JP2007063351A - Fluorine-containing polymerization monomer and its polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a norbornene compound having fluorine groups and excellent in polymerization reactivity such as ring-opening metathesis polymerization reactivity, and to provide its polymer. <P>SOLUTION: A fluorine-containing polymerization monomer is represented by formula (1) (wherein, R<SP>1</SP>and R<SP>2</SP>are each independently H or methyl; Rf<SP>1</SP>, Rf<SP>2</SP>, Rf<SP>3</SP>and Rf<SP>4</SP>are each independently F or a 1 to 20C polyfluoroalkyl which may contain one or more etheric oxygen atoms at one or more arbitrary positions). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fluorine-containing polymerization monomer having a norbornene skeleton and a polymer thereof.

Conventionally, a compound having a norbornene skeleton (hereinafter sometimes referred to as “norbornene compound”) has been widely used as a monomer for ring-opening polymerization by a metathesis reaction using a metal catalyst to obtain a polymer. Further, a polymer containing a structural unit based on this norbornene compound and its hydrogenated product are excellent in balance of various properties such as high glass transition temperature (high heat resistance), low water absorption, high light transmittance, etc. By various molding methods such as injection molding, extrusion molding, and compression molding, they are used in a wide variety of fields such as electric / electronic materials, semiconductor materials, and optical materials.
A norbornene compound having a fluorine atom or a substituent containing a fluorine atom (hereinafter sometimes referred to as “fluorine group”) (hereinafter also referred to as “fluorine-containing norbornene compound”) is synthesized and opened. It has been reported that a fluorine-containing polymer is synthesized by being used as a monomer for metathesis polymerization (see, for example, Non-Patent Document 1).
A polymer of a fluorine-containing norbornene compound is expected to be superior in chemical durability, weather resistance, and light transmittance than other norbornene compound polymers due to the characteristics of the fluorine group.
On the other hand, as part of addition reaction research, synthesis examples of fluorine-containing oxanorbornene compounds having an oxygen atom at the bridgehead of the fluorine-containing norbornene compounds have been reported (see Non-patent Documents 2 and 3).
POLYMER, 2003, 44, p6111-6121 Journal of Fluorine Chemistry, 2000, No. 104, p233-237 Izvestiia Akademii Nauk SSSR, Seriia Khimicheskaia 1988, No. 4, p897-900

However, the fluorine-containing norbornene compound of Non-Patent Document 1 has a yield of a polymer obtained by ring-opening metathesis (hereinafter sometimes referred to as “ring-opening metathesis polymer”) of only 30 to 55%. There is a problem that a polymer by ring-opening metathesis polymerization cannot be obtained more efficiently than a norbornene compound.
On the other hand, Non-Patent Documents 2 and 3 only show synthesis examples of fluorine-containing oxanorbornene compounds, and no attempt has been made to polymerize them. That is, it was not clear at all whether these fluorine-containing oxanorbornene compounds could become a polymer monomer.
The present invention has been made in view of the above circumstances, and provides a norbornene compound having a fluorine group and excellent in polymerization reactivity such as ring-opening metathesis polymerization, and a polymer thereof.

In order to achieve the above object, the present invention adopts the following configuration.
[1] A fluorine-containing polymerization monomer represented by the following formula (1).

In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and Rf ¹ , Rf ² , Rf ³ and Rf ⁴ are each independently a fluorine atom, or one or more ethers at any place It is a C1-C20 polyfluoroalkyl group which may contain a reactive oxygen atom.

[2] The fluorine-containing polymerization monomer according to [1], wherein any one of Rf ¹ , Rf ² , Rf ³ and Rf ⁴ is a trifluoromethyl group and the other is a fluorine atom.

[3] A fluorine-containing polymer containing a structural unit based on the monomer for fluorine-containing polymerization according to [1] or [2].
[4] The fluorine-containing polymer according to [3] obtained by ring-opening metathesis polymerization.

