WO2018038132A1 - Fluorine-containing polymer - Google Patents

Abstract

Provided is a polymer represented by formula (I): -(A-B)_n- (wherein, the respective symbols are as defined in the description).

Description

Fluoropolymer

The present invention relates to a fluorine-containing polymer.

Because of its high heat resistance and chemical resistance, many fluororesins are used in various fields. As such a fluororesin, for example, an alternating copolymer of fluorine-containing alkylene and non-fluorine alkylene is known (Non-Patent Document 1).

The above-mentioned copolymer can be obtained by polyaddition of a bisolefin and a fluorine-containing alkylene diiodide, but since the raw materials to be polyadded are limited, the structures that can be designed are limited. Therefore, it has been difficult to give such a polymer a desired function.

Therefore, an object of the present invention is to provide fluorine-containing resins having various structures.

As a result of intensive studies, the present inventors have paid attention to the fact that halogen atoms are introduced into the main chain as a result of the polyaddition reaction in the above-mentioned copolymer, and various grafts are present at the locations where the halogen atoms are present. It has been found that by introducing a chain, the copolymer can be imparted with characteristics corresponding to the structure of the graft chain.

That is, the present invention provides the following first aspect:
The following formula (I):
-(AB) _n- (I)
[Where:
A is —R ¹¹ _p —;
Each of R ¹¹ is independently a fluorine-containing alkylene group;
p is an integer from 1 to 10;
Each B is independently B ^a or B ^b ;
B ^a is ^{independently, -CHR 5 -CR 6 X-R} 2 -R 1 -R 3 -CR 6 X-CHR 5 - is and;
B ^b is independently —CR ⁵ ═CR ⁶ —R ² —R ¹ —R ³ —CR ⁶ ═CR ⁵ —:
Provided that at least one ^Ba is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene group -R ⁸ - a and;
R ² represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CH ₂ O—, —C (O) —, —C (O) —O— or —C (O) —NR ^9. -Is;
R ³ represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —OCH ₂ —, —C (O) —, —O—C (O) — or —NR ⁹ —C (O) —. Is;
Each R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ is independently a single bond or an alkylene group having 1 to 6 carbon atoms;
Each R ⁸ is independently a single bond, an oxyalkylene group having 1 to 6 carbon atoms or an alkylenedioxy group having 1 to 6 carbon atoms;
Each R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
X is a halogen atom or — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ :
Provided that at least one — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ is present;
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom, a halogen atom or an organic group;
R ¹⁹ is a hydrogen atom, a halogen atom or an organic group;
k is an arbitrary integer;
n is an arbitrary integer. ]
The polymer represented by these is provided.

In the second aspect, the present invention provides the following:
Formula (I ′) below:
− (A−B _x ) _n − (I ′)
[Where:
A is —R ¹¹ _p —;
Each of R ¹¹ is independently a fluorine-containing alkylene group;
p is an integer from 1 to 10;
Each B is independently B ^a or B ^b ;
B ^a is ^{independently, -CHR 5 -CR 6 X-R} 2 -R 1 -R 3 -CR 6 X-CHR 5 - is and;
B ^b is independently —CR ⁵ ═CR ⁶ —R ² —R ¹ —R ³ —CR ⁶ ═CR ⁵ —:
Provided that at least one ^Ba is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CH ₂ O—, —C (O) —, —C (O) —O— or —C (O) —NR ^9. -Is;
R ³ represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —OCH ₂ —, —C (O) —, —O—C (O) — or —NR ⁹ —C (O) —. Is;
Each R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ is independently a single bond or an alkylene group having 1 to 6 carbon atoms;
Each R ⁸ is independently a single bond, an oxyalkylene group having 1 to 6 carbon atoms or an alkylenedioxy group having 1 to 6 carbon atoms;
Each R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
X is a halogen atom or — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ :
Provided that at least one — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ is present;
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom, a chlorine atom or an organic group;
R ¹⁹ is a hydrogen atom, a halogen atom or an organic group;
k is an arbitrary integer;
x is each independently an integer of 1 to 5 in units enclosed in parentheses with n;
n is an arbitrary integer. ]
The polymer represented by these is provided.

According to the present invention, a polymer having various characteristics can be provided by introducing a graft chain into the molecular main chain of the polymer.

The polymer of the present invention is a polymer composed of unit A and unit B.

The unit A is represented by -R ¹¹ _p- .

In the above formula, each R ¹¹ is independently a fluorine-containing alkylene group, and p is an integer of 1 to 10. Such a fluorine-containing alkylene group may be linear or branched, and may have one or more substituents.

