JP2005248081A - Polymer having fluorine-containing alicyclic structure, its manufacturing process and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer having a fluorine-containing alicyclic structure excellent in transparency and heat resistance, has a low birefringence, and exhibits an excellent and lasting light resistance (weatherability); its manufacturing intermediate; their manufacturing process; and a molding molded from the polymer having the fluorine-containing alicyclic structure. <P>SOLUTION: A polymer (1) having a fluorine-containing alicyclic structure which contains 1-100 mole% repeating unit expressed by formula (1-1), based on the total repeating units, is obtained by the ring opening polymerization of a fluorine-containing cycloolefin compound (II). A polymer (2) having the fluorine-containing alicyclic structure which contains repeating units expressed by formula (1-2) is yielded by hydrogenating or fluorinating the polymer (1). A molding is obtained by molding a resin composition containing at least one kind of the polymer (1) and the polymer (2). In the formulas, A is represented by the formula: -C(R<SP>1</SP>)(R<SP>2</SP>)-(wherein R<SP>1</SP>and R<SP>2</SP>are each a hydrogen atom or a fluorine atom) and R<SP>3</SP>is a hydrogen atom or a fluorine atom. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fluorine-containing alicyclic structure-containing polymer having particularly excellent durability, a production intermediate thereof, a production method thereof, and a molded body formed by molding the fluorine-containing alicyclic structure-containing polymer.

  In recent years, alicyclic structure-containing polymers such as thermoplastic saturated norbornene resins have attracted attention as optical materials having excellent transparency, heat resistance, moisture resistance, low birefringence and the like. However, this alicyclic structure-containing polymer has a problem that it is inferior in light resistance or weather resistance.

  In order to solve this problem, Patent Document 1 proposes a technique for improving light resistance by adding a fluorophosphonite antioxidant to an alicyclic structure-containing polymer. However, according to this technique, although the light resistance of the resin molded body can be improved, the compatibility between the fluorophosphonite antioxidant to be added and the alicyclic structure-containing polymer is poor, and over time. The physical properties changed, and it was difficult to develop good physical properties over a long period of time.

  In Patent Documents 2 to 6, attempts have been made to improve the durability of the alicyclic structure-containing polymer by introducing fluorine atoms into the molecular skeleton of the alicyclic structure-containing polymer. According to the methods described in these documents, it is possible to introduce fluorine atoms having excellent durability into the alicyclic structure-containing polymer. However, the alicyclic structure-containing polymers described in these documents cannot be said to have sufficient light resistance even after the introduction of fluorine atoms.

  Therefore, the alicyclic structure-containing polymer that is excellent in transparency, heat resistance, moisture resistance, low birefringence, etc. and useful as an optical material has excellent light resistance (weather resistance) for a long time There was a need to develop polymers.

JP-A-6-80864 JP-A-6-199997 JP-A-6-206985 JP-A-8-256477 JP 2001-226467 A JP 2001-226468 A

  The present invention has been made in view of the situation of such prior art, and is an alicyclic structure-containing polymer that is excellent in transparency, heat resistance, moisture resistance, low birefringence, etc., and useful as an optical material. Provided are a novel fluorine-containing alicyclic structure-containing polymer having excellent light resistance (weather resistance) over a long period of time, a method for producing the same, and a molded product obtained by molding the fluorine-containing alicyclic structure-containing polymer. This is the issue.

As a result of intensive studies to solve the above problems, the present inventors have made a fluorine-containing alicyclic ring obtained by ring-opening polymerization of a fluorine-containing cyclic olefin compound obtained by reacting a specific fluorinated cyclic compound with cyclopentadiene. The structure-containing polymer (1) and the fluorinated alicyclic structure-containing polymer (2) obtained by hydrogenating or fluorinating this polymer are transparent, heat resistant, moisture resistant and low birefringent. It has been found that it has excellent light resistance over a long period of time, and the present invention has been completed.
Thus, according to the first aspect of the present invention, a compound of formula (I-1)

〔式中、Ａは、式：−Ｃ（Ｒ^１）（Ｒ^２）−（式中、Ｒ^１、Ｒ^２はそれぞれ独立して、水素原子又はフッ素原子を表す。）で表される基を表し、ｎは１〜６の整数を表す。〕で示される繰り返し単位を、全繰り返し単位に対して１〜１００モル％有することを特徴とする含フッ素脂環式構造含有重合体（１）が提供される。
本発明の含フッ素脂環式構造含有重合体（１）においては、フッ素含有量が、１０重量％以上であることが好ましい。
本発明の第２によれば、分子内に、式（Ｉ−２）

[Wherein, A represents a group represented by the formula: —C (R ¹ ) (R ² ) — (wherein R ¹ and R ² each independently represents a hydrogen atom or a fluorine atom). N represents an integer of 1-6. The fluorine-containing alicyclic structure containing polymer (1) characterized by having 1 to 100 mol% of the repeating units represented by the general repeating units is provided.
In the fluorine-containing alicyclic structure-containing polymer (1) of the present invention, the fluorine content is preferably 10% by weight or more.
According to a second of the present invention, the compound of formula (I-2)

(In the formula, A and n represent the same meaning as described above, and R ³ represents a hydrogen atom or a fluorine atom). A formula structure-containing polymer (2) is provided.
In the fluorine-containing alicyclic structure-containing polymer (2) of the present invention, the fluorine content is preferably 10% by weight or more.
According to a third of the present invention, the compound of formula (II)

(Wherein, A and n represent the same meaning as described above) of the fluorinated alicyclic structure-containing polymer (1) of the present invention, wherein the fluorinated cyclic olefin compound represented by the formula (1) is subjected to ring-opening polymerization. A manufacturing method is provided.