  [5] A fluorine-containing polymer represented by the following formula (2), obtained by ring-opening metathesis polymerization of the monomer for fluorine-containing polymerization according to [1] or [2].

^{However, R 1, R 2, Rf} 1, Rf 2, Rf 3 and Rf ⁴ in the formula (2) is as defined above, n is a positive integer.

  [6] The fluorine-containing polymer according to any one of [3] to [5], wherein the number average molecular weight is 1,000 to 500,000 in terms of polymethyl methacrylate.

  The monomer for fluorine-containing polymerization of the present invention is a norbornene compound having a fluorine group and excellent in polymerization reactivity, particularly ring-opening metathesis polymerizability. Moreover, the fluorine-containing polymer of the present invention, particularly the ring-opening metathesis polymer, has excellent characteristics of fluorine groups and can be produced efficiently.

[Monomer for fluorine-containing polymerization]
The monomer for fluorine-containing polymerization of the present invention is a fluorine-containing oxanorbornene compound represented by the following formula (1). In the present specification, the compound represented by the formula (1) is also referred to as “compound (1)”. The same applies to compounds represented by other formulas.

R ¹ and R ² in the formula (1) are each independently a hydrogen atom or a methyl group, but in order not to reduce the polymerizability due to the steric influence in the vicinity of the double bond of the monomer, both are hydrogen atoms. Preferably there is.

Rf ¹ , Rf ² , Rf ³ and Rf ⁴ in the formula (1) are each independently a fluorine atom, or the number of carbon atoms which may contain one or more etheric oxygen atoms in any place is 1 to 20 Of the polyfluoroalkyl group.
That is, when Rf ¹ , Rf ² , Rf ³ and Rf ⁴ are polyfluoroalkyl groups, they may or may not contain an etheric oxygen atom, and when they contain an etheric oxygen atom, It may be included anywhere.
In order to improve metathesis polymerizability, when it does not contain an etheric oxygen atom, it preferably has 1 to 8 carbon atoms, and when it contains an etheric oxygen atom, it preferably has 1 to 10 carbon atoms. .

In addition, when Rf ¹ , Rf ² , Rf ³ and Rf ⁴ are polyfluoroalkyl groups, it is preferable that the hydrogen atom of the alkyl group is replaced with a fluorine atom, which is a perfluoroalkyl group. Is particularly preferred. This is because the more fluorine atoms, the more excellent characteristics of the fluorine group can be obtained upon polymerization. Examples of the substituent other than the fluorine atom in Rf ¹ , Rf ² , Rf ³ and Rf ⁴ include a chlorine atom, but it is preferable that no substituent other than the fluorine atom is present.
Rf ¹ , Rf ² , Rf ³ and Rf ⁴ may be any of linear, branched and cyclic structures.

In addition, Rf ¹ , Rf ² , Rf ³ and Rf ⁴ are either a polyfluoroalkyl group from the viewpoint of compatibility between the heat resistance stability of the resulting polymer, chemical durability and polymerization activity of the monomer, The other is preferably a fluorine atom, any one is a perfluoroalkyl group, the other is more preferably a fluorine atom, any one is a trifluoromethyl group, and the other is a fluorine atom. Is particularly preferred.

  The monomer for fluorine-containing polymerization of the present invention is excellent in polymerization reactivity, particularly ring-opening metathesis polymerizability. It is presumed that this is because the oxygen atom at the bridgehead has an electron donating property, so that the influence of the electron withdrawing property of the fluorine atom can be alleviated to ensure the double bond reactivity.

[Method for producing monomer for fluorine-containing polymerization]
Compound (1) is synthesized by a Diels-Alder reaction between a furan derivative represented by the following formula (3) and a fluorine-containing alkene represented by the following formula (4).
^{R 1} and ^{R 2} in the formula (3) is the same as ^{R 1} and ^{R 2} in the formula (1). Further, ^{Rf 1,} Rf 2, Rf ³ and Rf ⁴ under formula (4) is the same as ^{Rf 1,} Rf 2, Rf ³ and Rf ⁴ in the formula (1).

