JP7036120B2 - Fluorine-containing compounds and fluoropolymers and methods for producing them - Google Patents

Description

The present invention relates to a fluorine-containing compound, a fluorine-containing polymer, and a method for producing the same. In particular, the present invention relates to a fluorinated norbornene derivative and a fluorinated polymer containing a structural unit derived from the fluorinated norbornene derivative and a method for producing the same.

Conventionally, a compound having a norbornene skeleton (hereinafter referred to as "norbornene derivative") is widely used as a monomer for ring-opening polymerization by a metal-catalyzed metathesis reaction to obtain a polymer. The polymer containing the structural unit based on this norbornene derivative and its hydrogen additive have an excellent balance of various properties such as high glass transition temperature (high heat resistance), low water absorption, and high light transmittance. It is used in a wide variety of fields such as electrical / electronic materials, semiconductor materials, and optical materials.

A polymer derived from a fluorine-containing norbornene derivative containing a fluorine atom in this norbornene derivative is expected to be superior in chemical durability, weather resistance, and light transmission to a polymer of a norbornene derivative containing no fluorine atom. (Patent Documents 1 to 3).

Japanese Patent No. 47523999 Japanese Patent Application Laid-Open No. 2004-107277 U.S. Patent Application Publication No. 2007-0191560

Analytica Chimica Acta (2004), 504 (1), 53-62 CHEMICAL REVIEWS (2015), 115, 871-930

Conventionally, it has been found that the reaction of an olefin derivative containing a fluorine atom is difficult to proceed, and a copolymer derived from a norbornene derivative containing no fluorine atom and a cyclopentene derivative having a substituent (Non-Patent Document 1) has been reported. .. However, there have been no reports of the production of a copolymer derived from a norbornene derivative containing a fluorine atom and a cyclopentene derivative having a substituent. Further, although a copolymer of a norbornene derivative containing a fluorine atom and cyclopentene (Non-Patent Document 2) has been reported, a copolymer derived from a norbornene derivative containing a fluorine atom and a cyclopentene derivative having a substituent is produced. There were no reports made.

Therefore, it is an object of the present invention to provide a novel fluorine-containing compound and a fluorine-containing polymer containing a norbornene derivative containing a fluorine atom and a structural unit derived from the norbornene derivative, and a method for producing the same.

The present invention relates to the following <1> to <15> as a configuration for achieving the above object.
<1> A fluorine-containing compound represented by the following general formula 1.

However, X ¹¹ and X ¹² are independently hydrogen atoms or fluorine atoms, R ¹¹ and R ¹² are independently monovalent organic groups, and a 11 and a 12 are independently 0, 1 or 2, respectively.
<2> A fluorine-containing compound represented by the following general formula 2.

However, X ²¹ and X ²² are independently hydrogen atoms or fluorine atoms, R ²¹ and R ²² are independently monovalent organic groups, and a 21 and a 22 are independently 1 or 2, respectively.
<3> A fluorine-containing compound represented by the following general formula 3.

However, Y ³¹ is independently CR ¹³¹ R ¹³² , O, S, NR ¹³³ or PR ¹³⁴ , and R ³¹ is a monovalent fluorine-containing organic group having 2 or more carbon atoms having an ethereal oxygen atom. , R ³² to R ³⁴ are independent hydrogen atoms or halogen atoms, R ¹³¹ to R ¹³⁴ are independent hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and j31 is 0 or 1. Is.
<4> A fluorine-containing polymer containing a structural unit represented by the following general formula 11 or a structural unit represented by the following general formula 12.

However, X ¹¹ and X ¹² are independently hydrogen atoms or fluorine atoms, R ¹¹ and R ¹² are independently monovalent organic groups, and a 11 and a 12 are independently 0, 1 or 2, respectively. m11 is a natural number representing the number of repetitions in the repeating unit.
<5> A fluorine-containing polymer containing a structural unit represented by the following general formula 21 or a structural unit represented by the following general formula 22.

However, X ²¹ and X ²² are independently hydrogen or fluorine atoms, R ²¹ and R ²² are independently monovalent organic groups, a21 and a22 are independently 1 or 2, and m21 is the number of repeating units. It is a natural number to represent.
<6> A fluorine-containing polymer containing a structural unit represented by the following general formula 31 or a structural unit represented by the following general formula 32.

However, Y ³¹ is independently CR ¹³¹ R ¹³² , O, S, NR ¹³³ or PR ¹³⁴ , and R ³¹ is a monovalent fluorine-containing organic group having 2 or more carbon atoms having an ethereal oxygen atom. , R ³² to R ³⁴ are independent hydrogen atoms or halogen atoms, R ¹³¹ to R ¹³⁴ are independent hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and j31 is 0 or 1. And m31 is a natural number representing the number of repetitions in the repetition unit.
<7> A fluorine-containing polymer containing a structural unit represented by the following general formula 11'.

However, X ¹¹ and X ¹² are independently hydrogen atoms or fluorine atoms, R ¹¹ and R ¹² are independently monovalent organic groups, and a 11 and a 12 are independently 0, 1 or 2, respectively. m11 is a natural number representing the number of repetitions in the repeating unit.
<8> A fluorine-containing polymer containing a structural unit represented by the following general formula 21'.

However, X ²¹ and X ²² are independently hydrogen atoms or fluorine atoms, R ²¹ and R ²² are independently monovalent organic groups, a21 and a22 are independently 1 or 2, and m21 is. It is a natural number that represents the number of repetitions in a repetition unit.
<9> A fluorine-containing polymer containing a structural unit represented by the following general formula 31'.

However, Y ³¹ is independently CR ¹³¹ R ¹³² , O, S, NR ¹³³ or PR ¹³⁴ , and R ³¹ is a monovalent fluorine-containing organic group having 2 or more carbon atoms having an ethereal oxygen atom. , R ³² to R ³⁴ are independent hydrogen atoms or halogen atoms, R ¹³¹ to R ¹³⁴ are independent hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and j31 is 0 or 1. And m31 is a natural number representing the number of repetitions in the repetition unit.
<10> A fluorine-containing polymer containing a structural unit represented by the following general formula I or a structural unit represented by the following general formula II.

However, the symbols in the above formula have the following meanings.
Y is independently CR ¹²¹ R ¹²² , O, S, NR ¹²³ or PR ¹²⁴ , respectively.
R ¹⁰¹ to R ¹⁰⁴ are organic groups that may independently have a hydrogen atom, a halogen atom, or a hetero atom, and R ¹⁰¹ or R ¹⁰² and R ¹⁰³ or R ¹⁰⁴ are bonded to form a ring. It may be formed, and at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ contains one or more hydrogen atoms.
R ¹⁰⁵ to R ¹¹⁰ are organic groups that may independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or a hetero atom, except that at least one group of R ¹⁰⁵ to R ¹¹⁰ is a halogen. An organic group that may have an atom, a hydroxyl group, an amino group or a heteroatom.
R ¹²¹ to R ¹²⁴ are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms.
j is 0 or 1 and
m and n are natural numbers representing the number of repetitions in the repeating unit, respectively.
<11> At least one group or atom of R ¹⁰¹ to R ¹⁰⁴ in the general formula I or the general formula II is a (pel) fluoroalkyl group having 1 to 20 carbon atoms and a (pel) having 1 to 20 carbon atoms. A fluoroalkoxy group, a (pel) fluoroalkyl group having 2 to 200 carbon atoms having an etheric oxygen atom between carbon atoms, and a carbon number of 2 to 200 including an etheric oxygen atom between carbon atoms. The fluorine-containing group according to the above <10>, which is a (pel) fluoroalkoxy group, a (pel) fluoroaryl group having 5 to 20 carbon atoms, a (pel) fluoroaryloxy group having 5 to 20 carbon atoms, or a fluorine atom. Polymer.
<12> A fluorine-containing polymer containing a structural unit represented by the following general formula I'.

However, the symbols in the above formula have the following meanings.
Y is independently CR ¹²¹ R ¹²² , O, S, NR ¹²³ or PR ¹²⁴ , respectively.
R ¹⁰¹ to R ¹⁰⁴ are organic groups that may independently have a hydrogen atom, a halogen atom, or a hetero atom, and R ¹⁰¹ or R ¹⁰² and R ¹⁰³ or R ¹⁰⁴ are bonded to form a ring. It may be formed, and at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ contains one or more hydrogen atoms.
R ¹⁰⁵ to R ¹¹⁰ are organic groups that may independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or a hetero atom, except that at least one group of R ¹⁰⁵ to R ¹¹⁰ is a halogen. An organic group that may have an atom, a hydroxyl group, an amino group or a heteroatom.
R ¹²¹ to R ¹²⁴ are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms.
j is 0 or 1 and
m and n are natural numbers representing the number of repetitions in the repeating unit, respectively.
<13> In the presence of a metal-carbene complex catalyst, a norbornene derivative containing a fluorine atom represented by the following general formula a is copolymerized with a cyclopentene derivative represented by the following general formula b, represented by the following general formula I. A method for producing a fluoropolymer containing a structural unit.

However, the symbols in the above formulas a, b and I have the following meanings.
Y is independently CR ¹²¹ R ¹²² , O, S, NR ¹²³ or PR ¹²⁴ , respectively.
R ¹⁰¹ to R ¹⁰⁴ are organic groups that may independently have a hydrogen atom, a halogen atom, or a hetero atom, and R ¹⁰¹ or R ¹⁰² and R ¹⁰³ or R ¹⁰⁴ are bonded to form a ring. It may be formed, and at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ contains one or more hydrogen atoms.
R ¹⁰⁵ to R ¹¹⁰ are organic groups that may independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or a hetero atom, except that at least one group of R ¹⁰⁵ to R ¹¹⁰ is a halogen. An organic group that may have an atom, a hydroxyl group, an amino group or a heteroatom.
R ¹²¹ to R ¹²⁴ are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms.
j is 0 or 1 and
m and n are natural numbers representing the number of repetitions in the repeating unit, respectively.
<14> A structural unit represented by the following general formula II, in which a norbornene derivative containing a fluorine atom represented by the following general formula a and a cyclopentene derivative represented by the following general formula b are copolymerized by an addition polymerization reaction. A method for producing a fluoropolymer containing a fluorinated polymer.

However, the symbols in the above formulas a, b and II have the following meanings.
Y is independently CR ¹²¹ R ¹²² , O, S, NR ¹²³ or PR ¹²⁴ , respectively.
R ¹⁰¹ to R ¹⁰⁴ are organic groups that may independently have a hydrogen atom, a halogen atom, or a hetero atom, and R ¹⁰¹ or R ¹⁰² and R ¹⁰³ or R ¹⁰⁴ are bonded to form a ring. It may be formed, and at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ contains one or more hydrogen atoms.
R ¹⁰⁵ to R ¹¹⁰ are organic groups that may independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or a hetero atom, except that at least one group of R ¹⁰⁵ to R ¹¹⁰ is a halogen. An organic group that may have an atom, a hydroxyl group, an amino group or a heteroatom.
R ¹²¹ to R ¹²⁴ are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms.
j is 0 or 1 and
m and n are natural numbers representing the number of repetitions in the repeating unit, respectively.
<15> In the presence of a metal-carbene complex catalyst, a norbornene derivative containing a fluorine atom represented by the following general formula a and a cyclopentene derivative represented by the following general formula b are copolymerized and represented by the following general formula I. A fluorinated polymer containing a structural unit represented by the following general formula I', which comprises a step of obtaining a fluorinated polymer containing the structural unit to be obtained and a step of hydrogenating the obtained fluorinated polymer. Production method.

However, the symbols in the above formulas a, b, I and I'represent the following meanings.
Y is independently CR ¹²¹ R ¹²² , O, S, NR ¹²³ or PR ¹²⁴ , respectively.
R ¹⁰¹ to R ¹⁰⁴ are organic groups that may independently have a hydrogen atom, a halogen atom, or a hetero atom, and R ¹⁰¹ or R ¹⁰² and R ¹⁰³ or R ¹⁰⁴ are bonded to form a ring. It may be formed, and at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ contains one or more hydrogen atoms.
R ¹⁰⁵ to R ¹¹⁰ are organic groups that may independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or a hetero atom, except that at least one group of R ¹⁰⁵ to R ¹¹⁰ is a halogen. An organic group that may have an atom, a hydroxyl group, an amino group or a heteroatom.
R ¹²¹ to R ¹²⁴ are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms.
j is 0 or 1 and
m and n are natural numbers representing the number of repetitions in the repeating unit, respectively.