The fluorinated alkylene group may be a fluorinated alkylene group having 1 to 10 carbon atoms, more preferably a fluorinated alkylene group having 2 to 6 carbon atoms. In a preferred embodiment, the fluorine-containing alkylene group may be a straight chain.

In the fluorine-containing alkylene group, the number of fluorine atoms is not particularly limited. That is, the fluorine-containing alkylene group may be a group in which a part of hydrogen atoms on the main chain carbon atom of the alkylene group is substituted with a fluorine atom, or the hydrogen atom on the main chain carbon atom of the alkylene group may be All of them may be substituted with fluorine atoms (so-called perfluoroalkylene group).

In one embodiment, R ¹¹ is a group represented by —R ¹³ _q —R ¹² —R ¹³ _r —.

In the formula, R ¹² is a C 1-8 perfluoroalkylene group, preferably perfluoromethylene or perfluoroethylene.

In the formula, each R ¹³ is independently CH ₂ or CHF. In one embodiment, R ¹³ is CH ₂ .

In the formula, q and r are each independently 0 or 1. In one embodiment, q and r are 0. In another embodiment, q and r are 1.

In a preferred embodiment, R ¹¹ is —CH ₂ CF ₂ —, —CH ₂ (CF ₂ ) ₆ CH ₂ —, —CH ₂ (CF ₂ ) ₈ CH ₂ —, — (CF ₂ ) ₂ —, — (CF _{2) 4} -, or - _{(CF 2) 6} - may be.

The units B are each independently ^Ba or ^Bb .

B ^a is a group represented by —CHR ⁵ —CR ⁶ XR ² —R ¹ —R ³ —CR ⁶ X—CHR ⁵ —.

B ^b is independently a group represented by —CR ⁵ ═CR ⁶ —R ² —R ¹ —R ³ —CR ⁶ ═CR ⁵ —.

In B ^a and B ^b , each code can be selected independently for each occurrence. That is, B ^a and B ^b may be the same or different for each repeating unit (AB) to which n is added. Preferably, B ^a and B ^b are the same in each repeating unit.

In one embodiment, the formula - _{(A-B) n} - in B is ^{B a.} _{That, - (A-B) n} - _{^{is, - (A-B a)}} n - is.

In another embodiment, some B in the _formula- (AB) _n -are B ^a and the remaining B is B ^b . That is,-(AB) _n -is-(AB ^a ) _{n '} -(AB ^b ) _{n "} -(where n' and n" are each independently an arbitrary integer) And the order in which the repeating units labeled n ′ or n ″ are present is not limited.

In the above formula, ^{R 1} is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - is.

The above “alkylene group” may be linear, branched, or cyclic. In one embodiment, the alkylene group is straight or branched. In one preferred embodiment, the alkylene group is linear. In this embodiment, the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and further preferably an alkylene group having 3 to 8 carbon atoms. In another preferred embodiment, the alkylene group is a cyclic alkylene. In this embodiment, the alkylene group is preferably a cyclic alkylene group having 3 to 20 carbon atoms, more preferably a cyclic alkylene group having 4 to 15 carbon atoms, still more preferably a cyclic alkylene group having 5 to 15 carbon atoms, and even more preferably. May be a cyclic alkylene group having 6 to 12 carbon atoms.

The above “arylene” is not particularly limited, but is a divalent group in which two hydrogen atoms are eliminated from an arene ring, for example, a benzene ring, a naphthalene ring, or an anthracene ring. Further, the bond with the other group may be in any position in the ring. For example, when the above “arylene” is phenylene, the bond with the other group is in the ortho, meta, or para position. It can be in either. Preferably, arylene is a phenylene group. Preferably, the phenylene group is a paraphenylene group.

The “(poly) oxyalkylene group” means one oxyalkylene group (so-called oxyalkylene group) and a group in which two or more oxyalkylene groups are linked (so-called polyoxyalkylene group). Including both. Preferably, it may be a group in which one or more oxyalkylene groups are linked.

The (poly) oxyalkylene group is preferably — (OC ₁ H _2l ) _m —. In the formula, C ₁ H _2l may be linear or branched.

In the formula, l is an integer of 1 to 5 independently for each unit to which m is attached. That is, the unit “OC ₁ H _2l ” to which m in the (poly) oxyalkylene group is attached is not necessarily the same in the (poly) oxyalkylene group, and may be different. For example, the (poly) oxyalkylene group may be — (OCH ₂ ) — (OCH ₂ CH ₂ ) —. In a preferred embodiment, the unit “OC ₁ H _2l ” to which m is attached is identical in the formula. In a preferred embodiment, l is an integer from 2 to 4.