According to the fourth aspect of the present invention, the fluorinated alicyclic structure-containing polymer (2) of the present invention (2), wherein the fluorinated alicyclic structure polymer (1) of the present invention is hydrogenated or fluorinated. ) Is provided.
According to a fifth aspect of the present invention, the compound of formula (II)

(Wherein, A and n represent the same meaning as described above).
According to a sixth aspect of the present invention, the formula (III)

(Wherein A and n represent the same meaning as described above) and a cyclopentadiene represented by the formula (II)

(Wherein, A and n represent the same meaning as described above).
According to the seventh aspect of the present invention, there is provided a molded body obtained by molding a resin composition containing at least one of the fluorine-containing alicyclic structure-containing polymer (1) or (2) of the present invention.

The fluorine-containing alicyclic structure-containing polymers (1) and (2) of the present invention are those in which the most unstable tertiary carbon atom present in the molecule is protected with a fluorine atom, and are excellent for a long period of time. It has light resistance (weather resistance). Further, the fluorine-containing alicyclic structure-containing polymers (1) and (2) of the present invention are useful as optical materials because they are excellent in transparency, heat resistance, moisture resistance, low birefringence and the like.
According to the method for producing a fluorinated alicyclic structure-containing polymer of the present invention, the fluorinated alicyclic structure-containing polymer of the present invention can be efficiently produced.
The fluorine-containing cyclic olefin compound of the present invention is a novel compound and is useful as a raw material for producing the fluorine-containing alicyclic structure-containing polymer resin of the present invention.
Since the molded article of the present invention is obtained by molding a resin composition containing the fluorinated alicyclic structure-containing polymer resin of the present invention, transparency, heat resistance, moisture resistance, low birefringence, etc. It has excellent light resistance (weather resistance) over a long period of time and is useful as an optical material.

Hereinafter, the present invention will be described in detail.
1) Fluorine-containing alicyclic structure-containing polymer (1)
The fluorine-containing alicyclic structure-containing polymer (1) of the present invention has 1 to 100 mol% of repeating units represented by the formula (I-1) in the molecule with respect to all repeating units. And
In the formula (I-1), A represents a group represented by the formula: —C (R ¹ ) (R ² ) —. Here, R ¹ and R ² each independently represent a hydrogen atom or a fluorine atom.
N represents an integer of 1 to 6.

  The fluorine-containing alicyclic structure-containing polymer (1) of the present invention may be a homopolymer consisting only of the repeating unit represented by the formula (I-1), but in the formula (I-1) In addition to the repeating units shown, it may be a copolymer having other repeating units.

  Examples of the other repeating unit include a repeating unit derived from a norbornene monomer and a repeating unit of a monocyclic olefin monomer.

As the norbornene-based monomer, bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: Dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene (common name: tetracyclododecene) and the like. These norbornene monomers may have a substituent in the ring. Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, and an alkoxycarbonyl group.

Examples of monocyclic olefin monomers include cyclic monoolefins or cyclic diolefins having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms.
Examples of the cyclic monoolefin include those described in JP-A No. 64-66216. Specific examples include cycloolefins such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene.
As cyclic diolefin, what is described in Unexamined-Japanese-Patent No. 7-258318 etc. is mentioned, for example. Specific examples include cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, phenylcyclooctadiene, and the like.

  In the present invention, these norbornene monomers and monocyclic olefin monomers can be used singly or in combination of two or more.

  When the fluorine-containing alicyclic structure-containing polymer (1) of the present invention is a copolymer containing the repeating unit represented by the formula (I-1) and the other repeating units described above, this copolymer May be a random copolymer or a block copolymer. In the case of a block copolymer, examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers.

  In the fluorine-containing alicyclic structure-containing polymer (1), the fluorine content is preferably 10% by weight or more, and preferably 30% by weight or more in order to have excellent light resistance (weather resistance) over a long period of time. Is more preferable, and 40% by weight or more is particularly preferable. The fluorine content in the polymer (1) can be measured by a known method. Examples thereof include a potassium carbonate capsule decomposition method, a pyrohydration combustion method, and an ion chromatography method.

  The molecular weight of the fluorine-containing alicyclic structure-containing polymer (1) is appropriately selected according to the purpose of use, but gel permeation chromatography of tetrahydrofuran solution (toluene solution when the polymer resin does not dissolve). When the polyisoprene or polystyrene-equivalent weight average molecular weight measured in (1) is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000. The mechanical strength and molding processability of the molded body are highly balanced and suitable.

  The glass transition temperature (Tg) of the fluorinated alicyclic structure-containing polymer (1) may be appropriately selected depending on the intended use, but is usually 80 ° C. or higher, preferably 100 to 250 ° C., more preferably. Is in the range of 120-200 ° C. Within this range, heat resistance and moldability are highly balanced and suitable.

2) Fluorinated cyclic olefin compound The fluorinated cyclic olefin compound represented by the formula (II) can be obtained by subjecting the fluorinated cyclic olefin compound represented by the formula (III) and cyclopentadiene to Diels-Alder reaction. it can.
In the formula (III), A and n have the same meaning as described above.
Specific examples of the compound represented by the formula (III) include tetrafluorocyclopropene, hexafluorocyclobutene, 1,2,3,4,5-pentafluorocyclopentene, 1,2,3,3,4,5. -Hexafluorocyclopentene, 1,2,3,3,4,4,5-heptafluorocyclopentene, 1,2,3,3,4,5,5-heptafluorocyclopentene, octafluorocyclopentene, decafluorocyclohexene, etc. Can be mentioned. The compound (II) can be identified by measuring a ¹ H-NMR spectrum. That is, it can be confirmed that the compound (II) was obtained by not observing a peak near 2.6 ppm in the ¹ H-NMR spectrum.

3) Method for producing fluorine-containing cyclic olefin compound The fluorine-containing cyclic olefin compound represented by the formula (II) is a mixture of the fluorinated cyclic olefin compound represented by the formula (III) and cyclopentadiene at a predetermined ratio, and heated. It can be produced by stirring. Since the fluorinated cyclic olefin compound and cyclopentadiene represented by the formula (III) are substances having a low boiling point, the reaction is preferably performed using a sealable reactor such as an autoclave.