The fluorine-containing polymer according to the present invention is expected to have excellent chemical durability, weather resistance, light transmission, transparency, liquid repellency, and a low dielectric constant.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified and carried out without departing from the gist of the present invention.
As used herein, the term "perfluoroalkyl group" means a group in which all hydrogen atoms of the alkyl group are replaced with fluorine atoms. Similarly, the perfluoroaryl group means a group in which all hydrogen atoms of the aryl group are substituted with fluorine atoms.
Further, the (per) fluoroalkyl group is used as a general term for a combination of a fluoroalkyl group and a perfluoroalkyl group. That is, the group is an alkyl group having one or more fluorine atoms. The same applies to the (pel) fluoroaryl group.
The aryl group means a monovalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms forming an aromatic ring in an aromatic compound, and is a carbon ring compound. It is used as a general term for a combination of an aryl group derived from and a heteroaryl group derived from a heterocyclic compound.
The number of carbon atoms of a hydrocarbon group means the total number of carbon atoms contained in the entire hydrocarbon group, and when the group does not have a substituent, the number of carbon atoms forming a hydrocarbon group skeleton is used. When the group has a substituent, it represents the total number obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the hydrocarbon group skeleton.
The hetero atom means an atom other than a carbon atom and a hydrogen atom, and is preferably one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom. be.
The compound represented by the general formula 1 is referred to as compound 1.

<Fluorine-containing compound (norbornene derivative)>
The fluorine-containing compound according to the present invention is a fluorine-containing compound represented by the following general formula 1, a fluorine-containing compound represented by the following general formula 2, or a fluorine-containing compound represented by the following general formula 3.

However, X ¹¹ and X ¹² are independently hydrogen atoms or fluorine atoms, R ¹¹ and R ¹² are independently monovalent organic groups, and a11 and a12 are independently 0, 1 or 2, respectively. Further, X ²¹ and X ²² are independently hydrogen atoms or fluorine atoms, R ²¹ and R ²² are independently monovalent organic groups, and a ²¹ and a ²² are independently 1 or 2, respectively. Further, Y ³¹ is independently CR ¹³¹ R ¹³² , O, S, NR ¹³³ or PR ¹³⁴ , and R ³¹ is a monovalent fluorine-containing organic group having 2 or more carbon atoms having an ethereal oxygen atom. , R ³² to R ³⁴ are independent hydrogen atoms or halogen atoms, R ¹³¹ to R ¹³⁴ are independent hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and j31 is 0 or 1. Is.

Examples of R ¹¹ and R ¹² include a monovalent hydrocarbon group and a monovalent hydrocarbon group containing a hetero atom, and a fluorine-containing hydrocarbon group having an ethereal oxygen atom is particularly preferable. The monovalent organic group preferably has 1 to 200 carbon atoms, more preferably 1 to 100 carbon atoms, and even more preferably 1 to 20 carbon atoms. That is, two or more etheric oxygens are used as the substituents (-(CH ₂ ) _a11 -O-CFX ¹¹ -R ¹¹ and-(CH ₂ ) _a12 -O-CFX ¹² -R ¹² ) of norbornene in the fluorine-containing compound 1. A fluorine-containing hydrocarbon group having an atom is preferable.
Specific examples of the substituents (-(CH ₂ ) _a11 -O-CFX ¹¹ -R ¹¹ and-(CH ₂ ) _a12 -O-CFX ¹² -R ¹² ) in the fluorine-containing compound 1 are as shown below. Can be mentioned.
-O-CF ₂ CHF- (O-CF ₂ CF ₂ CF ₂ ) _d22 -O-CF ₂ CF ₂ CF ₃ (d22 = 0-65)
-O-CF ₂ CHF- (O-CF ₂ ) _d23- (O-CF ₂ CF ₂ ) _d24 -O-CF ₃ (d23 = 0 to 198, d24 = 0 to 99)
-O-CF ₂ CHF- (O-CF ₂ CF ₂ CF ₂ CF ₂ -O-CF ₂ CF ₂ ) _d25 -O-CF ₃ (d25 = 0-33)
-O-CF ₂ CHF- (O-CF ₂ CF ₂ ) _d26 -O-CF ₃ (d26 = 0-99)
-O-CF ₂ CHF- (O-CF ₂ ) _d27 -O-CF ₃ (d27 = 0-198)
-O-CF ₂ CHF- (O-CF ₂ CF (CF ₃ )) _d28 -O-CF ₂ CF ₂ CF ₃ (d28 = 0-65)
-CH ₂ -O-CF ₂ CHF- (O-CF ₂ CF ₂ CF ₂ ) _d1 -O-CF ₂ CF ₂ CF ₃ (d1 = 0 to 65)
-CH ₂ -O-CF ₂ CHF- (O-CF ₂ ) _d2- (O-CF ₂ CF ₂ ) _d3 -O-CF ₃ (d2 = 0 to 198, d3 = 0 to 99)
-CH ₂ -O-CF ₂ CHF- (O-CF ₂ CF ₂ CF ₂ CF ₂ -O-CF ₂ CF ₂ ) _d4 -O-CF ₃ (d4 = 0-33)
-CH ₂ -O-CF ₂ CHF- (O-CF ₂ CF ₂ ) _d5 -O-CF ₃ (d5 = 0-99)
-CH ₂ -O-CF ₂ CHF- (O-CF ₂ ) _d6 -O-CF ₃ (d6 = 0-198)
-CH ₂ -O-CF ₂ CHF- (O-CF ₂ CF (CF ₃ )) _d19 -O-CF ₂ CF ₂ CF ₃ (d19 = 0-65)
-CH ₂ CH ₂ -O-CF ₂ CHF- (O-CF ₂ CF ₂ CF ₂ ) _d7 -O-CF ₂ CF ₂ CF ₃ (d7 = 0 to 65)
-CH ₂ CH ₂ -O-CF ₂ CHF- (O-CF ₂ ) _d8- (O-CF ₂ CF ₂ ) _d9 -O-CF ₃ (d8 = 0 to 198, d9 = 0 to 99)
-CH ₂ CH ₂ -O-CF ₂ CHF- (O-CF ₂ CF ₂ CF ₂ CF ₂ -O-CF ₂ CF ₂ ) _d10 -O-CF ₃ (d10 = 0 to 33)
-CH ₂ CH ₂ -O-CF ₂ CHF- (O-CF ₂ CF ₂ ) _d11 -O-CF ₃ (d11 = 0 to 99)
-CH ₂ CH ₂ -O-CF ₂ CHF- (O-CF ₂ ) _d12 -O-CF ₃ (d12 = 0 to 198)
-CH ₂ CH ₂ -O-CF ₂ CHF- (O-CF ₂ CF (CF ₃ )) _d20 -O-CF ₂ CF ₂ CF ₃ (d20 = 0 to 65)

As the substituents (-(CH ₂ ) _a11 -O-CFX ¹¹ -R ¹¹ and-(CH ₂ ) _a12 -O-CFX ¹² -R ¹² ) in the fluorine-containing compound 1,
-CH ₂ -O-CF ₂ CHF-O-CF ₂ CF ₂ CF ₃ ,
-CH ₂ -O-CF ₂ CHF-O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ CF ₃ ,
-CH ₂ -O-CF ₂ CHF-O-CF ₂ CF ₂ -O-CF ₂ -O-CF ₂ -O-CF ₃ ,
-CH ₂ -O-CF ₂ CF ₂ -O-CF ₂ CF ₂ -O-CF ₂ CF _3,
-CH ₂ -O-CF ₂ CF ₂ -O-CF ₂ CF ₂ -O-CF ₂ CF ₂ CF ₂ CF ₃ ,
-CH ₂ -O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ CF ₃ ,
-CH ₂ CH ₂ -O-CF ₂ CHF-O-CF ₂ CF ₂ CF ₃ ,
-CH ₂ CH ₂ -O-CF ₂ CHF-O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ CF ₃ ,
-CH ₂ CH ₂ -O-CF ₂ CHF-O-CF ₂ CF ₂ -O-CF ₂ -O-CF ₂ -O-CF ₃ ,
-CH ₂ CH ₂ -O-CF ₂ CF ₂ -O-CF ₂ CF ₂ -O-CF ₂ CF ₃ ,
-CH ₂ CH ₂ -O-CF ₂ CF ₂ -O-CF ₂ CF ₂ -O-CF ₂ CF ₂ CF ₂ CF ₃ ,
-CH ₂ CH ₂ -O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ CF ₃ and the like are particularly preferably exemplified.

The R ²¹ and R ²² are the same as those of R ¹¹ and R ¹² , including suitable embodiments.
Compound 3 can be synthesized, for example, by a Diels-Alder reaction between a diene having a five-membered ring structure such as cyclopentadiene and an olefin as described later. Y ³¹ can be defined by the structure of the diene of the five-membered ring structure. Among them, Y ³¹ is preferably CH ₂ , O, or NH from the viewpoint of reactivity and availability, and CH ₂ is particularly preferable.
The R ³¹ is preferably 1 having 2 or more carbon atoms including a monovalent fluorine-containing hydrocarbon group having 2 or more carbon atoms having an ethereal oxygen atom, an ethereal oxygen atom and a hetero atom (excluding the etheric oxygen atom). A valence-containing fluorine hydrocarbon group can be mentioned. That is, as the substituent (OR ³¹ ) of norbornene in compound 3, a fluorine-containing alkoxy group having 2 or more carbon atoms having two or more ethereal oxygen atoms (two or more including the oxygen atom at the base of the alkoxy group) is preferable. .. The monovalent fluorine-containing organic group preferably has 2 to 200 carbon atoms, more preferably 2 to 100 carbon atoms, and even more preferably 3 to 20 carbon atoms.
Specific examples of the OR ³¹ include the structure shown below.
-(O-CF ₂ CF ₂ CF ₂ ) _d13 -O-CF ₂ CF ₂ CF ₃ (d13 = 0-65)
-(O-CF ₂ ) _d14- (O-CF ₂ CF ₂ ) _d15 -O-CF ₃ (d14 = 0 to 199, d15 = 0 to 99)
-(O-CF ₂ CF ₂ CF ₂ CF ₂ -O-CF ₂ CF ₂ ) _d16 -O-CF ₃ (d16 = 0 to 33)
-(O-CF ₂ CF ₂ ) _d17 -O-CF ₃ (d17 = 0 to 99)
-(O-CF ₂ ) _d18 -O-CF ₃ (d18 = 0-199)
-(O-CF ₂ CF (CF ₃ )) _d21 -O-CF ₂ CF ₂ CF ₃ (d21 = 0-65)

As OR ³¹ ,
-O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ CF ₃ ,
-O-CF ₂ CF ₂ -O-CF ₂ -O-CF ₂ -O-CF ₃ ,
-O-CF ₂ CF ₂ CF ₂ -O-CF ₃ ,
-O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ CF ₃ and the like are particularly preferably exemplified.

R ³² to R ³⁴ are independently hydrogen atoms or halogen atoms, and hydrogen atoms or fluorine atoms are preferable.

The method for synthesizing compounds 1 to 3 is shown below.
The fluorine-containing compound 1 can be synthesized, for example, from a norbornene derivative having two hydroxyl groups and a fluorine-containing compound.
Specific examples of the method for synthesizing compound 1 include the following methods for synthesizing compound 1-1. Compound 1-1 is a symmetric compound because it is obtained by reacting a norbornene derivative with one kind of fluorine-containing compound in a double amount. An asymmetric fluorine-containing compound 1 can be obtained by reacting a norbornene derivative with different types of fluorine-containing compounds in 1-fold amounts.
a ¹¹ , a ¹² , and X ¹¹ are the same, including the definition and the preferred embodiment in the above-mentioned compound 1. R ^11'is preferably a fluorinated hydrocarbon group or a fluorinated hydrocarbon group having an ethereal oxygen atom. The carbon number of R ^11'is preferably 1 to 20.

The fluorine-containing compound 2 can be synthesized, for example, from a norbornene derivative having two hydroxyl groups and a fluorine-containing compound.
Specific examples of the method for synthesizing compound 2 include the following methods for synthesizing compound 2-1. Compound 2-1 is a symmetric compound because it is obtained by reacting a norbornene derivative with one kind of fluorine-containing compound in a double amount. An asymmetric fluorine-containing compound 2 can be obtained by reacting a norbornene derivative with different types of fluorine-containing compounds in 1-fold amounts.
a ²¹ , a ²² , and X ²¹ are the same, including the definition and the preferred embodiment in the above-mentioned compound 2. R ^21'is preferably a fluorine-containing hydrocarbon group or a fluorine-containing hydrocarbon group having an ethereal oxygen atom. The carbon number of R ^{21'preferably} 1 to 20.

The fluorine-containing compound 3 can be synthesized, for example, by a Diels-Alder reaction between a diene having a five-membered ring structure and an olefin. A fluorine-containing norbornene derivative having j31 = 0 can be synthesized by reacting a diene with an olefin, and a fluorine-containing norbornene derivative having j31 = 1 can be synthesized by further reacting with a diene. Here, Y ³¹ and R ³¹ to R ³⁴ are as described above, respectively.

<Fluorine-containing polymer>
One aspect of the fluorine-containing polymer according to the present invention is a copolymer containing the structural unit represented by the general formula I or the structural unit represented by the general formula II.

The copolymer containing the structural unit represented by the general formula I or the structural unit represented by the general formula II is at least a norbornene derivative (fluorine-containing norbornene derivative) containing a fluorine atom represented by the following general formula a. , The cyclopentene derivative represented by the following general formula b can be produced by using a raw material monomer and copolymerizing them.