  Compound (3) is easily available as a commercial product. Compound (4) can be easily synthesized by a conventionally known method such as a thermal decomposition reaction of tetrafluoroethylene or polyfluoroalkanoic acid fluoride.

  In order to suppress the production of by-products and efficiently proceed the Diels-Alder reaction between the compound (3) and the compound (4), the amount of the compound (4) used is 1 with respect to the compound (3). It is preferable to set it to -1.5 times equivalent, and it is more preferable to set it as 1-1.2 times equivalent.

In order to allow the Diels-Alder reaction to proceed efficiently, it is particularly preferable to carry out the reaction without a solvent.
A fluorine-containing solvent may be used in consideration of the solubility of the compound (4). As the fluorine-containing solvent, hydrochlorofluorocarbon, hydrofluorocarbon, and hydrofluoroether are preferable. These compounds may have a linear, branched or cyclic structure.
Specifically, hydrochlorofluorocarbons such as CF ₂ ClCF ₂ CHClF and CF ₂ ClCFCl ₂ , CF ₃ (CF ₂ ) ₄ CHF ₂ , CF ₃ (CHF) ₂ CF ₂ CF ₃ , CF ₃ CH ₂ CF ₂ CH ₃ And hydrofluoroethers such as CHF ₂ CF ₂ OCH ₂ CF ₃ and C ₄ F ₉ OCH ₃ . Among these, CF ₂ ClCF ₂ CHClF is preferable because it has a low environmental burden, is inert to the raw materials, and has high handling convenience.

  Compound (4) is a good dienophile, and Diels-Alder reaction with compound (3) proceeds efficiently. In order to further improve the reaction efficiency, the reaction temperature is preferably 100 ° C to 200 ° C. Moreover, although reaction time changes with kinds of compound (4), it is preferable to make it react for 40 to 100 hours, and it is more preferable to make it react for 72 to 100 hours.

 In order to purify the compound (1) from the reaction solution after completion of the Diels-Alder reaction, general separation techniques such as column chromatography, fractional distillation, recrystallization and the like can be used. In order to extract the highly pure compound (1) simply, it is preferable to perform separation by distillation under reduced pressure.

[Fluoropolymer]
Even if the fluoropolymer of the present invention is a homopolymer consisting only of structural units based on the compound (1), it is a monomer copolymerizable with the compound (1) (hereinafter sometimes referred to as “copolymerization monomer”). It may be a copolymer containing structural units based on In the case of a copolymer, the copolymerization monomer may be one type or a combination of a plurality of types.
In addition, the polymer of the present invention may be a ring-opening metathesis polymer obtained by ring-opening metathesis polymerization or a polymer obtained by radical polymerization (hereinafter sometimes referred to as a radical polymer). .
The number average molecular weight of the fluoropolymer is preferably 1,000 to 500,000 in terms of polymethyl methacrylate. Thereby, it is possible to obtain a fluorine-containing polymer having excellent mechanical properties and physical properties and excellent workability.

[Ring-opening metathesis polymer]
Compound (1) can be subjected to ring-opening metathesis polymerization alone. A homopolymer obtained by ring-opening metathesis polymerization of only the compound (1) is represented by the following formula.
In ^{R 1, R 2, Rf 1} , Rf 2, Rf 3 and Rf ⁴ are the same meaning as ^{R 1, R 2, Rf 1} , Rf 2, Rf 3 and Rf ⁴ in the formula (1) in the following formula (2) Yes, n is a positive integer.

  Compound (1) can be copolymerized with other ring-opening metases polymerizable monomers. As the copolymerization monomer, norbornene or a functional group-containing or non-functional norbornene derivative is preferably used. Examples of norbornene derivatives include the following compounds.

