indicating high heat resistance.

Example 3 The procedure of Example 1 was repeated, except that 5-ethylidene-2-norbornene was used instead of styrene.
A 5-ethylidene-2-norbornene copolymer was obtained (yield 98%). At this time, Mw of the produced polymer was 246 × 1
0 was ^3.

Further, a norbornene / 5-ethylidene-2-norbornene copolymer into which sulfonic acid was introduced was obtained in the same manner as in Example 1 (EW value: 513). As in the case of Example 1, no thermogravimetric loss and no glass transition point were observed in the sulfonated copolymer up to about 250 ° C., indicating that the sulfonated copolymer had high heat resistance.

Example 4 The procedure of Example 1 was repeated, except that 1,3-cyclohexadiene was used instead of styrene.
-Cyclohexadiene copolymer was obtained (yield 100
%), And the Mw of the resulting polymer was 198 × 10 ³ .

Further, a norbornene / 1,3-cyclohexadiene copolymer into which sulfonic acid was introduced was obtained in the same manner as in Example 1 (EW value: 770). As in the case of Example 1, no thermogravimetric loss and no glass transition point were observed in the sulfonated copolymer up to about 250 ° C., indicating that the sulfonated copolymer had high heat resistance.

Example 5 The same operation as in Example 1 except that after polymerization of norbornene was completed (styrene was not added, mixing with the catalyst solution was performed for 3 hours), a styrene monomer was added to the polymerization reaction solution. To obtain a norbornene / styrene block copolymer (100% yield).
%). At this time, Mw of the produced polymer was 352 × 10 ³ .

Further, a copolymer having sulfonic acid introduced therein was obtained in the same manner as in Example 1 (EW value: 599). As in the case of Example 1, no thermogravimetric loss and no glass transition point were observed in the sulfonated copolymer up to about 250 ° C., indicating that the sulfonated copolymer had high heat resistance.

(Example 6) In Example 5, styrene
Except that dicyclopentadiene was used instead of
By exactly the same operation, first, norbornene / dicyclopen
A tadiene block copolymer was obtained (yield 100%). This
Mw of the produced polymer is 387 × 10 ³Met.

Further, a copolymer into which sulfonic acid was introduced was obtained in the same manner as in Example 1 (EW value: 1002). As in the case of Example 1, no thermogravimetric loss and no glass transition point were observed in the sulfonated copolymer up to about 250 ° C., indicating that the sulfonated copolymer had high heat resistance.

Example 7 The procedure of Example 5 was repeated, except that 1,3-cyclohexadiene was used instead of styrene.
-Cyclohexadiene block copolymer was obtained (yield 1
00%). At this time, Mw of the produced polymer was 389 × 10
It was ³ .

Further, a sulfonic acid-introduced copolymer was obtained in the same manner as in Example 1 (EW value: 801). As in the case of Example 1, no thermogravimetric loss and no glass transition point were observed in the sulfonated copolymer up to about 250 ° C., indicating that the sulfonated copolymer had high heat resistance.

Example 8 The procedure of Example 3 was repeated, except that the sulfonation of the copolymer was carried out by the dropwise addition of a SO ₃ / trimethyl phosphate (2: 1) complex reagent. Norbornene / 5 with acid
-Ethylidene-2-norbornene copolymer (EW
Value 564). Similar to the case of Example 1, the copolymer sulfonated by this method showed no thermogravimetric loss and no glass transition point up to around 250 ° C., indicating high heat resistance.

Example 9 The same operation as in Example 1 was carried out except that phosphonic acid was introduced instead of sulfonic acid. Similar to the case of Example 1, the phosphonated copolymer showed no thermogravimetric loss and no glass transition point up to around 250 ° C., indicating high heat resistance.

Embodiment 2 An embodiment of the second invention will be described using Examples 1 to 5 and Comparative Example 1. (Example 1) In a glove box under a room-temperature argon atmosphere, 18 mg of bisallylnickel bromide (Ni-based catalyst), 0.58 g of methylaluminoxane, and 15 g of toluene were mixed to prepare a catalyst solution. On the other hand, FIG.
As shown in (a), 4 g of α, β, β-trifluorostyrene and 4 g of styrene are dissolved in 15 g of toluene in a glove box under an argon atmosphere at room temperature, and the solution is stirred while maintaining the temperature of the solution at room temperature. The whole amount was added to the whole amount of the catalyst solution while adding. The polymerization proceeded promptly in a homogeneous system to obtain a viscous polymer solution. The toluene solution containing the produced polymer was taken out of the glove box, and added to a large amount of hydrochloric acid-methanol to precipitate and isolate the polymer. Subsequently, methanol was removed by filtration, followed by vacuum drying at room temperature for 24 hours.
%) (Weight average molecular weight; Mw = 10,50)
0) was obtained.

When the 19F NMR of the produced polymer was measured, a strong peak having a chemical shift completely different from that of the monomer or dimer of trifluorostyrene was found to be -8.
3, -88, and -89 ppm were observed, respectively, and the formation of the styrene-trifluorostyrene copolymer shown in FIG. 2B was confirmed.

Example 2 The same operation as in Example 1 was carried out except that phenanthroline nickel dibromide was used instead of bisallyl nickel bromide. As a result, 6.1 g (yield 76%) of the polymer was obtained. (Weight average molecular weight; Mw: 11,000) was obtained.