  The mixing ratio of the fluorinated cyclic olefin compound represented by the formula (III) and cyclopentadiene is (molar ratio) (fluorinated cyclic olefin compound represented by the formula (III)) :( cyclopentadiene) = 1: 10. The range is 10: 1, preferably 1: 1 to 10: 1, more preferably 1: 1 to 5: 1.

Although reaction temperature is based also on the kind of fluorinated cyclic olefin compound, it is 50-350 degreeC normally, Preferably it is 100-300 degreeC, More preferably, it is 150-260 degreeC.
Although the reaction time depends on the type of fluorinated cyclic olefin compound and the reaction scale, it is usually several minutes to several tens of hours.

4) Method for producing fluorinated alicyclic structure-containing polymer (1) The method for producing the fluorinated alicyclic structure-containing polymer (1) of the present invention comprises a fluorinated cyclic olefin compound represented by the formula (II). Is characterized by ring-opening polymerization.

  The fluorine-containing alicyclic structure-containing polymer (1) of the present invention includes the fluorine-containing cyclic olefin compound represented by the formula (II), and, if desired, the norbornene-based monomer, the monocyclic olefin-based monomer, etc. These may be collectively referred to as “other monomers”) and subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst.

  The metathesis catalyst used is a metathesis capable of ring-opening polymerization of the fluorine-containing cyclic olefin compound represented by the formula (II) or a mixture of the fluorine-containing cyclic olefin compound represented by the formula (II) and another monomer. If it is a catalyst, it will not specifically limit.

The metathesis catalyst is a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom.
As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long period periodic table, the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include ruthenium and osmium. Can be mentioned.

  Metathesis catalysts having tungsten or molybdenum of group 6 as the central metal include metal halides such as tungsten hexachloride; metal oxyhalides such as tungsten chloroxide; metal oxides such as tungsten oxide; and tridodecyl ammonium molybdate And organic metal acid ammonium salts such as tri (tridecyl) ammonium molybdate can be used. In these, the organic molybdate ammonium salt is preferable. When these metathesis catalysts are used, it is preferable to use an organoaluminum compound or an organotin compound as an activator (cocatalyst) for the purpose of controlling the polymerization activity.

  Moreover, it is also preferable to use a metal carbene complex having a metal atom of Group 5, 6, or 8 as a central metal as a metathesis catalyst to be used. Among metal carbene complexes, group 8 ruthenium or osmium carbene complexes are preferred, and ruthenium carbene complexes are particularly preferred because of their excellent productivity. Specific examples of the ruthenium carbene complex include those disclosed in WO97 / 06185, JP-T-10-508891, JP-A-11-322953, and the like.

  In the polymerization reaction, a molecular weight modifier can be added to the reaction system in order to adjust the molecular weight of the polymer. Examples of molecular weight regulators include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; halogen-containing vinyl compounds such as allyl chloride; ethyl vinyl ether and isobutyl vinyl ether Oxygen-containing vinyl compounds such as allyl glycidyl ether, allyl acetate, allyl alcohol and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. The usage-amount of a molecular weight modifier is 0.1-100 mol% normally with respect to the fluorine-containing cyclic olefin compound shown by said Formula (II).

  The ring-opening polymerization of the fluorine-containing cyclic olefin compound can be preferably carried out in an inert gas such as nitrogen gas or argon gas, in the presence of a metathesis polymerization catalyst, in a solvent or without a solvent. When the hydrogenation or fluorination reaction is performed as it is without isolating the produced polymer after completion of the polymerization reaction, the polymerization is preferably carried out in a solvent.

  The solvent to be used is not particularly limited as long as it dissolves the produced polymer and does not inhibit the polymerization reaction. For example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane , Alicyclic hydrocarbons such as hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile; diethyl Ethers such as ether, tetrahydrofuran and dioxane; ketones such as acetone, ethyl methyl ketone, cyclopentanone and cyclohexanone; methyl acetate, ethyl acetate and propio Acid ethyl esters of benzoic acid, and the like; chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as chlorobenzene; and the like. Among these, the use of aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters is preferable.

  The concentration of the fluorine-containing cyclic olefin compound when using the solvent is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and still more preferably 5 to 40% by weight. If the concentration of the fluorine-containing cyclic olefin compound is less than 1% by weight, the productivity of the polymer may be deteriorated. If it exceeds 50% by weight, the viscosity after polymerization is too high, and subsequent hydrogenation becomes difficult. There is.

  The metathesis polymerization catalyst may be dissolved in a solvent to prepare a catalyst solution, which may be added to the reaction system, or may be added as it is without being dissolved. Examples of the solvent for preparing the catalyst solution include the same solvents as those used in the polymerization reaction.

  The polymerization temperature is not particularly limited, but is usually −100 ° C. to + 200 ° C., preferably −50 ° C. to + 180 ° C., more preferably −30 ° C. to + 160 ° C., and further preferably 0 ° C. to + 140 ° C. The polymerization time is usually from 1 minute to 100 hours, and can be appropriately adjusted according to the progress of the reaction.

  After completion of the polymerization reaction, the intended fluorine-containing alicyclic structure-containing polymer (1) can be isolated by performing a normal post-treatment operation. Examples of the post-treatment operation include solidification drying and heat drying.

5) Fluorine-containing alicyclic structure-containing polymer (2)
The fluorine-containing alicyclic structure-containing polymer (2) of the present invention has 1 to 100 mol% of repeating units represented by the formula (I-2) in the molecule with respect to all repeating units. And In the formula (I-2), R ³ represents a hydrogen atom or a fluorine atom.

  The fluorine-containing alicyclic structure-containing polymer (2) of the present invention has 1 to 100 mol% of repeating units represented by the following formula (I-2-1) in the molecule with respect to all repeating units. (Hereinafter referred to as “fluorinated alicyclic structure-containing polymer (2-1)”) or the repeating unit represented by the following formula (I-2-2) It is preferable that it is 1-100 mol% (hereinafter referred to as “fluorinated alicyclic structure-containing polymer (2-2)”).