Non-functional norbornene derivatives: norbornadiene, methylnorbornene, dimethylnorbornene, etc. Norbornene derivatives having a perfluoroalkyl group: 5-trifluoromethyl-2-norbornene, 5-pentafluoroethyl-2-norbornene, 5-heptafluoropropyl-2 -Norbornene, 5-trifluoromethoxy-2-norbornene, etc. Norbornene derivatives having other functional groups: 5-acetyl-2-norbornene, N-hydroxy-5-norbornene-2,3-dicarboximide, 5-norbornene- 2-carbonitrile, 5-norbornene-2-carboxaldehyde, 5-norbornene-2,3-dicarboxylic acid monomethyl ester, 5-norbornene-2,3-dicarboxylic acid dimethyl ester, 5,5-norbornene 2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2-methanol, 6-triethoxysilyl-2-norbornene, 5-norbornene-2-ol.
Polycyclic norbornene derivatives: Tricyclic norbornene such as dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, and dicyclopentadiene, tricyclopentadiene (cyclopentadiene trimer), tetracyclopentadiene (four of cyclopentadiene) Norbornene having 5 or more rings such as a polymer).

  Examples of copolymerizable monomers other than norbornene or norbornene derivatives include cycloalkenes such as cyclohexene, cycloheptene, cyclooctene, tetracyclododecene, methyltetracyclododecene, and dimethylcyclotetradodecene.

In order to cause ring-opening metathesis polymerization of the compound (1) or the compound (1) and the copolymerization monomer, it is preferable to use a catalyst. As the catalyst, a combination of a transition metal compound such as tungsten, molybdenum, rhenium, titanium, ruthenium, rhenium, iridium and a promoter such as alkylaluminum, or a conventionally known catalyst such as tungsten, molybdenum, osmium, and ruthenium carbene complex. Polymerization methods can be used. Among them, it is preferable to use a ruthenium carbene complex and an osmium carbene complex that exhibit sufficient polymerization activity even in the presence of oxygen and moisture. Further, these metathesis polymerization catalysts may be used alone or in combination with a ruthenium carbene catalyst and an osmium carbene catalyst, respectively.
The compounding amount of the catalyst is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers.

The ring-opening metathesis polymerization is preferably performed in the presence of a polymerization solvent. The polymerization solvent is not particularly limited as long as it does not reduce the activity of the catalyst, but from the viewpoint of the solubility of the compound (1), the use of a fluorinated solvent is preferred.
As the fluorine-based solvent, chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroether, and fluorine-containing aromatic compound are preferable. These compounds may have a linear, branched or cyclic structure. Specifically, chlorofluorocarbons such as CF ₃ CCl ₃ , hydrochlorofluorocarbons such as CF ₂ ClCF ₂ CHClF, CF ₂ ClCFCl ₂ , CF ₃ (CF ₂ ) ₄ CHF ₂ , CF ₃ (CHF) ₂ CF ₂ CF ₃ , CF ₃ CH ₂ CF ₂ CH ₃ , hydrofluorocarbons such as benzotrifluoride, CHF ₂ CF ₂ OCH ₂ CF ₃ , hydrofluoroethers such as C ₄ F ₉ OCH ₃ , fluorobenzene, hexafluorobenzene, benzofluoride, etc. And a fluorine-containing aromatic compound.

  The concentration of the monomer with respect to the solvent is preferably 1 to 80% by mass, and more preferably 1 to 20% by mass. By setting it as 1-20 mass%, the viscosity rise of the reaction solution after superposition | polymerization can be suppressed easily.

A chain transfer agent can be used for the purpose of adjusting the molecular weight of the polymer. Examples of chain transfer agents include 1-butene, 1-hexene, 1-octene, allyl alcohol, allyl isocyanate, allyl glycidyl ether, allyl triethoxysilane, allyl methacrylate, 2- (allyloxy) ethyl alcohol, diallyl maleate And allyl compounds such as o-allylphenol, vinyl compounds such as styrene, p-methoxystyrene, 4-vinyl-1-cyclohexene-1,2-epoxide, etc. The amount of chain transfer agent added depends on the desired molecular weight and catalyst. Although depending on the type, a polymer having a number average molecular weight (in terms of polymethyl methacrylate) of 1,000 to 500,000 can be easily obtained by adding 0 to 100 equivalents to the catalyst.