In the above formula, Y is independently CR ¹²¹ R ¹²² , O, S, NR ¹²³ or PR ¹²⁴ , and R ¹⁰¹ to R ¹⁰⁴ each independently have a hydrogen atom, a halogen atom or a hetero atom. It is an organic group which may be present, and R ¹⁰¹ or R ¹⁰² may be bonded to R ¹⁰³ or R ¹⁰⁴ to form a ring, and fluorine may be added to at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ . It contains one or more atoms, and R ¹⁰⁵ to R ¹¹⁰ are organic groups that may independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or a hetero atom, except that R ¹⁰⁵ to R. At least one group out of ¹¹⁰ is an organic group which may have a halogen atom, a hydroxyl group, an amino group or a hetero atom, and R ¹²¹ to R ¹²⁴ are independently hydrogen atoms or carbon atoms 1 to 20. It is an alkyl group, and j is 0 or 1.
Here, "R ¹⁰¹ to R ¹⁰⁴ " means R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ . Similarly, "R ¹⁰⁵ to R ¹¹⁰ " means R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ . Further, "R ¹²¹ to R ¹²⁴ " means R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ .

(Fluorine-containing norbornene derivative)
The fluorine-containing norbornene derivative serving as the raw material monomer is represented by the above general formula a.
In the general formula a, Y is independently CR ¹²¹ R ¹²² , O, S, NR ¹²³ or PR ¹²⁴ , respectively.
The fluorine-containing norbornene derivative can be synthesized, for example, by a Diels-Alder reaction between a diene having a five-membered ring structure such as cyclopentadiene and an olefin, as described later. Y can be determined by the structure of the diene of the five-membered ring structure.
Among them, it is preferable that Y is CH ₂ , O, and NH from the viewpoint of reactivity and availability.

In the general formula a, R ¹⁰¹ to R ¹⁰⁴ are organic groups each independently which may have a hydrogen atom, a halogen atom or a hetero atom, and R ¹⁰¹ or R ¹⁰² and R ¹⁰³ or R ¹⁰⁴ are They may be combined to form a ring. Further, at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ contains one or more fluorine atoms.
As long as at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ contains one or more fluorine atoms, the structure of the other groups or atoms represented by R ¹⁰¹ to R ¹⁰⁴ is not particularly limited.

At least one group or atom of R ¹⁰¹ to R ¹⁰⁴ is a (pel) fluoroalkyl group having 1 to 20 carbon atoms, a (pel) fluoroalkoxy group having 1 to 20 carbon atoms, and an ether between carbon atoms. A (pel) fluoroalkyl group having 2 to 200 carbon atoms having a sex oxygen atom, a (pel) fluoroalkoxy group having 2 to 200 carbon atoms including an ethereal oxygen atom between carbon atoms, and 5 to 20 carbon atoms. (Pel) fluoroaryl group, (pel) fluoroaryloxy group having 5 to 20 carbon atoms, or fluorine atom, preferably (pel) fluoroalkyl group having 1 to 10 carbon atoms, carbon atom and carbon atom. A (pel) fluoroalkyl group having 2 to 10 carbon atoms having an ethereal oxygen atom between them, a (pel) fluoroalkoxy group having 2 to 10 carbon atoms including an ethereal oxygen atom between carbon atoms, or fluorine. It is more preferably an atom.

Examples of the halogen atom of R ¹⁰¹ to R ¹⁰⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The organic groups of R ¹⁰¹ to R ¹⁰⁴ may be linear or branched, and may have a cyclic structure. As the organic group of R ¹⁰¹ to R ¹⁰⁴ , an organic group having 1 to 100 carbon atoms is preferable, and for example, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cycloalkyl group, a silicon-containing alkyl group, an alkoxycarbonyl group, and the like. Examples thereof include an alkylcarbonyl group, a cyano group, a cyano group-containing alkyl group, an ester group-containing alkyl group, an ether group-containing alkyl group, a hydroxycarbonyl group, a carboxy group-containing alkyl group, a hydroxy group, and a hydroxy group-containing alkyl. These may have a heteroatom, or may further have a substituent containing a heteroatom and having 1 to 100 carbon atoms. Further, the cyclic structure is not limited to a single ring, and may have a polycyclic structure in which a plurality of rings are bonded. The polycyclic structure may be a fused ring or a spiro ring. These cyclic structures are not limited to the carbocyclic compound, and may be a heterocyclic compound in which one or more carbon atoms are substituted with heteroatoms. Of the hydrogen atoms forming the ring, some or all of the hydrogen atoms may be replaced with halogen atoms.

In the general formula a, j is 0 or 1. As the fluorine-containing norbornene derivative represented by the general formula a, for example, as shown in the following scheme, a fluorine-containing norbornene derivative having j = 0 can be synthesized by a Diels-Alder reaction between a diene having a five-membered ring structure and an olefin. Further, by further reacting with diene, a fluorine-containing norbornene derivative having j = 1 can be synthesized. Here, Y and R ¹⁰¹ to R ¹⁰⁴ are as described above, respectively.

The raw material diene is cyclopentadiene and its derivative (Y = CR ¹²¹ R ¹²² ), furan (Y = O), thiophene (Y = S), azole and its derivative (Y = NR ¹²³ ), phosphole and its derivative (A). = PR ¹²⁴ ) can be used.
In the olefin compound as a raw material, R ¹⁰¹ to R ¹⁰⁴ are organic groups which may independently have a hydrogen atom, a halogen atom or a hetero atom, respectively, and are R ¹⁰¹ or R ¹⁰² and R ¹⁰³ or R ¹⁰⁴ . And may be bonded to form a ring, and it is sufficient that at least one group or atom of R ¹⁰¹ to R ¹⁰⁴ contains one or more hydrogen atoms.

The method for synthesizing the fluorine-containing norbornene derivative is not limited to the Diels-Alder reaction, and can be obtained by other synthetic methods. For example, it can be synthesized from a norbornene derivative having a reactive functional group and a fluorine-containing compound, and examples of the reactive functional group include a hydroxyl group, an amino group and a thiol group. Specific examples include the following reactions. In the formula, R'refers to be a (pel) fluoroalkyl group, a (pel) fluoroalkoxy group, a (pel) fluoroalkyl group having an ethereal oxygen atom between carbon atoms, and between carbon atoms and carbon atoms. Examples thereof include a (pel) fluoroalkoxy group containing an ethereal oxygen atom, a (pel) fluoroaryl group, a (pel) fluoroaryloxy group, and a fluorine atom.

Examples of the fluorine-containing compound represented by the general formula a include, but are not limited to, the following compounds.

(Cyclopentene derivative)
The cyclopentene derivative as the raw material monomer is represented by the above general formula b.
In the general formula b, R ¹⁰⁵ to R ¹¹⁰ are organic groups which may independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or a hetero atom, respectively, and at least among R ¹⁰⁵ to R ¹¹⁰ . The group 1 is an organic group which may have a halogen atom, a hydroxyl group, an amino group or a hetero atom, and may be bonded to each other to form a ring. The organic group may be linear or branched, and may have a cyclic structure.
That is, the cyclopentene derivative represented by the general formula b can be rephrased as a cyclopentene derivative having a substituent, and compounds in which R ¹⁰⁵ to R ¹¹⁰ in the general formula b are all hydrogen atoms are excluded.

The organic group which may have a hetero atom may contain, for example, one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. Examples thereof include a monovalent hydrocarbon group of 1 to 200, a cyano group, a carboxyl group, an isocyanate group and the like.
Examples of the monovalent hydrocarbon group having 1 to 200 carbon atoms include an alkyl group having 1 to 200 carbon atoms, an alkoxy group having 1 to 200 carbon atoms, an aryl group having 5 to 20 carbon atoms, and an aryloxy group having 5 to 20 carbon atoms. Can be exemplified. The monovalent hydrocarbon group may be linear or branched. Further, a ring may be formed as a divalent hydrocarbon group.
These preferred groups may have a halogen atom bonded to at least a part of the carbon atom. That is, for example, it may be a (pel) fluoroalkyl group or a (pel) fluoroalkoxy group. Further, these preferable groups may have an ethereal oxygen atom between carbon atoms. Further, these preferable groups may further have a substituent containing one or more atoms selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. Examples of the substituent include a hydroxyl group, an amino group, an imino group, a nitrile group, an amide group (carbonylamino group), a carbamate group (oxycarbonylamino group), a nitro group, a carboxyl group and an ester group (acyloxy group or an alkoxycarbonyl group). ), A silyl group (alkylsilyl group, alkoxysilyl group or halide silyl group), carbonyl group, alkoxy group and the like can be exemplified. These groups may be further substituted with an alkyl group or an aryl group. For example, the amino group (-NH ₂ ) may be a monoalkylamino group (-NHR), a monoarylamino group (-NHAr), a dialkylamino group (-NR ₂ ), or a diarylamino group (-NAr ₂ ). .. However, R is an alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms having an ethereal oxygen atom between carbon atoms, and Ar is an aryl group having 5 to 12 carbon atoms.

Among them, R ¹⁰⁵ to R ¹¹⁰ are independent (pel) fluoroalkyl groups having 1 to 10 carbon atoms, and (pel) fluoro having 1 to 10 carbon atoms having an ethereal oxygen atom between carbon atoms. An alkyl group, a (pel) fluoroalkoxy group having 1 to 10 carbon atoms including an ethereal oxygen atom between carbon atoms, an ester group having 1 to 12 carbon atoms, and an ethereal oxygen atom having 1 to 12 carbon atoms. An alkyl group having an alkyl group, an alkyl group having a cyano group having 1 to 12 carbon atoms, an alkyl group having a hydroxyl group having 1 to 12 carbon atoms, an alkyl group having a carboxyl group having 1 to 12 carbon atoms, and an isocyanate having 1 to 12 carbon atoms. An alkyl group having a group or the like is more preferable.
More specific examples of the cyclopentene derivative represented by the general formula b include the following compounds.

(Other raw material monomers)
In the fluorine-containing polymer according to the present invention, a monomer other than the fluorine-containing norbornene derivative represented by the general formula a and the cyclopentene derivative represented by the general formula b can be further used as a raw material monomer. The same applies to the polymer 11, 21 or 31. The other raw material monomer in this case may be a compound having an olefin structure, and examples thereof include α-olefins such as ethylene, propylene, 1-butene and 1-hexene, styrene, and cyclic olefins.

A further aspect of the fluoropolymer according to the present invention is a structural unit represented by the general formula 11, a structural unit represented by the general formula 12, a structural unit represented by the general formula 21, and the general formula. The structural unit represented by 22, the structural unit represented by the general formula 31, the structural unit represented by the general formula 32, the structural unit represented by the general formula 11', and the structural unit represented by the general formula 21'. It is a polymer containing a structural unit or a structural unit represented by the general formula 31'.

<Polymerization method>
The structural unit represented by the following general formula I or the following general formula II is obtained by carrying out a polymerization reaction using at least a fluorine-containing norbornene derivative represented by the general formula a and a cyclopentene derivative represented by the general formula b as raw material monomers. A fluorine-containing copolymer containing a structural unit represented by is obtained. The symbols in the formula have the same meanings as those described above.

By carrying out ring-opening polymerization (ring-opening metathesis polymerization, ROMP) by a metathesis reaction in the polymerization reaction, a fluoropolymer containing a structural unit represented by the general formula I can be obtained, and copolymerization by an addition polymerization reaction can be performed. By doing so, a fluorine-containing copolymer containing a structural unit represented by the general formula II can be obtained.

As the obtained copolymer, for example, an alternate copolymer, a block copolymer, and a random copolymer can be synthesized, and a desired copolymer can be obtained depending on the charging ratio of the raw material monomer and the polymerization conditions. can.

As the raw material monomer, a fluorine-containing norbornene derivative represented by the general formula a may be used as a main monomer or a comonomer, but using it as a main monomer improves chemical durability and liquid repellency. It is preferable from the point of view. Further, by further using another olefin compound as a raw material monomer, a ternary or higher multidimensional copolymer can be obtained.

Similarly, for compounds 1 to 3, a fluorine-containing polymer containing structural unit 11 can be obtained by ring-opening metathesis polymerization of compound 1, and a fluorine-containing polymer containing structural unit 12 can be obtained by addition polymerization of compound 1. .. Further, a fluorine-containing polymer containing structural unit 21 can be obtained by ring-opening metathesis polymerization of compound 2, and a fluorine-containing polymer containing structural unit 22 can be obtained by addition polymerization of compound 2. Further, a fluorine-containing polymer containing structural unit 31 can be obtained by ring-opening metathesis polymerization of compound 3, and a fluorine-containing polymer containing structural unit 32 can be obtained by addition polymerization of compound 3. The symbols in the formula have the same meanings as those described above.

The molecular weight of the polymer is preferably 1,000 to 1,000,000 from the viewpoint of mechanical and physical properties. The molecular weight is a weight average molecular weight and is measured under the conditions of a polymer solution using gel permeation chromatography (GPC).