本発明の含フッ素脂環式構造含有重合体（２）においては、フッ素含有量が、１０重量％以上であることが好ましく、３０重量％以上であるのがより好ましく、４０重量％以上であるのが特に好ましい。フッ素含有量を前記範囲とすることにより、長期間にわたって優れた耐光性（耐候性）を有する含フッ素脂環式構造含有重合体（２）が得られる。

In the fluorine-containing alicyclic structure-containing polymer (2) of the present invention, the fluorine content is preferably 10% by weight or more, more preferably 30% by weight or more, and 40% by weight or more. Is particularly preferred. By setting the fluorine content in the above range, a fluorine-containing alicyclic structure-containing polymer (2) having excellent light resistance (weather resistance) over a long period of time can be obtained.

  The molecular weight of the fluorine-containing alicyclic structure-containing polymer (2) of the present invention is appropriately selected depending on the purpose of use, but gel permeation of tetrahydrofuran solution (toluene solution when the polymer resin does not dissolve). When the polyisoprene or polystyrene-equivalent weight average molecular weight measured by chromatography is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000. In addition, the mechanical strength and molding processability of the molded body are highly balanced and suitable.

  The glass transition temperature (Tg) of the fluorinated alicyclic structure-containing polymer (2) of the present invention may be appropriately selected according to the purpose of use, but is usually 80 ° C. or higher, preferably 100 to 250 ° C. More preferably, it is the range of 120-200 degreeC. Within this range, heat resistance and moldability are highly balanced and suitable.

6) Production method of fluorinated alicyclic structure-containing polymer (2) The fluorinated alicyclic structure-containing polymer (2) of the present invention is the fluorinated alicyclic structure-containing polymer (1) of the present invention. It can be produced by hydrogenation or fluorination. That is, the said fluorine-containing alicyclic structure containing polymer (2-1) can be obtained by hydrogenating the fluorine-containing alicyclic structure containing polymer (1) of this invention. Moreover, the said fluorine-containing alicyclic structure containing polymer (2-2) can be obtained by fluorinating the fluorine-containing alicyclic structure containing polymer (1) of this invention.

(Hydrogenation)
The hydrogenation reaction of the fluorinated alicyclic structure-containing polymer (1) is carried out by using hydrogen gas in the presence of a hydrogenation catalyst, and carbon in the main chain of the fluorinated alicyclic structure-containing polymer (1). This can be done by converting a carbon double bond to a saturated single bond.

  The hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenation of olefin compounds can be used as appropriate.

  Examples of homogeneous catalysts include transitions such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium, etc. Ziegler catalyst comprising a combination of a metal compound and an alkali metal compound; ruthenium carbene complex catalyst, dichlorotris (triphenylphosphine) rhodium described in the above section of ring-opening metathesis polymerization catalyst, JP-A-7-2929, JP-A-7 -149823, JP-A-11-109460, JP-A-11-158256, JP-A-11-193323, JP-A-11-109460, etc. Noble metal complex catalyst consisting ruthenium compound; and the like.

  Examples of the heterogeneous catalyst include a hydrogenation catalyst in which a metal such as nickel, palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. More specifically, for example, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more.

  Among these, the carbon-carbon double bond in the polymer can be selectively hydrogenated without causing side reactions such as modification of the functional group contained in the fluorinated alicyclic structure-containing polymer (1). From the viewpoint, use of a noble metal complex catalyst such as rhodium or ruthenium and a palladium-supported catalyst such as palladium / carbon is preferable, and use of a ruthenium carbene complex catalyst or a palladium-supported catalyst is more preferable.

  The hydrogenation reaction is usually performed in an organic solvent. As an organic solvent, it can select suitably by the solubility of the hydride to produce | generate, The organic solvent similar to the said polymerization solvent can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added to the reaction solution or the filtrate obtained by filtering the metathesis polymerization catalyst from the reaction solution without changing the solvent to cause the hydrogenation reaction.

  The conditions for the hydrogenation reaction may be appropriately selected according to the type of hydrogenation catalyst used. The amount of the hydrogenation catalyst used is usually 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0 to 100 parts by weight of the fluorinated alicyclic structure-containing polymer (1). .1 to 10 parts by weight. The reaction temperature is usually −10 ° C. to + 250 ° C., preferably −10 ° C. to + 210 ° C., more preferably 0 ° C. to + 200 ° C. If it is less than -10 degreeC, reaction rate will become slow, and conversely when it exceeds 250 degreeC, a side reaction will occur easily. The pressure of hydrogen is usually 0.01 to 10 MPa, preferably 0.05 to 8 MPa, more preferably 0.1 to 5 MPa. When the hydrogen pressure is less than 0.01 MPa, the hydrogenation rate is slow, and when it exceeds 10 MPa, a high pressure reactor is required.

  The time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50% or more, preferably 70% or more, more preferably 80% or more, most preferably, of the carbon-carbon double bonds of the main chain in the polymer. Can hydrogenate more than 90%.

Examples of the method for separating and removing the used hydrogenation catalyst include the following methods.
When a homogeneous catalyst is used, an oxidizing agent or a basic compound and a poor solvent such as water or methanol are added to the reaction solution after polymerization to convert the homogeneous catalyst into a metal oxide or metal salt. , Extraction of the metal oxide or metal salt into a poor solvent, separation and removal by filtration or centrifugation, separation by adsorption on an adsorbent, extraction of a homogeneous catalyst into an acidic aqueous solution such as hydrochloric acid For example, a method for separating and removing can be used.
When a supported hydrogenation catalyst is used, a method of easily separating and removing by centrifugation or filtration can be used.

  In the fluorine-containing alicyclic structure-containing polymer (2-1) of the present invention obtained as described above, the hydrogenated ratio of carbon-carbon double bonds (hydrogenation rate) is usually 50% or more. From the viewpoint of heat resistance, it is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.