Although superposition | polymerization temperature changes with the superposition | polymerization solvent to be used, it is preferable that it is 0-100 degreeC. Moreover, it is more preferable that it is 0-30 degreeC from a viewpoint of suppressing a rapid polymerization reaction. However, when a chain transfer agent is used in combination, the polymerization reaction is preferably carried out at 40 to 80 ° C. in order to accelerate the polymerization rate and improve the reaction yield.
The reaction stops spontaneously once the monomer has reacted and is completely consumed. The time until the reaction is completed varies depending on the monomer composition, the type and addition amount of the catalyst, the amount of the solvent, and the reaction temperature, but is usually 10 minutes to 24 hours. The reaction is preferably continued until the reaction is stopped.

When all of the monomers have been reacted and consumed, the polymerization reaction stops spontaneously, but the catalyst remains active. For this reason, there is a possibility that the polymers are coupled to each other, or the catalyst component is oxidized and the polymer is colored.
In order to eliminate the adverse effects of these catalysts, a vinyl compound such as ethyl vinyl ether, n-butyl vinyl ether, vinyl acetate or the like may be added to inactivate the catalyst. Alternatively, the catalyst component may be removed by performing an adsorption treatment with an adsorbent such as alumina, celite, or activated carbon.

[Radical polymer]
Compound (1) can also be used as a radical polymerizable monomer. Further, it can be copolymerized with other radical polymerizable monomers in the presence of free radicals.
As the copolymerization monomer for radical polymerization, a substituted or unsubstituted alkene derivative is preferably used. A plurality of copolymerization monomers can be used in combination.
Specific examples include fluorine-containing alkene compounds such as tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride and chlorotrifluoroethylene, alkene compounds such as ethylene and propylene, perfluoro (n-methyl vinyl ether), perfluoro (n- Perfluoro (alkyl vinyl ether) compounds such as propyl vinyl ether), perfluoroalkylethylene compounds such as pentafluoroethylethylene and nonafluorobutylethylene, and vinyl ester compounds such as vinyl acetate and vinyl benzoate. A copolymerization monomer may be used individually by 1 type, and may use 2 or more types together.
As the copolymerization monomer, a fluorine-containing monomer is preferable, and tetrafluoroethylene is more preferable.

  In radical polymerization, various polymerization forms such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization can be employed. As the radical generating source, initiators such as various organic and inorganic peroxide compounds can be used, and are selected depending on the polymerization mode to be used.

The present invention is described in detail below, but the present invention is not limited thereto.
In the following examples, NMR and gas chromatography (hereinafter referred to as GC) were used to identify the produced compounds.
In the analysis by GC, a DB-1301 capillary column (60 m × 0.25 mmΦ manufactured by J & W) was used as an analysis column, and helium gas was used as a mobile phase. The mobile phase flow rate was 6.1 mL / min, the column temperature was 40 to 200 ° C. (temperature increase rate 10 ° C./min), and FID was used as the detector.

The number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography (hereinafter referred to as GPC) HLC-8220 GPC manufactured by Tosoh Corporation.
In the measurement by GPC, CF ₂ ClCF ₂ CHClF (hereinafter referred to as R-225) (manufactured by Asahi Glass Co., Ltd., trade name: Asahi Clin AK-225 SEC grade 1) and tetrahydrofuran (THF) (volume ratio 60:40). ) Using a mixed solvent as a mobile phase, two PLgel MIXED-C columns (manufactured by Polymer Laboratories) were connected in series to form an analytical column. As a standard sample for molecular weight measurement, molecular weight dispersion (weight average molecular weight / number average molecular weight) manufactured by Polymer Laboratories is less than 1.20, and number average molecular weights are 1944000, 790000, 281700, 144000, 79250, 28900, 13300, Ten types of polymethyl methacrylate of 5720, 1960, 1020 were used. The mobile phase flow rate was 1.0 mL / min, the column temperature was 37 ° C., and an ultraviolet absorption detector was used as the detector.