In the formula, m is an integer of 1 to 10, preferably an integer of 2 to 6.

In a preferred embodiment, the (poly) oxyalkylene group is — (O—CH ₂ CH ₂ ) _m — or — (O—CH (CH ₃ ) —CH ₂ ) _m — (wherein m is 2-6) Yes).

R ⁷ is independently a single bond or an alkylene group having 1 to 6 carbon atoms. The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.

Each R ⁸ is independently a single bond, an oxyalkylene group having 1 to 6 carbon atoms or an alkylenedioxy having 1 to 6 carbon atoms. The oxyalkylene group having 1 to 6 carbon atoms is preferably an oxyalkylene group having 1 to 3 carbon atoms, more preferably an oxyalkylene group having 1 or 2 carbon atoms. The alkylene dioxy having 1 to 6 carbon atoms is preferably alkylene dioxy having 1 to 3 carbon atoms, more preferably alkylene dioxy having 1 or 2 carbon atoms.

In the above formula, R ² represents a single bond, an alkylene group having 1 to 6 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms, such as an alkylene group having 1 or 2 carbon atoms), —O—, —CH ₂ O—, —C (O) —, —C (O) —O— or —C (O) —NR ⁹ —.

In the above formula, R ³ represents a single bond, an alkylene group having 1 to 6 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms such as 1 or 2 carbon atoms), —O—, —OCH ₂ —, — C (O) —, —O—C (O) — or —NR ⁹ —C (O) —.

Each R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (preferably a methyl group).

In the above formula, each R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (preferably a methyl group), preferably a hydrogen atom.

In the above formula, each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (preferably a methyl group), preferably a hydrogen atom.

In the above formula, X is — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ .

R ¹⁵ to R ¹⁸ may have any structure depending on the compound used when introducing the X group in the above formula.

R ¹⁵ to R ¹⁸ are each independently, for example, a hydrogen atom, a halogen atom or an organic group.

The halogen atom is chlorine, bromine or iodine, preferably chlorine.

In one embodiment, R ¹⁵ to R ¹⁸ are each independently a hydrogen atom, a chlorine atom or an organic group.

The above organic group means a group containing a carbon atom. The organic group is not particularly limited, and may be a group in which a hydrogen atom is eliminated from a hydrocarbon group. The “hydrocarbon group” means a group containing a carbon atom and a hydrogen atom. Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. In this hydrocarbon group, a hydrogen atom may be substituted with a halogen atom, and one or more N, O, S, Si, amide, sulfonyl, siloxane may be present at the terminal or molecular chain. , Carbonyl, carbonyloxy and the like.

R ¹⁹ may be any structure depending on the compound used when introducing the X group in the above formula.

R ¹⁹ is, for example, a hydrogen atom, a halogen atom, or an organic group, and is a terminal group in the graft reaction described below.

The halogen atom is chlorine, bromine, or iodine, preferably bromine or iodine, more preferably iodine.

R ¹⁹ is preferably a hydrogen atom or a halogen atom, more preferably bromine or iodine, and even more preferably iodine.

In one embodiment, the iodine content of the polymer of the present invention is 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably substantially 0% by weight. By setting the iodine content of the polymer to 15% by weight or less, the polymer is further stabilized. By reducing the iodine content of the polymer, the polymer becomes more stable. Stable polymers are suitable for use in harsh environments exposed to heat, chemicals and plasma, and in electronic materials or semiconductor applications where outgassing is avoided.

The above k are each independently an arbitrary integer. In a preferred embodiment, k is an integer from 1-20. In one embodiment, k is 1. In another embodiment, k is 2-20.

In a preferred embodiment, R ¹⁵ , R ¹⁶ and R ¹⁷ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms, more preferably methyl or ethyl).

In a further preferred embodiment, R ¹⁵ and R ¹⁶ are a hydrogen atom, and R ¹⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms, more preferably methyl). And preferably a hydrogen atom.

In a preferred embodiment, R ¹⁸ represents an alkyl group, an aryl group, a pyrrolidonyl group, —R ²¹ — (O—C _a H _2a ) _b —OR ²² , —R ²¹ —NR ²² , —R ²¹ —OH, —R ^21. It can be —COOR ²² , or —R ²¹ —OCOR ²² .