The hydrogenation rate of the fluorinated alicyclic structure-containing polymer (2-1) is derived from, for example, a carbon-carbon double bond in the ¹ H-NMR spectrum of the fluorinated alicyclic structure-containing polymer (1). Comparing the peak intensity around 5.9 ppm with the peak intensity derived from the carbon-carbon double bond in the ¹ H-NMR spectrum of the fluorinated alicyclic structure-containing polymer (2-1), which is a hydride. It can ask for.

(Fluorination)
The fluorination reaction of the fluorinated alicyclic structure-containing polymer (1) can be carried out by allowing a fluorinating agent to act on the fluorinated alicyclic structure-containing polymer (1).
The fluorinating agent to be used is not particularly limited as long as it adds a fluorine atom to the carbon-carbon double bond in the main chain of the fluorinated alicyclic structure-containing polymer (1), but fluorine gas is used. This is preferable because the target product can be obtained with good yield and the handling is simple.

  Fluorine gas can be used as it is, but it is preferable to use a product diluted with an inert gas in consideration of obtaining the target product with good yield and handling safety. Examples of the inert gas used include nitrogen gas, argon gas, and helium gas.

  The mixing ratio of the fluorine gas and the inert gas is not particularly limited, but is usually a fluorine gas: inert gas weight ratio, usually (fluorine gas) :( inert gas) = 1: 100 to 100: 1, preferably 5 : 95 to 95: 5, more preferably 10:90 to 90:10.

The fluorination reaction of the fluorinated alicyclic structure-containing polymer (1) is usually performed by dissolving the fluorinated alicyclic structure-containing polymer (1) in a suitable inert solvent and adding a fluorinating agent to the solution. And stirring can be performed. When a fluorine gas or a mixed gas of a fluorinating agent and an inert gas is used as the fluorinating agent, the inert solvent solution of the fluorine-containing alicyclic structure-containing polymer (1) is stirred, A fluorination reaction can be performed by introducing a fluorine gas or a mixed gas of a fluorinating agent and an inert gas at a constant flow rate.
The usage-amount of a fluorinating agent is 1-100 times mole normally with respect to 1 mol of carbon-carbon double bonds of a fluorine-containing alicyclic structure containing polymer (1).

Examples of the solvent used for dissolving the fluorinated alicyclic structure-containing polymer (1) include the same solvents listed as solvents that can be used for the hydrogenation reaction.
The reaction temperature of the fluorination reaction of the fluorinated alicyclic structure-containing polymer (1) is usually −150 to + 50 ° C., preferably −100 to + 20 ° C. The reaction time is usually several minutes to several tens of hours.

  After completion of the fluorination reaction, the target fluorinated alicyclic structure-containing polymer (2-2) can be obtained by performing an ordinary post-treatment operation after washing the reaction solution with alkali. In the case where fluorine gas or a mixed gas of fluorine gas and inert gas is used as the fluorinating agent, the post-treatment operation is carried out by introducing an inert gas into the reaction solution, and unreacted fluorine from the reaction system. After removing the gas.

The fluorination rate of the fluorinated alicyclic structure-containing polymer (2-2) of the present invention obtained as described above is, for example, ¹ H-NMR spectrum of the fluorinated alicyclic structure-containing polymer (1). -CFH- hydrogen atom in the ¹ H-NMR spectrum of the fluorinated alicyclic structure-containing polymer (2-2), which is a fluorinated product, and a peak intensity around 5.9 ppm derived from the carbon-carbon double bond in Can be obtained by comparing peak intensities in the vicinity of 4.7 ppm.

  The fluorinated ratio of the carbon-carbon double bond (fluorination rate) of the fluorinated alicyclic structure-containing polymer (2-2) of the present invention obtained as described above is usually 50% or more. From the viewpoint of heat resistance, it is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

7) Molded product The molded product of the present invention is at least one of the fluorinated alicyclic structure-containing polymer (1) or (2) of the present invention (hereinafter simply referred to as "fluorinated alicyclic structure-containing polymer"). And a resin composition containing the resin is molded.
The fluorine-containing alicyclic structure-containing polymer of the present invention is a thermoplastic resin, and various molded products can be produced by a known thermoplastic resin molding method in the same manner as ordinary thermoplastic resins.

  The resin composition containing the fluorine-containing alicyclic structure-containing polymer can be prepared according to a conventional method. Specifically, a method of mechanically blending at least one of the fluorine-containing alicyclic structure-containing polymer (1) or (2) and, if necessary, other additives with an extruder, a kneader, a roll or the like. Each of these components is dissolved in a suitable good solvent, for example, tetrahydrofuran, hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, etc. A method of mixing and removing the solvent; a method of combining these methods; and the like.

The additives are added for the purpose of improving physical properties, imparting functions, improving molding workability, etc. according to various uses and purposes, such as fillers, modifiers, antifoaming agents, and foaming agents. , Colorants, ultraviolet absorbers, light stabilizers, antioxidants, flame retardants and the like are used.
The usage-amount of an additive is 0.001-500 weight part normally with respect to 100 weight part of said fluorine-containing alicyclic structure containing polymers.

  The molded article of the present invention is obtained by molding a resin composition containing the above-mentioned fluorine-containing alicyclic structure-containing polymer. The method for molding the resin composition containing the fluorine-containing alicyclic structure-containing polymer is not particularly limited. For example, a general thermoplastic resin molding method such as injection molding, melt extrusion, hot pressing, solvent casting, stretching, or the like can be used.

  The obtained molded article of the present invention is a fluorine-containing alicyclic structure-containing polymer having excellent transparency, heat resistance, moisture resistance, low birefringence, etc., and excellent light resistance (weather resistance) over a long period of time. Since it is obtained by molding, it is suitable as various optical materials. Examples of the optical material include an optical lens, an optical disk, an optical fiber, an optical sheet, and an optical film. In addition, the molded body of the present invention can be used in a wide range of fields such as electronic component materials, mechanical component materials, and medical equipment.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example. In the following Examples and Comparative Examples, “part” is based on mass unless otherwise specified.