Example 1 Production Example of Compound (1a) and Compound (1b) (2-trifluoromethyl-2,3,3-trifluoro-7-oxabicyclo [2,2,1] hept-5-ene)

In a 100 mL stainless steel autoclave containing a magnetic stirrer, 30 g (0.54 mol) of the compound (3a) (furan, manufactured by Kanto Chemical Co., Inc.) was placed and capped. The autoclave was connected to a vacuum pump, cooled with liquid nitrogen until the compound (3a) in the container was frozen, and then the autoclave was vacuum degassed. Thereafter, the temperature of the autoclave was raised in a water bath. This cooling, deaeration, and temperature raising operations were repeated twice more, and after the inside of the autoclave was completely deaerated, it was connected to the cylinder of the compound (4a) (propylene hexafluoride, manufactured by Asahi Glass Co., Ltd.) Was charged with 85 g (0.57 mol) of the compound (4a). Next, the autoclave was placed in an oil bath at 180 ° C. and reacted for 80 hours while stirring with a stirrer. After completion of the reaction, the autoclave was cooled, the residual pressure was purged, and the lid was opened.
The reaction solution is taken out, diluted with R-225 (manufactured by Asahi Glass Co., Ltd.) until the mass is doubled, poured into a separatory funnel, a saturated aqueous sodium hydrogen carbonate solution is added, and ion-exchanged water is added twice. Washed twice. Magnesium sulfate powder was added to the organic layer for dehydration, followed by concentration with an evaporator to obtain a crude product. The crude product was distilled under reduced pressure to give a colorless solution (51.0 g).
As a result of analyzing the fraction by NMR and GC, it was confirmed that a mixture of the compound (1a) and the compound (1b) (purity 98.6%, yield 50.7%) was formed. The ratio of compound (1a) (exo type) to compound (1b) (endo type) in the mixture was 33:67.

The NMR spectrum of the mixture of compound (1a) and compound (1b) is as follows.
¹ H-NMR (399.8 MHz, solvent: CDCl ₃ ) δ (ppm): 4.88 to 4.98 (m, exo-1H + endo-1H), 5.01 to 5.10 (m, exo-1H) 5.17 (s, endo-1H), 6.54 to 6.59 (m, exo-1H), 6.62 to 6.72 (m, endo-1H + exo-1H).
¹⁹ F-NMR (376.2 MHz, solvent: CDCl ₃ standard: CF ₂ ClCFCl ₂ ) δ (ppm): −73.4 (dd, J = 11.5, 8.6 Hz, endo-3F), −76. 3 (dd, J = 11.5, 8.6, exo-3F), -107.8 (d, J = 236.2 Hz, endo-1F), -109.3 (dd, J = 236.1, 8.7 Hz, exo-1F), -115.7 (dd, J = 236.1, 14.4 Hz, exo-1F), -117.7 (d, J = 236.1, 14.4 Hz, endo- 1F), -170.8 (s, endo-1F), -176.7 (s, exo-1F).

ただし、式中のｎは正の整数である。 Example 2 Production Example 1 of Compound (2a) (Poly (2-trifluoromethyl-2,3,3-trifluoro-7-oxabicyclo [2,2,1] hept-5-ene))-1

However, n in a formula is a positive integer.