R ²¹ is a single bond, an alkylene group having 1 to 6 carbon atoms (preferably having 1 to 3 carbon atoms, more preferably —CH ₂ — or —CH ₂ CH ₂ —, more preferably —CH ₂ —), A phenylene group or CO.

R ²² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (preferably an ethyl group or a methyl group, more preferably a methyl group).

The — (O—C _a H _2a ) _b — may be linear or branched. Preferably, — (O—C _a H _2a ) _b — is linear. A is an integer of 1 to 5, preferably an integer of 2 to 4, for example 2, independently for each unit to which b is attached. That is, the unit “OC _a H _2a ” to which b is attached may be the same or different in — (O—C _a H _2a ) _b —. In a preferred embodiment, the unit “OC _a H _2a ” to which b is attached is the same in the formula.

In one embodiment, CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ may have a repeating structure having styrenes, methacrylates, or acrylates as monomer units.

In one embodiment, CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ can be the following hydrophilic group:

[In the formula, each R ²⁵ independently represents a hydrogen atom or a methyl group;
k is an arbitrary integer, preferably an integer of 1 to 20,
n is an arbitrary integer, preferably an integer of 1 to 20. ]

Preferably, CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ may be the following group:

More preferably, CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ may be the following groups:

In another embodiment, CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ can be the following hydrophobic group.

[Wherein, each R ²⁶ independently represents an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group,
k is an arbitrary integer, preferably an integer of 1 to 20. ]

In a preferred embodiment, ^Ba is
—CH ₂ —CHX-alkylene-CHX—CH ₂ —;
—CH ₂ —CHX—CO—O-alkylene-O—CO—CHX—CH ₂ —;
—CH ₂ —CHX—CO—NR ⁹ -alkylene-NR ⁹ —CO—CHX—CH ₂ —;
—CH ₂ —CHX—CO—O—adamantane—O—CO—CHX—CH ₂ —;
—CH ₂ —CHX—CH ₂ —O-adamantane—O—CH ₂ —CHX—CH ₂ —;
—CH ₂ —CHX-phenylene-CHX—CH ₂ —; or —CH ₂ —CHX—CH ₂ —polyoxyalkylene—O—CH ₂ —CHX—CH ₂ —
It can be.

In a preferred embodiment, ^Ba is
—CH ₂ —CHX-alkylene-CHX—CH ₂ —;
—CH ₂ —CHX—CO—O-alkylene-O—CO—CHX—CH ₂ —;
—CH ₂ —CHX—CO—NR ⁹ -alkylene-NR ⁹ —CO—CHX—CH ₂ —;
—CH ₂ —CHX-phenylene-CHX—CH ₂ —; or —CH ₂ —CHX—CH ₂ —polyoxyalkylene—O—CH ₂ —CHX—CH ₂ —
It can be.

In a preferred embodiment, ^Ba is
—CH ₂ —CHX-alkylene-CHX—CH ₂ —;
—CH ₂ —CHX—CO—O-alkylene-O—CO—CHX—CH ₂ —; or —CH ₂ —CHX—CH ₂ —polyoxyalkylene—O—CH ₂ —CHX—CH ₂ —
It can be.

In a preferred embodiment, ^Ba is
-CH ₂ -CHX-alkylene-CHX-CH _2- ; or -CH ₂ -CHX-CO-O-alkylene-O-CO-CHX-CH _2-
It can be.

In one embodiment, ^Ba is
-CH ₂ -CHX-alkylene-CHX-CH _2- , or -CH ₂ -CHX-CO-O-alkylene-O-CO-CHX-CH _2- ;
CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ is

It can be. In such a combination, the main chain is hydrophobic B ^a, since X is a hydrophilic, by adjusting the type and amount of X groups, adjusting the hydrophilicity and hydrophobicity of the resulting polymer Can do.

In another embodiment, ^Ba is
-CH ₂ -CHX-CH ₂ - polyoxyalkylene _{-O-CH 2 -CHX-CH 2} -
CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ is

It can be. In such a combination, the main chain is hydrophilic B ^a, since X is a hydrophobic, by adjusting the type and amount of X groups, adjusting the hydrophilicity and hydrophobicity of the resulting polymer Can do.

In the above formula, n can be any integer. n is appropriately selected according to the desired degree of polymerization (or molecular weight).

The terminal of the polymer represented _by- (AB) _n -is not particularly limited, and may have a structure corresponding to the raw material or stopper used in the synthesis.