The test method is as follows.
(1) Identification of synthetic monomer The purified synthetic reaction product is analyzed by ¹ H-NMR spectral analysis.
(2) Weight average molecular weight (Mw)
Measured by gel permeation chromatography (GPC), the solvent is determined in terms of polystyrene using tetrahydrofuran.
(3) Hydrogenation rate and fluorination rate
Obtained by ¹ H-NMR spectral analysis.
(4) Fluorine content Measured by ion chromatography.
(5) Glass transition temperature (Tg)
Using a differential scanning calorimeter, the temperature is measured at a rate of 10 ° C. per minute.

(6) Carbon arc lamp accelerated weathering test A fluororesin is dissolved in tetrahydrofuran to prepare a 20% solution, which is applied onto a glass plate using an applicator with a gap of 500 μm, and is allowed to stand at room temperature for 12 hours and then at 60 ° C. In an oven for 6 hours, and then the film is peeled off from the glass plate to produce a cast film.
The obtained cast film was subjected to a carbon arc lamp accelerated weather resistance test according to JIS K5400 9.8.1, the appearance of the cast film after 4000 hours was visually observed, and the haze was measured using a haze meter (NDH2000, Japan). Measured using Denshoku Industries Co., Ltd. The appearance is evaluated according to the following criteria.
(Double-circle): A crack is not seen at all.
○: A few cracks are seen.
X: Many large cracks are seen.
The appearance and haze of the cast film before the test are also measured.

(Example 1)
To an autoclave equipped with a stirrer and a thermometer, 96 parts of octafluorocyclopentene (trade name: Zeolora OFE, manufactured by Nippon Zeon Co., Ltd.) and 10 parts of dicyclopentadiene were added and reacted at 200 ° C. for 3 hours. After completion of the reaction, the inside of the autoclave was cooled and opened, and the obtained reaction product was poured into 200 parts of water to separate the organic layer and the aqueous layer. Thereafter, the organic layer is separated, and low-boiling substances are removed by an evaporator, followed by precision vacuum distillation under conditions of 70 ° C. and 21 mmHg (2.8 × 10 ³ Pa), whereby a colorless and transparent reaction product is obtained. 48 parts were obtained. The fluorine content of this reaction product was measured by ion chromatography and found to be 54.5%. When the structure of this product was confirmed by ¹ H-NMR measurement, the desired 2,3,3,4,4,5,5,6-octafluorotricyclo [5.2.1.0 ^2,6 ] Decene (hereinafter abbreviated as “OFTCD”). This reaction product was found to be a mixture of two isomers (isomer 1 and isomer 2), and the ¹ H-NMR peak of each isomer was as follows.

(Isomer 1)
¹ H-NMR (CDCl ₃ , δ ppm); 6.07 (s, 2H), 3.19 (m, 2H), 2.39-2.13 (dd, 2H)
In isomer 1, protons bonded to carbons at positions 8 and 9 corresponding to the double bond portion of OFCD at 6.07 ppm were bonded to carbons at positions 1 and 7 of OFCD at 3.19 ppm. Protons were observed from 2.39 to 2.13 ppm of protons derived from the methylene structure of OFCD.

(Isomer 2)
¹ H-NMR (CDCl ₃ , δ ppm); 6.42 (s, 2H), 3.34 (d, 2H), 1.83 to 1.65 (m, 2H)
In isomer 2, protons bonded to carbons at positions 8 and 9 corresponding to the double bond portion of OFCD at 6.42 ppm were bonded to carbons at positions 1 and 7 of OFCD at 3.34 ppm, respectively. A methine proton was observed at 1.83 to 1.65 ppm in protons derived from the methylene structure of OFCD.

(Example 2)
In a nitrogen atmosphere, dehydrated tetrahydrofuran (THF) 500 parts, 1-hexene 0.82 parts, dibutyl ether 0.15 parts and triisobutylaluminum 0.30 parts were put in a reactor and mixed at room temperature, then 80 ° C. While maintaining the temperature, 300 parts of OFCD obtained in Example 1 and 80 parts of tungsten hexachloride (0.7 wt% toluene solution) were continuously added over 10 hours for polymerization. To the obtained polymerization solution, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol are added to inactivate the polymerization catalyst, and the polymerization reaction is stopped to obtain a polymerization reaction liquid containing the OFTCD ring-opening polymer. It was.

Subsequently, the obtained polymerization reaction liquid was put into methanol, and the precipitate was collected by filtration. The filtrate was dried under reduced pressure to obtain 120 parts of the desired OFTCD ring-opening polymer (fluororesin 1).
The obtained fluororesin 1 had a weight average molecular weight (Mw) of 35,000, a fluorine content of 54.8%, and a glass transition temperature (Tg) of 190 ° C.

The ¹ H-NMR data of the fluororesin 1 was as follows.
¹ H-NMR (acetone-d6, δ ppm); 5.9 (2H), 3.3 (2H), 2.1 (2H)
The proton of the double bond part of the OFTCD ring-opening polymer at 5.9 ppm, the methine proton next to the double bond part of the OFTCD ring-opening polymer at 3.3 ppm, and the methylene structure of the OFTCD polymer at 2.1 ppm Each proton was observed.
A carbon arc lamp accelerated weather resistance test was performed using the obtained fluororesin. The results are shown in Table 1.

(Example 3)
In a nitrogen atmosphere, dehydrated THF (500 parts) was charged with 1-hexene (0.82 parts), dibutyl ether (0.15 parts) and triisobutylaluminum (0.30 parts), mixed at room temperature, and maintained at 80 ° C. Of OFTCD obtained in Step 1, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 40 parts of dodec-3-ene (hereinafter abbreviated as “ETCD”) and 80 parts of tungsten hexachloride (0.7 wt% toluene solution) were continuously added dropwise over 10 hours for polymerization. did. A reaction solution containing OFTCD-ETCD ring-opening copolymer by adding 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol to the obtained polymerization solution to inactivate the polymerization catalyst to stop the polymerization reaction. Got.