In the structural unit represented by the general formula I or the general formula II, the number of repetitions of the repeating unit represented by m is preferably 1 to 10,000 from the viewpoint of mechanical and physical properties, and more preferably 5. It is ~ 6,500. The number of repetitions of the repeating unit represented by n is preferably 1 to 10,000, more preferably 5 to 6,500 from the viewpoint of mechanical and physical properties. Further, the total number of repeating units is preferably 2 to 10,000, more preferably 5 to 6,500.
The structural unit represented by the general formula 11, the general formula 12, the general formula 21, the general formula 22, the general formula 31, or the general formula 32, and the general formula 11', the general formula 21', or the general formula 31'described later. Similarly, the number of repetitions m11, m21, or m31 of the repetition unit in the above is preferably 1 to 10,000, and more preferably 5 to 6 from the viewpoint of mechanical and physical properties. , 500.

The obtained polymer has properties such as high heat resistance, low water absorption, high light transmittance (transparency), high chemical durability, high weather resistance, and high liquid repellency, and also balances these properties. Since it is excellent, it can be used in a wide variety of fields such as electric / electronic materials, semiconductor materials, optical materials, medical instruments / cell culture materials, liquid repellent materials, elastomer materials, and cross-linking agents.

[Ring-opening metathesis polymerization]
A structure represented by the general formula I is obtained by copolymerizing a fluorine-containing norbornene derivative represented by the general formula a and a cyclopentene derivative represented by the general formula b as a raw material monomer in the presence of a metal-carbene complex catalyst. A fluoropolymer containing a unit can be obtained.
The symbols in each formula are as described above.

Further, by using compound 1 as a raw material monomer and polymerizing in the presence of a metal-carbene complex catalyst, a fluorine-containing polymer containing a structural unit represented by the general formula 11 can be obtained. Further, by using compound 2 as a raw material monomer and polymerizing in the presence of a metal-carbene complex catalyst, a fluorine-containing polymer containing a structural unit represented by the general formula 21 can be obtained. Further, by using compound 3 as a raw material monomer and polymerizing in the presence of a metal-carbene complex catalyst, a fluorine-containing polymer containing a structural unit represented by the general formula 31 can be obtained. The symbols in each formula are as described above.

The ring-opening metathesis polymerization reaction proceeds in the presence of a catalyst, but is not particularly limited as long as it is a catalyst for ring-opening metathesis polymerization. The metal-carbene complex compound represented by [L] M = CA ¹ A ² is a typical example. Examples of the metal-carbene complex compound include a ruthenium-carbene complex, a molybdenum-carbene complex, and a tungsten-carbene complex (hereinafter, also collectively referred to as “metal-carbene complex”).

The metal-carbene complex compound having olefin metathesis reaction activity plays a role as a catalyst in the method for producing a fluorine-containing polymer, but means both those added as a reagent and those produced during the reaction (catalytically active species). do. Here, it is known that the metal-carbene complex compound exhibits catalytic activity by dissociating some of the ligands under reaction conditions, and exhibits catalytic activity without dissociation of the ligands. However, the present invention is not limited to any of them. In general, ring-opening metathesis polymerization proceeds by repeating the coordination, ring-opening, and dissociation of the cyclic olefin to the catalyst. Therefore, how many ligands other than the cyclic olefin are coordinated on the catalyst during the reaction? Not always clear. Therefore, in the present specification, [L] does not specify the number or type of ligand. Further, the metal in the metal-carbene complex compound is preferably ruthenium, molybdenum, or tungsten.

Among these catalysts, those having a ruthenium central metal are generally referred to as "ruthenium-carbene complexes", and are, for example, Vougioukarakis, G. et al. C. et al. , Chem. Rev. , 2010, 110, 1746-1787. The ruthenium-carbene complex described in 1 can be utilized. Further, for example, a ruthenium-carbene complex commercially available from Aldrich and Umicore can be used.

Specific examples of the rutenium-carbene complex include bis (triphenylphosphine) benzylphosphine dichloride, bis (tricyclohexylphosphine) benzylphosphenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenilidene ruthenium dichloride, (tricyclohexylphosphine). 1,3-Diisopropylimidazole-2-iriden) (tricyclohexylphosphine) benzylidene lutenium dichloride, (1,3-dicyclohexylphosyl-2-iriden) (tricyclohexylphosphine) benzylhosyl imidazolide, (1,3-dicyclohexylphosphine) -2-Ilidene) (Tricyclohexylphosphin) benzylidene lutenium dichloride, (1,3-dimesityl-4,5-dihydroimidazole-2-iriden) (tricyclohexylphosphine) benzylidene lutenium dichloride, [1,3-bis (2,) 6-Diisopropylphenyl) -4,5-dihydroimidazole-2-iriden] (tricyclohexylphosphine) benzylphostenium dichloride, [1,3-bis (2-methylphenyl) -4,5-dihydroimidazole-2-iriden] (Tricyclohexylphosphine) benzylphosphine dichloride, [1,3-dicyclohexyl-4,5-dihydroimidazole-2-iriden] (tricyclohexylphosphine) benzylphosphine dichloride, bis (tricyclohexylphosphine) ethoxymethylphosdentium dichloride, (1) , 3-Dimesityl-4,5-dihydroimidazole-2-iriden) (tricyclohexylphosphine) ethoxymethylphosdentium dichloride, (1,3-dimesityl-4,5-dihydroimidazole-2-iriden) [bis (3-) Bromopyridine)] benzylidene lutenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-iriden) (2-isopropoxyphenylmethylidene) lutenium dichloride, (1,3-dimesityl-4,5-dihydro) Imidazole-2-iriden) [(Tricyclohexylpholanyl) methylidene] Dichlorolutenium tetrafluoroborate, UmicoreM2, UmicoreM51, UmicoreM52, UmicoreM71SIMs, UmicoreM71SITr, UmicoreM73SIMs, UmicoreM73 SIPr and the like include (1,3-dimeshtyl-4,5-dihydroimidazol-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimeshtyl-4,5-dihydroimidazol-2-ylidene). ) (2-Isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimeshtyl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphoranyl) methylidene] dichlororuthenium tetrafluoroborate, UmicoreM2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, and Umicore M73 SIPr are particularly preferable. Among the above complexes, the name starting with "Umicore" is a trade name of a product of Umicore.
The ruthenium-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina, or a polymer.

Among these catalysts, those whose central metal is molybdenum or tungsten are generally referred to as "molybdenum-carbene complex" or "tungsten-carbene complex", and are, for example, Grela, K. et al. (Ed) Olefin Mathesis: Theory and Practice, Wiley, 2014. The molybdenum-carbene complex or the tungsten-carbene complex described in 1 can be used. Further, for example, a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich, Strem, or Ximo can be used.
The molybdenum-carbene complex or the tungsten-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina, or a polymer.

Specific examples are shown below. In addition, Me means a methyl group, i-Pr means an isopropyl group, t-Bu means a tertiary butyl group, and Ph means a phenyl group.

From the viewpoint of improving the yield of the target product, it is preferable to use a degassed and dehydrated monomer as a raw material. There are no particular restrictions on the degassing operation, but freeze degassing may be performed. The dehydration operation is not particularly limited, but is usually brought into contact with a molecular sieve or the like. For the raw material monomer, the degassing and dehydrating operations are usually performed before contacting with the metal-carbene complex.
Further, since the monomer as a raw material may contain a trace amount of impurities (for example, peroxide), it may be purified from the viewpoint of improving the yield of the target product. There are no particular restrictions on the purification method. For example, it can be carried out according to the method described in the literature (Armarego, LF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).

The monomers used as raw materials are charged into the reaction vessel, but two or more kinds of monomers used as raw materials may be mixed in the reaction vessel in advance and then charged, or they may be charged separately.

The metal-carbene complex may be charged as a reagent or generated in the system.
When charged as a reagent, a commercially available metal-carbene complex may be used as it is, or a non-commercially available metal-carbene complex synthesized from a commercially available reagent by a known method may be used.
When generated in a system, a metal-carbene complex prepared from a metal complex as a precursor by a known method can be used in the present invention.

The amount of the metal-carbene complex to be used is not particularly limited, but is usually 0.000001 (1 ppm) with respect to 1 mol of the fluorine-containing norbornene derivative represented by the general formula a as a reference among the monomers used as raw materials. It is used in an amount of about 1 mol, preferably about 0.00001 (10 ppm) to 0.2 mol.

The metal-carbene complex to be used is usually put into the reaction vessel as a solid, but it may be put into the reaction vessel after being dissolved or suspended in a solvent. The solvent used at this time is not particularly limited as long as it does not adversely affect the reaction, and an organic solvent, a fluorine-containing organic solvent, an ionic liquid, water and the like can be used alone or in combination. In these solvent molecules, some or all hydrogen atoms may be substituted with deuterium atoms.
When the monomer is a liquid (including the case of liquefying by heating), it is preferable to carry out bulk polymerization without using a solvent. In this case, it is preferable that the metal-carbene complex compound is dissolved in the fluorine-containing norbornene derivative represented by the general formula a.

When performing ring-opening metathesis polymerization, olefins or dienes can be used as chain transfer agents for the purpose of controlling the molecular weight and its distribution.
As the olefin, for example, α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene, or fluorine-containing olefins thereof can be used. Furthermore, vinyltrimethylsilane, allyltrimethylsilane, vinyltriethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, allyltriethylsilane, allyltriisopropylsilane, trichlorovinylsilane, trichloroallylsilane, and trimethoxy (2-tri). Methoxysilyl ethenyl) silane, bis (triethoxysilyl) ethylene, trichloro (2-trichlorosilylethenyl) silane, 1,4-bis (trimethoxysilyl) -2-butene, 1,4-bis (triethoxysilyl) silane ) -2-Buten, silicon-containing olefins such as 1,4-bis (trichlorosilyl) -2-butene, or these fluorine and silicon-containing olefins can also be used as the chain transfer agent.
Examples of the diene include non-conjugated diene such as 1,4-pentadiene, 1,5-hexadiene and 1,6-heptadiene, or fluorine-containing non-conjugated diene thereof. These olefins, fluorine-containing olefins or dienes may be used alone or in combination of two or more.

Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, chloroform, 1 and 2. -Halogen solvents such as dichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as tetrahydrofuran (THF), dioxane, diethyl ether, glyme and diglyme can be used. Examples of the fluorine-containing organic solvent include hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, dichloropentafluoropropane and the like. Can be used. As the ionic liquid, for example, various pyridinium salts, various imidazolium salts and the like can be used. Among the above solvents, benzene, toluene, o-, m-, p-xylene, mesitylene, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, diethyl ether, dioxane, THF, etc., in terms of solubility of the metal-carbene complex, etc. , Hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene and the like, and mixtures thereof are preferable.
From the viewpoint of improving the yield of the target product, it is preferable to use a degassed and dehydrated solvent. There are no particular restrictions on the degassing operation, but freeze degassing may be performed. The dehydration operation is not particularly limited, but is usually brought into contact with a molecular sieve or the like. The degassing and dehydrating operations are usually performed prior to contact with the metal-carbene complex.

The atmosphere in which the monomer and the metal-carbene complex are brought into contact with each other is not particularly limited, but is preferably under an inert gas atmosphere, particularly preferably under a nitrogen or argon atmosphere, in terms of extending the life of the catalyst. However, when a compound that becomes a gas under the reaction conditions is used as the raw material monomer, it can be carried out under these gas atmospheres.
The phase for contacting the monomer and the metal-carbene complex is not particularly limited, but a liquid phase is usually used in terms of reaction rate. When the monomer as a raw material is a gas under the reaction conditions, it is difficult to carry out in the liquid phase, so it can also be carried out in the gas-liquid two-phase. In addition, when carrying out in a liquid phase, a solvent can be used. As the solvent used at this time, the same solvent as that used for dissolving or suspending the metal-carbene complex can be used. If the monomer used as a raw material contains a liquid under reaction conditions, it may be possible to carry out without a solvent (bulk polymerization).

The container for contacting the monomer and the metal-carbene complex is not particularly limited as long as it does not adversely affect the reaction, and for example, a metal container or a glass container can be used. Since ring-opening metathesis polymerization may handle a monomer compound in a gaseous state under reaction conditions, a pressure-resistant container capable of high airtightness is preferable.

The temperature at which the monomer and the metal-carbene complex are brought into contact with each other is not particularly limited, but can usually be carried out in the range of -100 to 200 ° C., and 0 to 150 ° C. is preferable in terms of the reaction rate. Since the reaction does not start at low temperature and rapid decomposition of the complex may occur at high temperature, it is necessary to appropriately set the lower and upper limits of the temperature. Usually, it is carried out at a temperature equal to or lower than the boiling point of the solvent used.
The time for contacting the monomer and the metal-carbene complex is not particularly limited, but is usually carried out in the range of 1 minute to 48 hours.
The pressure for bringing the monomer into contact with the metal-carbene complex is not particularly limited, but may be under pressure, normal pressure, or reduced pressure. It is usually about 0.001 to 10 MPa, preferably about 0.01 to 1 MPa.
The molecular weight of the obtained polymer can be targeted by appropriately adjusting the reaction conditions such as the charging ratio of the monomers, the reaction temperature, the reaction time, and the reaction pressure.