The average molecular weight of the polymer represented _by- (AB) _n -is not particularly limited, and can be appropriately set according to the purpose such as use. For example, in one embodiment, the polymer of the present invention has a weight average molecular weight of 5 × 10 ² to 5 × 10 ⁶ , preferably 1 × 10 ³ to 3 × 10 ⁶ , such as 5 × 10 ^2. ˜1 × 10 ⁵ , preferably 1 × 10 ³ to 3 × 10 ⁴ .

In one embodiment, the molecular weight distribution of the polymer of the present invention may be 1.3 to 3.0, preferably 1.3 to 2.5, more preferably 1.3 to 2.0. Here, the molecular weight distribution is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and is determined by Mw / Mn. When the molecular weight distribution is reduced, the viscosity of the polymer becomes lower, and the distribution of the crosslinked structure at the time of crosslinking becomes uniform, resulting in an increase in mechanical strength. It is also advantageous when the polymer is further subjected to a modification reaction, polymerization, cross-linking reaction, surface treatment, etc. even after completion of the polymerization.

The above polymer is obtained by polyadding a dihalide corresponding to the A structure and a diene corresponding to the B structure, and then reacting the obtained polymer with a monomer corresponding to X to introduce an X group. Can be obtained.

In particular,
(Step 1) The following formula (A1):
Hal-A-Hal (A1)
Wherein A is as defined above,
Hal is a halogen atom. ]
And a dihalide represented by the following formula (B1):
CHR ⁵ = CR ⁶ -R ² -R ¹ -R ³ -CR ⁶ = CHR ⁵ (B1)
[Wherein R ¹ , R ² , R ³ , R ⁵ and R ⁶ have the same meanings as described above. ]
And a diene represented by the following formula (C1):
— (A—CHR ⁵ —CR ⁶ Hal—R ² —R ¹ —R ³ —CR ⁶ Hal—CHR ⁵ ) _n — (C1)
[Wherein, A, Hal, R ¹ , R ² , R ³ , R ⁵ and R ⁶ are as defined above]. ]
To obtain a compound represented by
(Step 2) Next, the following formula (D1) corresponding to X is added to the compound represented by formula (C1):
CR ¹⁵ R ¹⁶ = CR ¹⁷ R ¹⁸ (D1)
A compound represented by the following formula (I):
-(AB) _n- (I)
[Wherein, A and B are as defined above. ]
Can be obtained.

(Process 1)
The conditions for the above polyaddition are not particularly limited, and those skilled in the art can appropriately select them according to the raw materials used and the desired products. For example, it can be performed as described in Non-Patent Document 1.

The halogen atom represented by Hal in the above formula (A1) is a chlorine atom, an iodine atom or a bromine atom, preferably an iodine atom or a bromine atom, more preferably an iodine atom.

The polyaddition in step 1 is preferably initiated by generating radicals by UV irradiation, visible light irradiation in the presence of a photoredox catalyst, addition of a one-electron reducing agent, or addition of a radical generator. .

The ultraviolet light source is not limited as long as it emits ultraviolet light. Examples thereof include a mercury lamp, a xenon lamp, a UV lamp, a halogen lamp, and an LED, and a high-pressure mercury lamp is preferably used. .

Examples of the photoredox catalyst include rhodamine B, ethion Y, [Ru (bpy) ₃ ] ⁺ analog, [Ir (bpy) ₃ ] ⁺ analog, and the like.

Examples of the one-electron reducing agent include lithium dithionite, sodium dithionite, potassium dithionite, cesium dithionite, copper (I) iodide, copper (I) bromide, copper (I) chloride, Examples thereof include triethylamine, tributylamine, ascorbic acid, ascorbate and the like, preferably sodium dithionite, copper (I) iodide, copper (I) bromide, and particularly preferably sodium dithionite.

Examples of the radical generator include organic peroxides, inorganic peroxides, and organic azo compounds, and organic peroxides are preferably used. Although not limited to the following, for example, benzoyl peroxide is used as the organic peroxide, potassium persulfite is used as the inorganic peroxide, and AIBN is used as the organic azo compound.

(Process 2)
The conditions for the graft reaction in step 2 are not particularly limited, and those skilled in the art can appropriately select the conditions according to the raw materials used and the desired products.

The graft reaction in Step 2 is preferably performed in the presence of a radical generator, a one-electron reducing agent, and a polymerization catalyst. These may be used alone or in admixture of two or more.

In one embodiment, the graft reaction in step 2 is performed using a combination of two or more selected from the above radical generator, one-electron reducing agent and polymerization catalyst. In a preferred embodiment, the graft reaction in step 2 is performed using a combination of two or more of the above radical generator and polymerization catalyst.