  Next, 270 parts of cyclohexane is added to 100 parts of the obtained reaction solution, and 5 parts of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added as a hydrogenation catalyst, and the pressure is increased to 6 MPa with hydrogen while stirring. By heating to 240 ° C. and reacting for 6 hours, a reaction liquid 2 containing a hydrogenated OFCD-ETCD ring-opening copolymer was obtained. The obtained reaction solution 2 was filtered to remove the hydrogenation catalyst, and then the filtrate was put into methanol, and the precipitate was collected by filtration. The filtrate was dried under reduced pressure to obtain 30 parts of the desired OFTCD-ETCD ring-opening copolymer hydride (fluororesin 2).

When ¹ H-NMR of the fluororesin 2 was measured, the peak derived from the hydrogen atom of the carbon-carbon double bond confirmed before hydrogenation was decreasing.
^When the hydrogenation rate of the fluororesin 2 was measured by ¹ H-NMR, the hydrogenation rate was 99.9%. Moreover, the obtained fluororesin 2 had a weight average molecular weight (Mw) of 33,000, a fluorine content of 46.2%, and a glass transition temperature (Tg) of 184 ° C.
A carbon arc lamp accelerated weather resistance test was performed using the obtained fluororesin. The results are shown in Table 1.

Example 4
The OFTCD-ETCD ring-opening copolymer 2 was produced in the same manner as in Example 3 except that the charged monomer in Example 2 was changed to 50 parts of OFCD and 170 parts of ETCD. Next, the ring-opening copolymer was hydrogenated by the same operation as in Example 3 to obtain 28 parts of an OFTCD-ETCD ring-opening copolymer hydride (fluororesin 3).
The obtained fluororesin 3 had a weight average molecular weight (Mw) of 36,000, a fluorine content of 11.2%, and a glass transition temperature (Tg) of 154 ° C.
A carbon arc lamp accelerated weather resistance test was performed using the obtained fluororesin. The results are shown in Table 1.

(Example 5)
To a four-necked flask equipped with a stirrer, a gas introduction tube, and a gas discharge tube, 2.50 parts of the OFTCD-ETCD ring-opening copolymer obtained in Example 4 and 800 parts of chloroform were added and completely dissolved at room temperature. . The solution was cooled to −40 ° C. while flowing nitrogen gas at 200 ml / min. Next, a mixed gas of nitrogen and fluorine (nitrogen / fluorine (weight ratio) = 90/10) was brought into contact with this solution at a flow rate of 20 ml / min so as to be 35.75 mmol in terms of fluorine gas. Thereafter, the mixture was stirred for 50 minutes, and nitrogen gas was circulated for 30 minutes at a flow rate of 200 ml / min. The reaction solution was returned to room temperature and washed twice with a saturated aqueous sodium carbonate solution. The resulting reaction solution was concentrated and poured into methanol, and the precipitate was collected by filtration. The filtrate was dried under reduced pressure to obtain 53 parts of the desired OFTCD-ETCD ring-opening copolymer fluorinated product (fluororesin 4).

When ¹ H-NMR of fluororesin 4 was measured, the peak derived from the hydrogen atom of the carbon-carbon double bond that was confirmed before fluorination decreased, and it was attributed to the hydrogen atom of —CHF— at 4.7 ppm. A new peak was observed. ^When the fluorination rate of the polymer was measured by ¹ H-NMR, the fluorination rate was 92%.
The obtained fluororesin 4 had a weight average molecular weight (Mw) of 35,000, a fluorine content of 13.5%, and a glass transition temperature (Tg) of 159 ° C.
A carbon arc lamp accelerated weather resistance test was performed using the obtained fluororesin. The results are shown in Table 1.

(Comparative Example 1)
To an autoclave equipped with a stirrer and a thermometer, 20 parts of hexafluoropropene and 17 parts of dicyclopentadiene were added and reacted at 180 ° C. for 6 hours. After completion of the reaction, the inside of the autoclave was cooled, the reaction mixture was poured into 200 parts of water, and separated into an organic layer and an aqueous layer. After separating the organic layer and removing low-boiling substances with an evaporator, 14 parts of a colorless and transparent reaction product was obtained by performing precision vacuum distillation at 70 ° C. and 21 mmHg (2.8 × 10 ³ Pa). Obtained.

The fluorine content of this reaction product was 40.5%. The structure of this product was confirmed by ¹ H-NMR measurement, and was found to be 8,9,9-trifluoro-8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter abbreviated as “FMTCD”).
The ¹ H-NMR peak of the obtained reaction product was as follows.
¹ H-NMR (CDCl ₃ , δ ppm); 6.1 (2H), 3.1 (2H), 2.6 (4H), 1.5 (4H)

  In this reaction product, protons bonded to carbons at positions 3 and 4 corresponding to the double bond portion of FMTCD at 6.1 ppm, and methine protons at positions 2 and 5 of FMTCD at 3.1 ppm, The methine protons at the 1st, 6th, 7th and 10th positions were observed at 2.6 ppm, and the proton derived from the methylene structure of FMTCD was observed at 1.5 ppm. In addition, since a peak of methine proton is observed at 2.6 ppm, there is a portion where a hydrogen atom is bonded to a tertiary carbon atom other than the tertiary carbon atom adjacent to the carbon-carbon double bond. It was confirmed.

  Next, 0.82 part of 1-hexene, 0.15 part of dibutyl ether and 0.30 part of triisobutylaluminum were put into a reactor in 500 parts of dehydrated THF under a nitrogen atmosphere, mixed at room temperature, and then heated to 80 ° C. While maintaining, 160 parts of ETCD, 60 parts of FMTCD and 80 parts of tungsten hexachloride (0.7 wt% toluene solution) were continuously dropped over 10 hours for polymerization. Polymerization containing FMTCD-ETCD ring-opening copolymer by adding 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol to inactivate the polymerization catalyst to stop the polymerization reaction. A reaction solution was obtained.