When the monomer and the metal-carbene complex are brought into contact with each other, an inorganic salt, an organic compound, a metal complex or the like may coexist as long as the reaction is not adversely affected. Further, the mixture of the monomer and the metal-carbene complex may be stirred as long as it does not adversely affect the reaction. At this time, as a stirring method, a mechanical stirrer, a magnetic stirrer, or the like can be used.

After the polymerization reaction is completed by contacting the monomer with the metal-carbene complex, the target polymer may be isolated by a known method. As an isolation method, for example, in the case of a solution, a reaction solution is discharged into a poor solvent under stirring to precipitate a polymer hydride to form a slurry, which is then recovered by a filtration method, a centrifugation method, a decantation method, or the like. Examples include a steam stripping method in which steam is blown into a reaction solution to precipitate a polymer, a method in which the solvent is directly removed from the reaction solution by heating, etc., and in the case of a slurry, a filtration method, a centrifugation method, a decantation method, etc. A method of collecting the solution can be mentioned. In addition, column chromatography, recycled preparative HPLC and the like can be mentioned, and these can be used alone or in combination as needed.

The target product obtained by this reaction can be identified by a known method similar to that of a normal polymer compound. For example, ¹ H-, ¹⁹ F-, ¹³ C-NMR, GPC, static light scattering, SIMS, GC-MS and the like can be mentioned, and these can be used alone or in combination as needed.

When the obtained polymer is a copolymer, the ratio of two or more unit structures constituting the fluorine-containing copolymer depends on the charging ratio of the monomers. Normally, assuming that the number of repetitions of the repeating unit derived from the fluorine-containing norbornene derivative represented by the general formula a as a reference is 1, the number of repetitions of the repeating unit derived from the cyclopentene derivative represented by the general formula b is 0.01 to 100. It is about 0.1 to 10. Further, in the case of a ternary or higher multi-dimensional copolymer, the total number of repeating units derived from other olefins is about 0.001 to 1000, preferably about 0.01 to 100.

[Hydrogenated ring-opening metathesis polymer]
The hydrogenated additive of the fluorine-containing copolymer (ring-opening metathesis polymer) containing the structural unit represented by the general formula I in the present invention is mainly the fluorine-containing copolymer containing the structural unit represented by the general formula I. It is hydrogenated to the chain double bond portion and contains a structural unit represented by the general formula I'.
Similarly, the hydrogenated product of the fluoropolymer containing structural unit 11 is hydrogenated to the main chain double bond portion of the fluoropolymer containing structural unit 11, and is represented by the general formula 11'. Includes structural units. The hydrogenated product of the fluoropolymer containing the structural unit 21 is hydrogenated to the main chain double bond portion of the fluoropolymer containing the structural unit 21, and has a structure represented by the general formula 21'. Includes units. The hydrogenated product of the fluoropolymer containing structural unit 31 is hydrogenated to the main chain double bond portion of the fluoropolymer containing structural unit 31, and has a structure represented by the general formula 31'. Includes units.
Of the structural units of the fluorine-containing copolymer containing the structural unit represented by the general formula I', the reaction in which the structural unit represented by the general formula I is hydrogenated to the structural unit represented by the general formula I'. The rate (reduction rate) is preferably 50% or more and 100% or less, and more preferably 80% or more and 100% or less. Similarly, among the constituent units of the fluorine-containing polymer containing the structural unit 11', the reduction rate is preferably 50 to 100%, more preferably 80 to 100%. Further, among the constituent units of the fluorine-containing polymer containing the structural unit 21', the reduction rate is preferably 50 to 100%, more preferably 80 to 100%. Further, among the constituent units of the fluorine-containing polymer containing the structural unit 31', the reduction rate is preferably 50 to 100%, more preferably 80 to 100%.
The symbols in the formula are as described above.

When the fluorine-containing polymer according to the present invention contains a large amount of a main chain double bond that absorbs light at a specific wavelength, particularly at a wavelength in the ultraviolet region, the light transmittance with respect to the wavelength in the ultraviolet region is lowered and optical. There is a risk of impairing the characteristics. This light transmittance can be controlled to the required transmittance by adding (adding) a hydrogen atom to the main chain double bond of the ring-opening metathesis polymer to form a saturated bond.
Further, when the amount of double bonds contained in the fluorine-containing polymer is large, the refractive index becomes high, and when the amount of saturated bonds is increased by hydrogenation, the refractive index can be lowered. The refractive index can be arbitrarily adjusted by increasing or decreasing the rate of hydrogen atom addition (hereinafter, may be referred to as hydrogenation rate).

On the other hand, these backbone double bonds have a geometrically planar structure that limits the free movement of the polymer. That is, if there are many double bonds, the glass transition temperature becomes high and the heat resistance characteristics are improved. However, the double bond may deteriorate the stability against oxidation, and the problem is solved by appropriately adding an antioxidant or the like that can be generally used for an olefin polymer for the purpose of preventing oxidation. be able to. Further, the double bond may be oxidized to have an epoxiside structure.

Furthermore, the amount of these double bonds also affects the mechanical strength and impact resistance of the polymer, and if the amount is large, the rigidity is increased, and if the double bonds are hydrogenated and converted into saturated bonds, the flexibility is increased. And impact resistance can be increased. The ratio of hydrogenation of this main chain double bond can be arbitrarily determined by the balance of polymer physical properties such as light transmission, heat resistance, weather resistance, mechanical strength, and impact resistance.

The molecular weight of the ring-opening metathesis polymer hydrogenated product is preferably 1,000 to 1,000,000 from the viewpoint of mechanical and physical properties. The molecular weight is a value represented by a weight average molecular weight, and is measured under the condition of a polymer solution using GPC.

[Addition polymerization]
By copolymerization by an addition polymerization reaction using a fluorine-containing norbornene derivative represented by the general formula a and a cyclopentene derivative represented by the general formula b as a raw material monomer, a fluorine-containing co-container containing a structural unit represented by the general formula II. A polymer can be obtained.
The symbols in the formula are as described above.

Similarly, by addition polymerization using compound 1 as a raw material monomer, a fluorine-containing polymer containing a structural unit represented by the general formula 12 can be obtained. Further, by addition polymerization using compound 2 as a raw material monomer, a fluorine-containing polymer containing a structural unit represented by the general formula 22 can be obtained. Further, by addition polymerization using compound 3 as a raw material monomer, a fluorine-containing polymer containing a structural unit represented by the general formula 32 can be obtained.
The symbols in the formula are as described above.

Examples of the polymerization method include radical polymerization, cationic polymerization, anionic polymerization and coordination polymerization, and radical polymerization or coordination polymerization is preferable.

The addition polymerization reaction can be carried out by a known method. A method of addition polymerization of a fluorine-containing cyclic olefin is preferable. As for the conditions of addition polymerization, conditions well known to those skilled in the art can be appropriately optimized and adopted.

For isolation and identification after completion of the polymerization reaction, the same method as for ring-opening metathesis polymerization can be used.

When the obtained polymer is a copolymer, the ratio of the unit structures constituting the fluorine-containing copolymer depends on the charging ratio of the monomers. Normally, assuming that the number of repetitions of the repeating unit derived from the fluorine-containing norbornene derivative represented by the general formula a as a reference is 1, the number of repetitions of the repeating unit derived from the cyclopentene derivative represented by the general formula b is 0.01 to 100. It is about 0.1 to 10. Further, in the case of a ternary or higher multi-dimensional copolymer, the total number of repeating units derived from other olefins is about 0.01 to 100, preferably about 0.1 to 10.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
<Commercial reagent>
In this example, as the catalyst and the reagent, unless otherwise specified, commercially available products were used as they were in the reaction. As the solvent, a commercially available product dehydrated and deoxidized was used.
<Evaluation method>
In this example, the structure of the synthesized compound was identified by performing ¹ H-NMR and ¹⁹ F-NMR measurements with a nuclear magnetic resonance apparatus (JNM-AL300) manufactured by JEOL Ltd.
The molecular weight was determined by a chemical ionization method (CI) using a gas chromatograph mass spectrometer (GCMS-QP2010Ultra) manufactured by Shimadzu Corporation.
The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the fluorine-containing polymer are known from the chromatogram obtained by a high-speed gel permeation chromatography (GPC) apparatus (HLC-8220, manufactured by Toso Co., Ltd.). It was determined using a calibration curve prepared using a standard polymethylmethacrylate sample.
The contact angle of water and n-hexadecane conforms to JIS R3257 (wetness test method for substrate glass surface) using a solid surface energy analyzer CA-XE manufactured by Kyowa Surface Science Co., Ltd., and a droplet of about 2 μL is produced. It was dropped on the surface of the base material, and the contact angle was measured within 1 minute after the liquid enemy came into contact with the surface of the base material by the static drip method.

Among the examples shown below, Examples 1-1 to 1-3 and Examples 6-1 to 6-3 are comparative examples, and Examples 2-1 to 2-3 and Examples 3-1 to 3- 3. Examples 4-1 to 4-3, 5-1 to 5-2, and 7-1 to 7-3 are examples.
In addition, Example 8-1 to Example 8-2, Example 9-1 to Example 9-2, Example 10-1 to Example 10-2, Example 11-1 to Example 11-2, Example 12-1 to Example 12- 2 is an example.

<Example 1-1> Synthesis of fluorine-containing norbornene derivative NM-PPVE Potassium hydroxide (3.56 g, 63.4 mmol), acetonitrile (25 mL), bicyclo [2.2.1] hepta-5-ene-2-methanol (4.10 g, 33.0 mmol) and perfluoro (propyl vinyl ether) (18.6 g, 70.1 mmol) were placed in a 100 mL round bottom flask, and a Dimroth was attached and reacted at 50 ° C. for 3 hours. 150 g of ice-cold water was placed in a 300 mL beaker and stirred, and the above reaction solution was slowly and continuously introduced into the ice-cold water. Further, AK-225 (dichloropentafluoropropane: manufactured by AGC, 40 mL) was added and stirred, and then the organic phase was separated. AK-225 (40 mL) was added to the aqueous layer of the pre-divided liquid and re-extracted, and the obtained organic phase was combined with the previously obtained organic phase. Anhydrous sodium sulfate was added to the organic phase, and the mixture was stirred, and then insoluble matter was removed by vacuum filtration. The obtained organic phase was concentrated by an evaporator and then purified by silica gel column chromatography (mobile phase: n-hexane) to obtain a compound represented by NDM-2PPVE. The yield was 11.7 g and the yield was 91%.
^{1 1} H-NMR (CDCl3): δ (ppm) 6.1 to 5.7 (m, 3H), 4.1 to 3.5 (m, 2H), 2.9 to 0.5 (m, 7H) ..
¹⁹ F-NMR (CDCl3): δ (ppm) -81.8 (3F), -85.0 to -85.6 (1F), -87.2 to -87.7 (1F), -89.0 ~ 91.1 (2F), -130.3 (s, 2F), -144.8 ~ -145.2 (1F).
GC-MS (CI): [M + H] ⁺ = 391

<Example 1-2> Ring-opening metathesis polymerization of NM-PPVE In a 10 mL screw tube bottle under nitrogen, Grubbs second generation catalyst (22 mg, 0.026 mmol) was dissolved in dichloromethane (5 mL), and the solution (A) was added. Prepared. Next, the NM-PPVE (2.0 g, 5.13 mmol) and dichloromethane (19 mL) obtained in Example 1-1 were charged into a 100 mL screw tube bottle and dissolved, and then the previously prepared solution (A) was added. 1 mL (corresponding to 0.1 mol% of catalyst) was added and the mixture was reacted at room temperature for 3 hours. Next, ethyl vinyl ether (419 μL) was added to the reaction solution to terminate the polymerization, and then AE-3000 (1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether: manufactured by AGC) was added. 40 mL was added to dilute the reaction solution. After the diluted reaction solution was continuously added to methanol (200 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 50 ° C. The yield of the target polymer (P-NM-PPVE) was 98%.
A series of these reactions is shown below. In the formula, m is a positive integer indicating the number of repetitions in the repeating unit.

<Example 1-3>
The polymer (P-NM-PPVE) synthesized in Example 1-2 was dissolved in HFE-7200 manufactured by 3M at a concentration of 3 wt% to prepare an HFE-7200 solution of the polymer. Next, an HFE-7200 solution of P-NM-PPVE was applied to a glass substrate, coated uniformly using a spin coater, and then dried at 150 ° C. for 10 minutes to prepare an evaluation substrate. The water contact angle of the coated surface was 108 degrees, and the contact angle of n-hexadecane was 63 degrees.