Example 3 The same operation as in Example 1 was carried out except that the following catalyst A was used instead of bisallylic nickel bromide. As a result, 6.7 g (yield 84%) of polymer was obtained. (Weight average molecular weight; Mw = 16,1
00).

[0094]

Embedded image

Example 4 The same operation as in Example 1 was carried out except that 4 g of norbornene was added instead of styrene. As a result, 6.8 g (yield: 85%) of polymer (weight average molecular weight; (Mw = 18,600).

Example 5 The same operation as in Example 3 was carried out except that 4 g of propylene was added instead of styrene. As a result, 6.5 g (yield 81%) of a polymer (weight average molecular weight; Mw = 10,900).

(Comparative Example 1) In Example 1, AIBN (2,2'-azobisisobutyronitrile) was used instead of the bisallylnickel bromide / methylaluminoxane catalyst, and polymerization was carried out at 100 ° C. Except for, the same operation was performed. After purification and isolation, 3.9 g of a polymer was obtained, but as a result of 19F NMR measurement, formation of a copolymer was not confirmed (only polystyrene was formed). As a result of analyzing methanol used for the isolation, unreacted monomers and dimers of trifluorostyrene were detected.

[0098]

According to the present invention, there is provided a norbornene-olefin copolymer excellent in heat resistance, a method for synthesizing the same, and a method for synthesizing a trifluorostyrene (co) polymer having high synthesis efficiency by a polymerization reaction. be able to.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a method for synthesizing a norbornene copolymer in the present invention.

FIG. 2 shows trifluorostyrene (co) in the present invention.
FIG. 4 is an explanatory view showing a method for synthesizing a polymer.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Arimitsu Usuki 41-1, Oku-cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture F-term in Toyota Central R & D Laboratories Co., Ltd. 4J028 AA01A AB00A AC45A AC46A AC47A AC48A BA00A BA01B BB00A BB01B BC15B BC16B BC17B BC19B BC25B CA14C CB23C CB43C CB53C CB54C CB81C CB84C CB86C CB91C CB94C CB98C EB12 EB17 EB18 EB21 EC01 EC02 FA01 FA02 FA03 FA04 FA07 GA18 GA19 4J100 AA03Q AB02Q AC53P AR11P AR18Q AR22Q AS15Q BA56H BA64H BC08Q CA04 CA31 FA10 HA61 HB50 HB52 HB58 JA43

Claims (7)

[Claims] 1. a step of using a transition metal catalyst to copolymerize norbornene or a derivative thereof and a double bond-containing monomer into which an ion dissociating group can be introduced; A step of introducing a dissociating group, wherein the transition metal catalyst is a compound represented by the following formula (IV): {Where, M represents a transition metal element belonging to Groups 8, 9 and 10 of the periodic table, L represents a ligand having 1 to 3 π bonds, X represents at least one σ bond and 0 to 3 Represents a ligand having π bonds, n is 0, 1 or 2, m is 0 or 1, and both n and m are not simultaneously 0, and when m is 0 a is 2, m is a is 1 when 1, a _denotes an anion for ^{_{[L n MX m] a +}} . Or (a) a transition metal compound of a transition metal element belonging to Groups 8, 9 and 10 of the periodic table;
A method for synthesizing a norbornene-based copolymer, which is a multi-component catalyst containing (b) an organoaluminum compound and / or (c) an electron-donating component. 2. The double bond-containing monomer according to claim 1, wherein the double bond-containing monomer into which the ionic dissociating group can be introduced has an aromatic ring, has a plurality of double bonds, and has one of the two A method for synthesizing a norbornene-based copolymer, characterized in that either a double bond is involved or a reactive group is formed at a new position after polymerization. 3. The method according to claim 1, wherein the transition metal in the transition metal catalyst is at least one of nickel, palladium, cobalt, and iron. 4. A norbornene-based copolymer comprising norbornene or a derivative thereof and a double bond-containing monomer into which an ion dissociating group has been introduced. 5. A method for synthesizing a trifluorostyrene (co) polymer by (co) polymerizing a trifluorostyrene monomer using a transition metal catalyst, wherein the transition metal catalyst has the following formula: A compound represented by the formula (IV): {Where, M represents a transition metal element belonging to Groups 8, 9 and 10 of the periodic table, L represents a ligand having 1 to 3 π bonds, X represents at least one σ bond and 0 to 3 Represents a ligand having π bonds, n is 0, 1 or 2, m is 0 or 1, when n and m are not both 0 at the same time, and when m is 0 a is 2, m is a is 1 when 1, a _denotes an anion for ^{_{[L n MX m] a +}} . Or (a) a transition metal compound of a transition metal element belonging to Groups 8, 9 and 10 of the periodic table;
A method for synthesizing a trifluorostyrene (co) polymer, comprising a multi-component catalyst containing (b) an organoaluminum compound and / or (c) an electron-donating component. 6. The method for synthesizing a trifluorostyrene (co) polymer according to claim 5, wherein the trifluorostyrene monomer and an olefin compound are copolymerized. 7. The synthesis of a trifluorostyrene (co) polymer according to claim 5, wherein the transition metal in the transition metal catalyst is at least one of nickel, palladium, cobalt and iron. Method.