Next, 270 parts of cyclohexane is added to 100 parts of the obtained polymerization reaction solution, and 5 parts of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added as a hydrogenation catalyst, and the pressure is increased to 6 MPa with hydrogen while stirring. The reaction solution containing a hydrogenated FMTCD-ETCD ring-opening copolymer was obtained by heating to 200 ° C. and reacting for 6 hours. The obtained reaction solution was filtered to remove the hydrogenation catalyst, and then poured into an acetone / methanol mixed solution (50/50 weight ratio), and the precipitate was collected by filtration. The filtrate was dried under reduced pressure to obtain 25 parts of an intended FMTCD-ETCD ring-opening copolymer hydride (fluororesin 5).
The obtained fluororesin 5 had a weight average molecular weight (Mw) of 45,000, a fluorine content of 11.0%, and a glass transition temperature (Tg) of 154 ° C.
A carbon arc lamp accelerated weather resistance test was performed using the obtained fluororesin. The results are shown in Table 1.

(Comparative Example 2)
In a nitrogen atmosphere, dehydrated THF (500 parts) was charged with 1-hexene (0.82 parts), dibutyl ether (0.15 parts) and triisobutylaluminum (0.30 parts) and mixed at room temperature. 300 parts of the obtained FMTCD and 80 parts of tungsten hexachloride (0.7% by weight toluene solution) were continuously added over 10 hours for polymerization. To the obtained polymerization solution, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol were added to deactivate the polymerization catalyst, the polymerization reaction was stopped, and a polymer reaction solution containing an FMTCD ring-opening polymer was obtained. Obtained.

Next, 270 parts of cyclohexane is added to 100 parts of the obtained reaction solution, and 5 parts of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added as a hydrogenation catalyst. The reaction solution containing the hydride of FMTCD ring-opening polymer was obtained by heating to 0 ° C. and allowing the reaction to proceed for 6 hours. The resulting reaction solution was filtered to remove the hydrogenation catalyst, and then poured into methanol, and the precipitate was collected by filtration. The filtrate was dried under reduced pressure to obtain 27 parts of the target FMTCD ring-opening polymer hydride (fluororesin 6).
The obtained fluororesin 6 had a weight average molecular weight (Mw) of 40,000, a fluorine content of 40.1%, and a glass transition temperature (Tg) of 180 ° C.
A carbon arc lamp accelerated weather resistance test was performed using the obtained fluororesin. The results are shown in Table 1.

From Table 1, the fluororesins of Examples 2 and 3 (fluororesins 1 and 2) retain excellent transparency even after the accelerated weather resistance test, and do not cause cracks on the surface, and are excellent over a long period of time. It was shown to have excellent weather resistance (light). Since the fluororesins of Examples 4 and 5 (fluororesins 3 and 4) have a lower fluorine content than Examples 2 and 3, there are 2 slight cracks after the accelerated weathering test. Three places were seen. On the other hand, the fluororesin 5 of Comparative Example 1 was remarkably reduced in transparency and cracked on the surface after the accelerated weather resistance test. Moreover, although the fluororesin 6 of the comparative example 2 did not produce cracks on the surface after the accelerated weather resistance test, the transparency was remarkably lowered.

Claims (9)

In the molecule, formula (I-1)

[Wherein, A represents a group represented by the formula: —C (R ¹ ) (R ² ) — (wherein R ¹ and R ² each independently represents a hydrogen atom or a fluorine atom). N represents an integer of 1-6. ]
The fluorine-containing alicyclic structure containing polymer (1) characterized by having 1 to 100 mol% of repeating units represented by the formula (1).   The fluorine-containing alicyclic structure-containing polymer (1) according to claim 1, wherein the fluorine content is 10% by weight or more. In the molecule, formula (I-2)

[Wherein, A represents a group represented by the formula: —C (R ¹ ) (R ² ) — (wherein R ¹ and R ² each independently represents a hydrogen atom or a fluorine atom). N represents an integer of 1 to 6, and R ³ represents a hydrogen atom or a fluorine atom. ]
The fluorine-containing alicyclic structure containing polymer (2) characterized by having 1 to 100 mol% of repeating units represented by the formula (1).   The fluorine-containing alicyclic structure-containing polymer (2) according to claim 3, wherein the fluorine content is 10% by weight or more. Formula (II)

[Wherein, A represents a group represented by the formula: —C (R ¹ ) (R ² ) — (wherein R ¹ and R ² each independently represents a hydrogen atom or a fluorine atom). N represents an integer of 1-6. ]
The method for producing a fluorine-containing alicyclic structure-containing polymer (1) according to claim 1 or 2, wherein the fluorine-containing cyclic olefin compound represented by formula (1) is subjected to ring-opening polymerization.   The fluorine-containing alicyclic structure-containing polymer (1) according to claim 3 or 4, wherein the fluorine-containing alicyclic structure polymer (1) according to claim 1 or 2 is hydrogenated or fluorinated. 2) Production method. Formula (II)

[Wherein, A represents a group represented by the formula: —C (R ¹ ) (R ² ) — (wherein R ¹ and R ² each independently represents a hydrogen atom or a fluorine atom). N represents an integer of 1-6. ]
The fluorine-containing cyclic olefin compound shown by these. Formula (III)

[Wherein, A represents a group represented by the formula: —C (R ¹ ) (R ² ) — (wherein R ¹ and R ² each independently represents a hydrogen atom or a fluorine atom). N represents an integer of 1-6. ]
Wherein the fluorinated cyclic olefin compound represented by formula (II) is reacted with cyclopentadiene

[Wherein, A represents a group represented by the formula: —C (R ¹ ) (R ² ) — (wherein R ¹ and R ² each independently represents a hydrogen atom or a fluorine atom). N represents an integer of 1-6. ]
The manufacturing method of the fluorine-containing cyclic olefin compound shown by these. A resin composition comprising at least one of the fluorine-containing alicyclic structure-containing polymer (1) according to claim 1 or 2, or the fluorine-containing alicyclic structure-containing polymer (2) according to claim 3 or 4. A molded body formed by molding.