<Example 2-1> Synthesis of fluorine-containing norbornene derivative NDM-2PPVE Potassium hydroxide (3.64 g, 64.8 mmol), acetonitrile (50 mL), bicyclo [2.2.1] hepta-5-en-2,2 -Dimethanol (2.5 g, 16.2 mmol) and perfluoro (propyl vinyl ether) (17.3 g, 64.8 mmol) were placed in a 100 mL round bottom flask, and a Dimroth was attached and reacted at 50 ° C. for 3 hours. 25 g of ice and 25 g of tap water were placed in a 200 mL beaker and stirred, and the above reaction solution was continuously introduced into ice-cold water. Further, n-pentane (50 mL) was added and stirred, and then the organic phase was separated. AK-225 (30 mL) was added to the aqueous layer of the pre-divided liquid and re-extracted, and the obtained organic phase was combined with the previously obtained organic phase. Anhydrous sodium sulfate was added to the organic phase, and the mixture was stirred, and then insoluble matter was removed by vacuum filtration. The obtained organic phase was concentrated by an evaporator and then purified by silica gel column chromatography (mobile phase: n-pentane) to obtain a compound represented by NDM-2PPVE. The yield was 9.3 g and the yield was 84%.
^{1 1} H-NMR (CDCl3): δ (ppm) 6.3 to 6.0 (m, 2H), 6.0 to 5.7 (m, 2H), 4.1 to 3.9 (m, 2H) 3.8 to 3.6 (m, 2H), 2.91 (s, 1H), 2.68 (s, 1H), 1.6 to 0.8 (m, 4H).
¹⁹ F-NMR (CDCl3): δ (ppm) -81.9 (t, 6F, J = 3.1Hz), -85.2 to -85.8 (m, 2F), -87.1 to -87 .7 (m, 2F), -89.1 to -89.8 (m, 2F), -90.6 to -91.8 (m, 2F), -130.4 (s, 4F), 145 .0 to -145.3 (m, 2F).
GC-MS (CI): [M + H] ⁺ = 687

<Example 2-2> Ring-opening metathesis polymerization of NDM-2PPVE A Grubbs second generation catalyst (6.2 mg, 0.0073 mmol) is dissolved in dichloromethane (5 mL) in a 10 mL screw tube bottle under nitrogen, and a solution (B) is used. ) Was prepared. Next, NDM-2PPVE (1.0 g, 1.46 mmol) and dichloromethane (9 mL) obtained in Example 2-1 were charged into a 50 mL screw tube bottle and dissolved, and then the previously prepared solution (B) was added. 1 mL (corresponding to 0.1 mol% of catalyst) was added and the mixture was reacted at room temperature for 3 hours. Then, ethyl vinyl ether (119 μL) was added to the reaction solution to terminate the polymerization, and then 30 mL of AE-3000 was added to dilute the reaction solution. After the diluted reaction solution was continuously added to methanol (200 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 50 ° C. The yield of the target polymer (P-NDM-2PPVE) was 95%.
A series of these reactions is shown below. In the formula, m is a positive integer indicating the number of repetitions in the repeating unit.

<Example 2-3>
The polymer (P-NDM-2PPVE) synthesized in Example 2-2 was dissolved in HFE-7300 manufactured by 3M at a concentration of 3 wt% to prepare an HFE-7300 solution of the polymer. Next, an HFE-7300 solution of P-NDM-2PPVE was applied to a glass substrate, coated uniformly using a spin coater, and then dried at 150 ° C. for 10 minutes to prepare an evaluation substrate. The water contact angle of the coated surface was 115 degrees, and the contact angle of n-hexadecane was 84 degrees.

<Example 3-1> Synthesis of fluorine-containing norbornene derivative NDM-2PHVE Potassium hydroxide (4.4 g, 78.4 mmol), acetonitrile (40 mL), bicyclo [2.2.1] hepta-5-en-2,2 -Dimethanol (3.0 g, 19.5 mmol) and fluorine-containing olefin (33.6 g, 77.8 mmol) represented by the following formula 1 are placed in a 300 mL round-bottom flask, and a Dimroth is attached to the flask for 3 hours. It was reacted. 35 g of ice and 35 g of tap water were placed in a 500 mL beaker and stirred, and the above reaction solution was slowly and continuously introduced into cold ice water. Further, AK-225 (30 mL) was added and stirred, and then the organic phase was separated. AK-225 (30 mL) was added to the aqueous layer of the pre-divided liquid and re-extracted, and the obtained organic phase was combined with the previously obtained organic phase. Anhydrous sodium sulfate was added to the organic phase, and the mixture was stirred, and then insoluble matter was removed by vacuum filtration. The obtained organic phase was concentrated by an evaporator and then purified by silica gel column chromatography (mobile phase: n-hexane) to obtain a compound represented by NDM-2PHVE. The yield was 16.0 g and the yield was 81%.
^{1 1} H-NMR (CDCl3): δ (ppm) 6.25 (m, 1H), 6.06 (m, 1H), 5.93 (m, 1H), 5.76 (m, 1H), 4. 03 (m, 2H), 3.72 (m, 2H), 2.90 (s, 1H), 2.67 (s, 1H), 1.59 to 1.50 (m, 3H), 0.84 (M, 1H).
¹⁹ F-NMR (CDCl3): δ (ppm) -80.7 (m, 6F), -81.9 (t, 6F, J = 6.5Hz), -82.1 to -82.5 (m, 4F), -83.8 to -86.7 (m, 4F), -89.3 to -91.3 (m, 4F), -130.3 (s, 4F), -144.8 to 145 .5 (m, 2F), -145.7 (q, 2F, J = 23.1Hz).

<Example 3-2> Ring-opening metathesis polymerization of NDM-2PHVE A Grubbs second generation catalyst (16.7 mg, 0.020 mmol) is dissolved in dichloromethane (10 mL) in a 20 mL screw tube bottle under nitrogen, and a solution (C) is used. ) Was prepared. Next, NDM-2PHVE (2.0 g, 1.96 mmol), dichloromethane (19 mL) and 1,3-bis (trifluoromethyl) benzene obtained in Example 3-1 were charged into a 100 mL screw tube bottle and dissolved. After that, 1 mL (corresponding to 0.1 mol% of catalyst) of the previously prepared solution (C) was added, and the mixture was reacted at room temperature for 3 hours. Then, ethyl vinyl ether (160 μL) was added to the reaction solution to terminate the polymerization, and then 20 mL of AK-225 was added to dilute the reaction solution. After the diluted reaction solution was continuously added to methanol (200 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 50 ° C. The yield of the target polymer (P-NDM-2PHVE) was 95%.
A series of these reactions is shown below. In the formula, m is a positive integer indicating the number of repetitions in the repeating unit.

<Example 3-3>
The polymer (P-NDM-2PHVE) synthesized in Example 3-2 was dissolved in HFE-7300 manufactured by 3M at a concentration of 3 wt% to prepare an HFE-7300 solution of the polymer. Next, an HFE-7300 solution of P-NDM-2PHVE was applied to a glass substrate, coated uniformly using a spin coater, and then dried at 150 ° C. for 10 minutes to prepare an evaluation substrate. The water contact angle of the coated surface was 124 degrees, and the contact angle of n-hexadecane was 87 degrees.

<Example 4-1> Synthesis of fluorine-containing norbornene derivative NDM-2,3-2PHVE Potassium hydroxide (7.28 g, 129.7 mmol), acetonitrile (100 mL), bicyclo [2.2.1] hepta-5-ene -2,3-Dimethanol (5.0 g, 32.4 mmol) and a fluorine-containing olefin represented by the following formula 1 (56.0 g, 129.7 mmol) were placed in a 200 mL round-bottom flask, and a Dimroth was attached to 70. The reaction was carried out at ° C. for 4 hours. 50 g of ice and 50 g of tap water were placed in a 500 mL beaker and stirred, and the above reaction solution was slowly and continuously introduced into cold ice water. Further, AK-225 (100 mL) was added and stirred, and then the organic phase was separated. AK-225 (50 mL) was added to the aqueous layer of the pre-divided liquid and re-extracted, and the obtained organic phase was combined with the previously obtained organic phase. Anhydrous sodium sulfate was added to the organic phase, and the mixture was stirred, and then insoluble matter was removed by vacuum filtration. The obtained organic phase was concentrated by an evaporator and then purified by silica gel column chromatography (mobile phase: n-hexane) to obtain a compound represented by NDM-2,3-2PHVE. The yield was 26.4 g and the yield was 80%.
^{1 1} H-NMR (CDCl3): δ (ppm) 6.18 (m, 2H), 5.93 (m, 1H), 5.75 (m, 1H), 3.6-4.1 (m, 4H) ), 2.95 (s, 2H), 2.8-2.50 (m, 2H), 1.3-1.6 (m, 2H).
¹⁹ F-NMR (CDCl3): δ (ppm) -80.7 (m, 6F), -81.9 (m, 6F), -82.1 to -82.5 (m, 4F), -83. 8 to -86.7 (m, 4F), -89.5 to 90.9 (m, 4F), -130.2 (s, 4F), -144.9 to -145.2 (m, 2F) ), -145.6 to -145.8 (m, 2F).

<Example 4-2> Ring-opening metathesis polymerization of NDM-2,3-2PHVE Grubbs second generation catalyst (16.7 mg, 0.020 mmol) is dissolved in dichloromethane (10 mL) in a 20 mL screw tube bottle under nitrogen. , Solution (D) was prepared. Next, NDM-2,3-2PHVE (2.0 g, 1.96 mmol) and dichloromethane (19 mL) obtained in Example 4-1 were charged into a 100 mL screw tube bottle and dissolved, and then the solution prepared above was prepared. 1 mL (corresponding to 0.1 mol% of catalyst) of (D) was added, and the mixture was reacted at room temperature for 3 hours. Then, ethyl vinyl ether (160 μL) was added to the reaction solution to terminate the polymerization, and then 20 mL of AK-225 was added to dilute the reaction solution. After the diluted reaction solution was continuously added to methanol (200 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 50 ° C. The yield of the target polymer (P-2,3-NDM-2PHVE) was 79%.
A series of these reactions is shown below. In the formula, m is a positive integer indicating the number of repetitions in the repeating unit.

<Example 4-3>
The polymer (P-2,3-NDM-2PHVE) synthesized in Example 4-2 was dissolved in HFE-7300 manufactured by 3M at a concentration of 3 wt% to prepare an HFE-7300 solution of the polymer. Next, an HFE-7300 solution of P-2,3-NDM-2PHVE was applied to a glass substrate, coated uniformly using a spin coater, and then dried at 150 ° C. for 10 minutes to prepare an evaluation substrate. The water contact angle of the coated surface was 130 degrees, and the contact angle of n-hexadecane was 87 degrees.

<Example 5-1> Synthesis of fluorine-containing norbornene derivative NDM-2,2-2PEVE Under a nitrogen atmosphere, potassium hydroxide (14.8 g, 263 mmol), acetonitrile (269 mL) and bicyclo [2.2] were placed in a 1 L round-bottom flask. .1] Hepta-5-en-2,2-dimethanol (13.5 g, 87.6 mmol) was charged and stirred under ice-cooling to bring the internal temperature to 1.5 ° C. Then, C7PEVE (109 g, 262 mmol) was added dropwise over 10 minutes, a Dimroth condenser was attached, and the mixture was reacted at 85 ° C. for 7 hours in an oil bath. AE3000 (288 g) was added to the reaction solution, filtered through cerite, and the filtrate was concentrated with an evaporator. The concentrate was purified by silica gel column chromatography (mobile phase: AE3000) to obtain a compound represented by 2,2-NDM-2PEVE. The yield was 79.2 g and the yield was 92%.
1H-NMR (CDCl3): δ (ppm) 6.3 to 6.1 (m, 2H), 5.9 to 5.7 (m, 2H), 4.1 to 4.0 (m, 2H), 3.8 to 3.7 (m, 2H), 2.90 (s, 1H), 2.68 (s, 1H), 1.6 to 1.5 (m, 3H), 0.85 (m, 1H).
19F-NMR (CDCl3): δ (ppm) -53.9 to -54.0 (m, 4F), -56.1 (q, 4F, J = 9.16Hz), -57.6 (t, 6F) , J = 9.16Hz), -89.5 to -92.0 (m, 12F), -145.0 to 145.4 (m, 2F).