2.96 g of the mixture of the compound (1a) and the compound (1b) obtained in Example 1 was put into a 50 mL Schlenk tube containing a magnetic stir bar connected to an argon gas line while flowing argon gas. Furthermore, 31.3 g of R-225 (manufactured by Asahi Glass Co., Ltd.) is put using a syringe, and finally 2.1 mg of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (manufactured by Kanto Chemical Co., Inc.) is put. And put the lid on. The Schlenk tube was set on a stirrer and stirred at room temperature for 24 hours. After completion of the reaction, 1.0 g of ethyl vinyl ether (manufactured by Kanto Chemical Co., Inc.) was added to the reaction solution, and the mixture was further stirred for 10 minutes.
When 200 mL of n-hexane (manufactured by Kanto Chemical Co., Inc.) was placed in a 500 mL plastic container and the reaction solution was slowly added with vigorous stirring, a rubbery white polymer was precipitated. The precipitate was taken out by suction filtration and then dried in a vacuum dryer at 25 ° C. for 5 hours to obtain 2.21 g (yield 75%) of compound (2a). When the GPC analysis of this compound (2a) was conducted, the number average molecular weight of polyacryl conversion was 419,000 and the molecular weight dispersion (weight average molecular weight / number average molecular weight) was 1.79.

The NMR spectrum of the compound (2a) is as follows.
¹ H-NMR (399.78 MHz, solvent: CDCl ₃ / CF ₂ ClCFCl ₂ ) δ (ppm): 4.50 to 5.27 (2H), 5.87 to 6.21 (2H).

Example 3 Production Example 2 of Compound (2a)

3.51 g of the mixture of the compound (1a) and the compound (1b) obtained in Example 1 was put into a 50 mL Schlenk tube containing a magnetic stir bar connected to an argon gas line while flowing argon gas. Furthermore, 22.0 g of benzotrifluoride (manufactured by Kanto Chemical Co., Inc.) and 4.4 mg of 1-hexene were added using a syringe. Finally, 10.2 mg of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (manufactured by Kanto Chemical Co., Inc.) was added and the lid was covered. The Schlenk tube was set on a stirrer and stirred at 60 ° C. for 8 hours. After completion of the reaction, 1.0 g of ethyl vinyl ether (manufactured by Kanto Chemical Co., Inc.) was added to the reaction solution, and the mixture was further stirred for 10 minutes.
When 300 mL of n-hexane (manufactured by Kanto Chemical Co., Inc.) was placed in a 500 mL plastic container and the reaction solution was slowly added with vigorous stirring, a rubbery white polymer was precipitated. The precipitate was taken out by suction filtration and then dried in a vacuum dryer at 25 ° C. for 5 hours to obtain 1.51 g (yield 43%) of compound (2a). When the GPC analysis of this compound (2a) was conducted, the number average molecular weight of polyacryl conversion was 83,900, and molecular weight dispersion (weight average molecular weight / number average molecular weight) was 1.66.

The polymer of the fluorine-containing norbornenyl ester compound of the present invention can be applied to various uses such as electric / electronic materials, semiconductor materials, optical materials, optical fibers, and optical waveguide materials after necessary treatment.

Claims (6)

A monomer for fluorine-containing polymerization represented by the following formula (1).

In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and Rf ¹ , Rf ² , Rf ³ and Rf ⁴ are each independently a fluorine atom, or one or more ethers at any place It is a C1-C20 polyfluoroalkyl group which may contain a reactive oxygen atom. Rf ^1, of ^Rf 2, Rf ³ and Rf ^4, any one is trifluoromethyl group, a fluorine-containing monomer for polymerization according to claim 1 other is a fluorine atom.   A fluorine-containing polymer comprising a constitutional unit based on the monomer for fluorine-containing polymerization according to claim 1 or 2.   The fluorine-containing polymer according to claim 3, obtained by ring-opening metathesis polymerization. A fluorine-containing polymer represented by the following formula (2), obtained by ring-opening metathesis polymerization of the fluorine-containing polymerization monomer according to claim 1 or 2.

^{However, R 1, R 2, Rf} 1, Rf 2, Rf 3 and Rf ⁴ in the formula (2) is as defined above, n is a positive integer. 6. The fluorine-containing polymer according to claim 3, wherein the number average molecular weight is 1,000 to 500,000 in terms of polymethyl methacrylate.