<Example 5-2> Ring-opening metathesis polymerization of 2,2-NDM-2PEVE in the presence of a chain transfer agent Grubbs first generation catalyst (921 mg, 1.12 mmol) is added to dichloromethane (921 mg, 1.12 mmol) in a 100 mL screw tube bottle under nitrogen. It was dissolved in 92 mL) to prepare a catalytic solution. Next, 2,2-NDM-2PEVE (55.1 g, 56.1 mmol), dichloromethane (412 mL) and hexafluorobenzene (56 mL) obtained in Example 5-1 were placed in a 1 L round-bottom flask and placed in ice water. Cooled. After degassing the inside of the reaction vessel under reduced pressure, the mixture was replaced with ethylene, and the mixture was placed in an ethylene atmosphere with a gas collection bag. After stirring at room temperature for 45 minutes, all the catalyst solutions prepared above were added and reacted at room temperature for 23 hours each. The reaction mixture was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain a compound represented by E-2,2-NDM-2PEVE. The yield was 47.3 g and the yield was 83%.
1H-NMR (CDCl3): δ (ppm) 5.93 to 5.69 (m, 4H), 5.09 to 4.94 (m, 4H), 3.94 to 3.71 (m, 4H), 2.63 to 2.52 (m, 2H), 2.00 to 1.76 (m, 2H), 1.57 to 1.42 (m, 2H).
19F-NMR (CDCl3): δ (ppm) -53.83 to -53.98 (m, 4F), -56.11 (td, 4F, J = 18.3, 9.2Hz), -57.56 (T, 6F, J = 9.2Hz), -89.48 to -92.31 (m, 12F), -144.66 to -145.16 (m, 2F).

<Example 6-1> Synthetic of fluorine-containing norbornene derivative N-PPVE Stainless steel (SUS316) high-pressure miniature cylinder with perfluoro (propyl vinyl ether) (20.0 g, 75.2 mmol), dicyclopentadiene (4.95 g, 37). .5 mmol), diethyl ether (8 mL) and hydroquinone (0.12 g, 1.12 mmol) were charged and reacted at 100-150 ° C. for 11 hours. The reaction solution was transferred to a 30 mL flask, and the fraction containing N-PPVE was fractionated by vacuum distillation (distillation conditions 30 to 50 mmHg, 60 to 65 ° C.). Further, purification was performed by silica gel column chromatography (mobile phase: n-hexane) to obtain a compound represented by N-PPVE. The yield was 1.83 g and the yield was 7%.
^{1 1} H-NMR (CDCl3): δ (ppm) 6.3 to 5.6 (m, 2H), 3.9 to 3.1 (m, 2H), 2.8 to 2.0 (m, 2H) ..
¹⁹ F-NMR (CDCl3): δ (ppm) -79.3 to -86.6 (2F), -81.7 to -81.9 (3F), -105.0 to -126.5 (3F) , -130.2 to -130.4 (2F).

<Example 6-2> Ring-opening metathesis polymerization of N-PPVE Grubbs second generation catalyst (9.8 mg, 0.011 mmol) is dissolved in dichloromethane (10 mL) in a 20 mL screw tube bottle under nitrogen, and the solution (A). ) Was prepared. Next, N-PPVE (0.38 g, 1.15 mmol), 1-hexene (2 μL) and dichloromethane (3 mL) obtained in Example 6-1 were charged into a 20 mL screw tube bottle and dissolved, and then first. 1 mL (corresponding to 0.1 mol% of catalyst) of the prepared solution (A) was added, and the mixture was reacted at room temperature for 3 hours. Then, ethyl vinyl ether (93 μL) was added to the reaction solution to terminate the polymerization, and then 5 mL of AE-3000 (manufactured by AGC) was added. Next, the reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography (mobile phase: AE-3000) to obtain a compound represented by PN-PPVE. The yield of the target polymer (PN-PPVE) was 66%. A series of these reactions is shown below. In the formula, m is a positive integer indicating the number of repetitions in the repeating unit.

<Example 6-3>
The polymer (PN-PPVE) synthesized in Example 6-2 was dissolved in HFE-7200 manufactured by 3M at a concentration of 3 wt% to prepare an HFE-7200 solution of the polymer. Next, an HFE-7200 solution of P-NM-PPVE was applied to a glass substrate, coated uniformly using a spin coater, and then dried at 150 ° C. for 10 minutes to prepare an evaluation substrate. The water contact angle of the coated surface was 104 degrees, and the contact angle of n-hexadecane was 54 degrees.

<Example 7-1> Fluorine-containing olefin (25.4 g, 61.0 mmol) represented by the following formula 2 and dicyclopentadiene (25.4 g, 61.0 mmol) in a high-pressure miniature cylinder made of synthetic stainless steel (SUS316) of a fluorine-containing norbornene derivative N-PEVE. 3.93 g, 29.7 mmol) and hydroquinone (0.10 g, 0.92 mmol) were charged and reacted at 180 ° C. for 20 hours. The reaction mixture was transferred to a 30 mL flask and purified by vacuum distillation to obtain a compound represented by N-PEVE (57 to 62 ° C., 5 mmHg). The yield was 14.6 g and the yield was 51%.
^{1 1} H-NMR (CDCl3): δ (ppm) 6.3 to 5.6 (m, 2H), 3.8 to 3.1 (m, 2H), 2.8 to 2.0 (m, 2H) ..
¹⁹ F-NMR (CDCl3): δ (ppm) -53.7 to -54.1 (2F), -56.0 to -56.3 (2F), -57.4 to -57.7 (3F) , -81.8 to -91.0 (4F), -104.9 to -132.2 (3F).
GC-MS (EI): [M] + = 480

<Example 7-2> Ring-opening metathesis polymerization of N-PEVE A Grubbs second generation catalyst (7.1 mg, 0.0083 mmol) is dissolved in dichloromethane (10 mL) in a 20 mL screw tube bottle under nitrogen, and a solution (B) is used. ) Was prepared. Next, N-PEVE (0.40 g, 0.83 mmol), 1-hexene (2 μL) and dichloromethane (4 mL) obtained in Example 7-1 were charged into a 30 mL screw tube bottle and dissolved, and then first. 1 mL (corresponding to 0.1 mol% of catalyst) of the prepared solution (B) was added, and the mixture was reacted at room temperature for 3 hours. Then, ethyl vinyl ether (68 μL) was added to the reaction solution to terminate the polymerization, and then 5 mL of AE-3000 (manufactured by AGC) was added. Next, the reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography (mobile phase: AE-3000) to obtain a compound represented by PN-PEVE. The yield of the target polymer (PN-PEVE) was 76%. A series of these reactions is shown below. In the formula, m is a positive integer indicating the number of repetitions in the repeating unit.

<Example 7-3>
The polymer (PN-PEVE) synthesized in Example 7-2 was dissolved in HFE-7200 manufactured by 3M at a concentration of 3 wt% to prepare an HFE-7200 solution of the polymer. Next, an HFE-7200 solution of PN-PEVE was applied to a glass substrate, coated uniformly using a spin coater, and then dried at 150 ° C. for 10 minutes to prepare an evaluation substrate. The water contact angle of the coated surface was 119 degrees, and the contact angle of n-hexadecane was 73 degrees.

From the comparison between Example 1-3 (Comparative Example) and Example 2-3, Example 3-3 and Example 4-3 (Example), a polymer of a norbornene derivative having 2 or more substitutions of a fluorine-containing organic group was found. It was found that it has high liquid repellency. From the comparison between Example 6-3 (Comparative Example) and Example 7-3 (Example), the polymer of the norbornene derivative containing two or more ethereal oxygen atoms in the fluorine-containing organic group has high liquid repellency. I understood.

<Example 8-1> ROMP copolymerization of NM-PPVE and cyclopentene derivative (MCPC) Under a nitrogen atmosphere, NM-PPVE (1.0 g, 2.56 mmol) obtained in Example 1-1 was used as a main monomer, and 3-. Methyl cyclopentene-1-carboxylate (MCPC, 0.32 g, 2.56 mmol) was put into a 20 mL screw tube bottle as a copolymer, and finally a Grubbs second generation catalyst (2.2 mg, 0.0026 mmol) was charged at room temperature. Was reacted for 3 hours. Then, ethyl vinyl ether (209 μL) was added to the reaction solution to terminate the polymerization, and then chloroform (7 mL) and AK-225 (2 mL) were added to dissolve the polymer. After dropping the polymer solution into methanol (150 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 50 ° C. The yield was 1.13 g. The obtained polymer was dissolved in a mixed solution of deuterated chloroform and hexafluorobenzene, and ¹ H-NMR was measured. As a result, the obtained polymer was a copolymer represented by the initial copolymer A. The mol ratio of the components in the polymer was main monomer: commonomer = 1.0: 0.34. From this, the monomer conversion rate was 100% for the main monomer and 35% for the comonomer. From GPC analysis, the weight average molecular weight (Mw) of this polymer was 303,611, and the molecular weight distribution (Mw / Mn) was 2.091.
A series of these reactions is shown below. In the formula, m and n are positive integers indicating the number of repetitions in the repeating unit, respectively.

<Example 8-2> ROMP copolymerization of NM-PPVE and cyclopentene derivative (CPMO) Under a nitrogen atmosphere, NM-PPVE (1.0 g, 2.56 mmol) obtained in Example 1-1 was used as a main monomer and 4-. Hydroxymethyl-1-cyclopentene (CPMO, 0.25 g, 2.56 mmol) is put into a 20 mL screw tube bottle as a copolymer, and finally a Grubbs second generation catalyst (2.2 mg, 0.0026 mmol) is charged at room temperature. The reaction was carried out for 3 hours. Then, ethyl vinyl ether (209 μL) was added to the reaction solution to terminate the polymerization, and then chloroform (3 mL), AK-225 (3 mL) and methanol (1 mL) were added to dilute the polymerization suspension. After introducing the entire amount of the polymer suspension into n-pentane (150 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 50 ° C. The yield was 0.85 g. The obtained polymer was dissolved in deuterated chloroform and measured by ¹ H-NMR. As a result, the obtained polymer was a copolymer represented by the initial copolymer B. The mol ratio of the components in the polymer was main monomer: commonomer = 1.0: 0.53. From this, the monomer conversion rate was 75% for the main monomer and 40% for the comonomer.

<Example 9-1> ROMP copolymerization of NDM-2PPVE and cyclopentene derivative (MCPC) Under a nitrogen atmosphere, NDM-2PPVE (1.0 g, 1.46 mmol) obtained in Example 2-1 was used as the main monomer, and 3-. Methyl cyclopentene-1-carboxylate (MCPC, 0.184 g, 1.46 mmol) was put into a 6 mL screw tube bottle as a copolymer, and finally a Grubbs second generation catalyst (2.5 mg, 0.0029 mmol) was charged at room temperature. Was stirred for 30 minutes. Then, the reactor was heated in an oil bath at 80 ° C. for 5 minutes, returned to room temperature, and reacted for 4 hours. Then, ethyl vinyl ether (238 μL) was added to the reaction solution to terminate the polymerization, and then chloroform (2 mL) and AK-225 (1 mL) were added to dissolve the polymer. After dropping the polymer solution into methanol (100 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 60 ° C. The yield was 0.94 g. The obtained polymer was dissolved in a mixed solution of deuterated chloroform and hexafluorobenzene, and ¹ H-NMR was measured. As a result, the obtained polymer was a copolymer represented by the initial copolymer C. The mol ratio of the components in the polymer was main monomer: commonomer = 1.0: 0.67. From this, the monomer conversion rate was 83% for the main monomer and 56% for the comonomer. From GPC analysis, the weight average molecular weight (Mw) of this polymer was 240,525, and the molecular weight distribution (Mw / Mn) was 6.674.

<Example 9-2> ROMP copolymerization of NDM-2PPVE and cyclopentene derivative (CPMO) Under a nitrogen atmosphere, NDM-2PPVE (1.0 g, 1.46 mmol) obtained in Example 2-1 was used as a main monomer and 4-. Hydroxymethyl-1-cyclopentene (CPMO, 0.14 g, 1.46 mmol) was put into a 6 mL screw tube bottle as a copolymer, and finally a Grubbs second generation catalyst (2.5 mg, 0.0029 mmol) was charged at room temperature. The mixture was stirred for 30 minutes. Then, the reactor was heated in an oil bath at 80 ° C. for 5 minutes, returned to room temperature, and reacted for 4 hours. Then, ethyl vinyl ether (238 μL) was added to the reaction solution to terminate the polymerization, and then chloroform (2 mL) and methanol (1 mL) were added to dilute the polymerization suspension. After introducing the entire amount of the polymer suspension into n-hexane (150 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 60 ° C. to obtain a copolymer represented by the copolymer D. The yield was 0.80 g.

<Example 10-1> ROMP copolymerization of NDM-2PHVE and cyclopentene derivative (MCPC) Under a nitrogen atmosphere, NDM-2PHVE (1.0 g, 0.98 mmol) obtained in Example 3-1 was used as a main monomer, and 3-. Methyl cyclopentene-1-carboxylate (MCPC, 0.125 g, 0.98 mmol) was put into a 6 mL screw tube bottle as a copolymer, and finally a Grubbs second generation catalyst (0.79 mg, 0.0009 mmol) was charged at 60 ° C. Was reacted for 2 hours. Then, ethyl vinyl ether (80 μL) was added to the reaction solution to terminate the polymerization, and then AK-225 (4 mL) was added to dissolve the polymer. After dropping the polymer solution into methanol (100 mL), the precipitated polymer was recovered by vacuum filtration and dried under reduced pressure at 60 ° C. The yield was 0.72 g. The obtained polymer was dissolved in deuterated chloroform and measured by ¹ H-NMR. As a result, the obtained polymer was a copolymer represented by the initial copolymer E. The mol ratio of the components in the polymer was main monomer: commonomer = 1: 0.59. From this, the monomer conversion rate was 67% for the main monomer and 39% for the comonomer.

<Example 10-2> ROMP copolymerization of NDM-2PHVE and cyclopentene derivative (CPMO) Under a nitrogen atmosphere, NDM-2PHVE (1.0 g, 0.98 mmol) obtained in Example 3-1 was used as a main monomer and 4-. Hydroxymethyl-1-cyclopentene (CPMO, 97 mg, 0.99 mmol) was charged into a 6 mL screw tube bottle as a copolymer, and finally a Grubbs second generation catalyst (1.09 mg, 0.0013 mmol) was charged at 60 ° C. 1. The reaction was carried out for 5 hours. Then, ethyl vinyl ether (80 μL) was added to the reaction solution to terminate the polymerization, chloroform (1 mL) and methanol (2 mL) were added, and the mixture was stirred to prepare a polymer suspension. The polymer precipitated in the polymer suspension was recovered by vacuum filtration and dried under reduced pressure at 60 ° C. to obtain a copolymer represented by the copolymer F. The yield was 1.0 g.

<Example 11-1> Synthesis of fluorine-containing norbornene derivative (4) (1) Bicyclo [2.2.1] Hepta-5-en-2,2-dimethanol (3.50 g, 22.7 mmol), dichloromethane ( 45 mL) and 2,6-lutidine (5.82 g, 54.4 mmol) are placed in a 100 mL round-bottom flask and stirred under ice-cooling. Trifluoromethanesulfonic anhydride (14.0 g, 49.6 mmol) is added dropwise to the reaction solution under ice-cooling stirring. The reaction solution is purified by silica gel column chromatography to obtain a compound represented by NDM-Tf.

(2) Under a nitrogen atmosphere, NDM-Tf (1.30 g, 3.1 mmol), diethylene glycol dimethyl ether (20 mL), a fluorine-containing compound represented by the following formula 3 (2.16 g, 6.2 mmol) and cesium fluoride (2). 1.88 g, 12.4 mmol) is placed in a 100 mL round bottom flask and stirred at room temperature for 16 hours. Dichloromethane (50 mL) and saturated aqueous sodium hydrogen carbonate solution (50 mL) are added to the reaction solution, and the mixture is stirred and then the organic phase is separated. After adding anhydrous sodium sulfate to the organic phase and stirring, the insoluble matter is removed by vacuum filtration. The obtained organic phase is concentrated by an evaporator and then purified by silica gel column chromatography to obtain the compound represented by (4).

<Example 11-2> ROMP homopolymerization of fluorine-containing norbornene (2) Under a nitrogen atmosphere, a Grubbs second generation catalyst (9.9 mg, 0.012 mmol) was weighed in a 10 mL screw tube bottle and dissolved in dichloromethane (5 mL). Prepare a catalytic solution. Next, the compound (4) (2.0 g, 2.34 mmol) and dichloromethane (19 mL) obtained in Example 11-1 were charged into a 100 mL screw tube bottle and dissolved, and then 1 mL of the catalyst solution prepared above was added. (Equivalent to 0.1 mol% of catalyst) is added and reacted at room temperature for 3 hours. Then, ethyl vinyl ether (422 μL) is added to the reaction solution to terminate the polymerization, and then 40 mL of chloroform is added to dilute the polymerization suspension. After continuously introducing the polymer suspension into methanol (250 mL), the precipitated polymer is recovered by vacuum filtration and dried under reduced pressure at 50 ° C. to obtain the desired polymer.

<Example 12-1> Synthesis of Fluorine-Containing Norbornene Derivative (5) (1) Bicyclo [2.2.1] Hepta-5-en-2,3-dimethanol (3.50 g, 22.7 mmol), dichloromethane ( 45 mL) and 2,6-lutidine (5.82 g, 54.4 mmol) are placed in a 100 mL round-bottom flask and stirred under ice-cooling. Trifluoromethanesulfonic anhydride (14.0 g, 49.6 mmol) is added dropwise to the reaction solution under ice-cooling stirring. The reaction solution is purified by silica gel column chromatography to obtain a compound represented by 2,3-NDM-Tf.

(2) Under a nitrogen atmosphere, 2,3-NDM-Tf (1.30 g, 3.1 mmol), diethylene glycol dimethyl ether (20 mL), a fluorine-containing compound represented by the following formula 3 (2.16 g, 6.2 mmol) and Cesium fluoride (1.88 g, 12.4 mmol) is placed in a 100 mL round bottom flask and stirred at room temperature for 16 hours. Dichloromethane (50 mL) and saturated aqueous sodium hydrogen carbonate solution (50 mL) are added to the reaction solution, and the mixture is stirred and then the organic phase is separated. After adding anhydrous sodium sulfate to the organic phase and stirring, the insoluble matter is removed by vacuum filtration. The obtained organic phase is concentrated by an evaporator and then purified by silica gel column chromatography to obtain the compound represented by (5).

<Example 12-2> ROMP homopolymerization of fluorine-containing norbornene (5) Under a nitrogen atmosphere, a Grubbs second generation catalyst (9.9 mg, 0.012 mmol) was weighed in a 10 mL screw tube bottle and dissolved in dichloromethane (5 mL). Prepare a catalytic solution. Next, the compound (5) (2.0 g, 2.34 mmol) and dichloromethane (19 mL) obtained in Example 12-1 were charged into a 100 mL screw tube bottle and dissolved, and then 1 mL of the catalyst solution prepared above was added. (Equivalent to 0.1 mol% of catalyst) is added and reacted at room temperature for 3 hours. Then, ethyl vinyl ether (422 μL) is added to the reaction solution to terminate the polymerization, and then 40 mL of chloroform is added to dilute the polymerization suspension. After continuously introducing the polymer suspension into methanol (250 mL), the precipitated polymer is recovered by vacuum filtration and dried under reduced pressure at 50 ° C. to obtain the desired polymer.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on September 21, 2017 (Japanese Patent Application No. 2017-181540), the contents of which are incorporated herein by reference.

According to the present invention, a novel fluoropolymer containing a constituent unit derived from a fluorine-containing norbornene derivative and a constituent unit derived from a cyclopentene derivative can be obtained, and the polymer can be used as a functional polymer as an electric / electronic material or a semiconductor material. , Optical materials, medical instruments / cell culture materials, liquid repellent materials, elastomer materials, cross-linking agents, etc.

Claims (16)

A fluorine-containing compound represented by the following general formula 1.

However, X ¹¹ and X ¹² are independently hydrogen atoms or fluorine atoms, and R ¹¹ and R ¹² are monovalent fluorine-containing hydrocarbon groups having 1 to 200 carbon atoms each independently having an ethereal oxygen atom . , A11, a12 are 0, 1 or 2, respectively. The R ¹¹ And R ¹² The fluorine-containing compound according to claim 1, which is a monovalent fluorine-containing hydrocarbon group having 1 to 100 carbon atoms, each independently having an ethereal oxygen atom. A fluorine-containing compound represented by the following general formula 2.

However, X ²¹ and X ²² are independently hydrogen atoms or fluorine atoms, and R ²¹ and R ²² are monovalent fluorine-containing hydrocarbon groups having 1 to 200 carbon atoms each independently having an ethereal oxygen atom . , A21 and a22 are 1 or 2 independently, respectively. The R ²¹ And R ²² The fluorine-containing compound according to claim 3, wherein each is a monovalent fluorine-containing hydrocarbon group having 1 to 100 carbon atoms and each independently has an ethereal oxygen atom. A fluorine-containing polymer containing a structural unit represented by the following general formula 11 or a structural unit represented by the following general formula 12.

However, X ¹¹ and X ¹² are independently hydrogen atoms or fluorine atoms, and R ¹¹ and R ¹² are monovalent fluorine-containing hydrocarbon groups having 1 to 200 carbon atoms each independently having an ethereal oxygen atom . , A11 and a12 are independently 0, 1 or 2, respectively, and m11 is a natural number representing the number of repetitions in the repetition unit. The fluorine-containing polymer according to claim 5, wherein R ¹¹ and R ¹² are monovalent fluorine-containing hydrocarbon groups having 1 to 100 carbon atoms each independently having an ethereal oxygen atom . A fluorine-containing polymer containing a structural unit represented by the following general formula 21 or a structural unit represented by the following general formula 22.

However, X ²¹ and X ²² are independently hydrogen atoms or fluorine atoms, and R ²¹ and R ²² are monovalent fluorine-containing hydrocarbon groups having 1 to 200 carbon atoms each independently having an ethereal oxygen atom , a21 and a22. Are independently 1 or 2 , and m21 is a natural number representing the number of repetitions in the repeating unit. The fluorine-containing polymer according to claim 7, wherein R ²¹ and R ²² are monovalent fluorine-containing hydrocarbon groups having 1 to 100 carbon atoms, each of which has an ethereal oxygen atom independently . A fluorine-containing polymer containing a structural unit represented by the following general formula 11'.

However, X ¹¹ and X ¹² are independently hydrogen atoms or fluorine atoms, and R ¹¹ and R ¹² are monovalent fluorine-containing hydrocarbon groups having 1 to 200 carbon atoms each independently having an ethereal oxygen atom . , A11 and a12 are independently 0, 1 or 2, respectively, and m11 is a natural number representing the number of repetitions in the repetition unit. A fluorine-containing polymer containing a structural unit represented by the following general formula 21'.

However, X ²¹ and X ²² are independently hydrogen atoms or fluorine atoms, and R ²¹ and R ²² are monovalent fluorine-containing hydrocarbon groups having 1 to 200 carbon atoms each independently having an ethereal oxygen atom . , A21 and a22 are independently 1 or 2, respectively, and m21 is a natural number representing the number of repetitions in the repetition unit. A method for producing a fluorine-containing polymer containing a structural unit represented by the following general formula 11 by polymerizing a fluorine-containing compound represented by the following general formula 1 in the presence of a metal-carbene complex catalyst.

However, X ¹¹ , X ¹² Are independently hydrogen or fluorine atoms, and R ¹¹ , R ¹² Is a monovalent fluorine-containing hydrocarbon group having 1 to 200 carbon atoms independently having an ethereal oxygen atom, a11 and a12 are independently 0, 1 or 2, respectively, and m11 is the number of repetitions in the repeating unit. It is a natural number to represent. A method for producing a fluorine-containing polymer containing a structural unit represented by the following general formula 12, which polymerizes a fluorine-containing compound represented by the following general formula 1.

However, X ¹¹ , X ¹² Are independently hydrogen or fluorine atoms, and R ¹¹ , R ¹² Is a monovalent fluorine-containing hydrocarbon group having 1 to 200 carbon atoms independently having an ethereal oxygen atom, a11 and a12 are independently 0, 1 or 2, respectively, and m11 is the number of repetitions in the repeating unit. It is a natural number to represent. A method for producing a fluorine-containing polymer containing a structural unit represented by the following general formula 21, which polymerizes a fluorine-containing compound represented by the following general formula 2 in the presence of a metal-carbene complex catalyst.

However, X ²¹ , X ²² Are independently hydrogen or fluorine atoms, and R ²¹ , R ²² Is a monovalent fluorine-containing hydrocarbon group having 1 to 200 carbon atoms independently having an ethereal oxygen atom, a21 and a22 are independently 1 or 2, and m21 is a natural number representing the number of repetitions of the repeating unit. Is. A method for producing a fluorine-containing polymer containing a structural unit represented by the following general formula 22, which polymerizes the fluorine-containing compound represented by the following general formula 2.

However, X ²¹ , X ²² Are independently hydrogen or fluorine atoms, and R ²¹ , R ²² Is a monovalent fluorine-containing hydrocarbon group having 1 to 200 carbon atoms independently having an ethereal oxygen atom, a21 and a22 are independently 1 or 2, and m21 is a natural number representing the number of repetitions of the repeating unit. Is. A method for producing a fluorinated polymer containing a structural unit represented by the following general formula 11', which hydrogenates a fluorinated polymer containing the structural unit represented by the following general formula 11.

However, X ¹¹ , X ¹² Are independently hydrogen or fluorine atoms, and R ¹¹ , R ¹² Is a monovalent fluorine-containing hydrocarbon group having 1 to 200 carbon atoms independently having an ethereal oxygen atom, a11 and a12 are independently 0, 1 or 2, respectively, and m11 is the number of repetitions in the repeating unit. It is a natural number to represent. A method for producing a fluorinated polymer containing a structural unit represented by the following general formula 21', which hydrogenates a fluorinated polymer containing the structural unit represented by the following general formula 21.

However, X ²¹ , X ²² Are independently hydrogen or fluorine atoms, and R ²¹ , R ²² Is a monovalent fluorine-containing hydrocarbon group having 1 to 200 carbon atoms independently having an ethereal oxygen atom, a21 and a22 are independently 1 or 2, and m21 is a natural number representing the number of repetitions of the repeating unit. Is.