As the radical generator, the above-mentioned organic peroxides, inorganic peroxides, organic azo compounds and the like can be used.

Examples of the one-electron reducing agent include lithium dithionite, sodium dithionite, potassium dithionite, cesium dithionite, copper (I) iodide, copper (I) bromide, copper (I) chloride, Triethylamine, tributylamine, ascorbic acid, ascorbate and the like can be used.

Examples of the polymerization catalyst include phenols such as BHT, vitamin E and vitamin C (ascorbic acid and its salts), cyclohexadiene, diethoxyhydrophosphonium oxide, tetraalkylphosphonium iodide, tetraalkylammonium iodide, N -Iodosuccinimide, sodium iodide or the like can be used.

Formula (D1):
CR ¹⁵ R ¹⁶ = CR ¹⁷ R ¹⁸ (D1)
Is a so-called graft monomer and has an ethylenic double bond.

Examples of the compound represented by the formula (D1) include vinyl pyrrolidone, α-alkyl olefin, vinyl ether, allyl ether, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, styrene, vinyl acetate, It can be a derivative.

The compound represented by the formula (D1) may preferably be the following compound.

[In the formula, each R ²⁵ independently represents a hydrogen atom or a methyl group;
Each R ²⁶ independently represents an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group;
n is an arbitrary integer, preferably an integer of 1 to 20. ]

In step 1 above, preferably A and B are polymerized alternately. However, in Step 1, a portion in which B is continuously polymerized may occur. Specifically, a structure represented by -AB _{x '} -A- (wherein x' is an integer of 2 to 5) may occur. The present invention relates to such a polymer, namely the following formula (I ′):
− (A−B _x ) _n − (I ′)
[Where:
A is —R ¹¹ _p —;
Each of R ¹¹ is independently a fluorine-containing alkylene group;
p is an integer from 1 to 10;
Each B is independently B ^a or B ^b ;
B ^a is ^{independently, -CHR 5 -CR 6 X-R} 2 -R 1 -R 3 -CR 6 X-CHR 5 - is and;
B ^b is independently —CR ⁵ ═CR ⁶ —R ² —R ¹ —R ³ —CR ⁶ ═CR ⁵ —:
Provided that at least one ^Ba is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CH ₂ O—, —C (O) —, —C (O) —O— or —C (O) —NR ^9. -Is;
R ³ represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —OCH ₂ —, —C (O) —, —O—C (O) — or —NR ⁹ —C (O) —. Is;
Each R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ is independently a single bond or an alkylene group having 1 to 6 carbon atoms;
Each R ⁸ is independently a single bond, an oxyalkylene group having 1 to 6 carbon atoms or an alkylenedioxy group having 1 to 6 carbon atoms;
Each R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
X is a halogen atom or — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ :
Provided that at least one — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ is present;
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom, a chlorine atom or an organic group;
R ¹⁹ is a hydrogen atom, a halogen atom or an organic group;
k is an arbitrary integer;
x is each independently an integer of 1 to 5 in units enclosed in parentheses with n;
n is an arbitrary integer. ]
The polymer represented by these is provided.

In one embodiment, the abundance ratio of the unit A and the unit B in the polymer represented by the formula (I ′) is, for example, 1: 1 to 1: 1.5, preferably 1: 1 to 1: 1. 3, for example 1: 1 to 1: 1.2 or 1: 1 to 1: 1.1.

In one embodiment, the polymer represented by the above formula (I) of the present invention is used as a hydrophilizing agent. For example, the polymer of the present invention is used as a hydrophilizing agent for other polymer materials. The hydrophilization method is not particularly limited, and examples thereof include a method of molding after mixing with another polymer material, or a method of molding the polymer material and applying the polymer of the present invention to the surface thereof. The polymer of the present invention is particularly suitably used as a hydrophilizing agent for a polymer porous membrane formed from a polymer material.

Therefore, the present invention also provides mixing of the polymer of the present invention with other polymer materials.

Further, in one embodiment, the polymer represented by the formula (I) of the present invention described above can be used as a paint itself or as an additive to the paint. The polymer represented by the formula (I) of the present invention can have various functions, for example, can have a desired hydrophilicity and hydrophobicity, and thus is used as a coating material for various substrates and applications. be able to.

Moreover, this invention is an intermediate compound before introduce | transducing a graft chain, following formula (Ia):
-(AB _x ') _n- (Ia)
[Where:
A is —R ¹¹ _p —;
Each of R ¹¹ is independently a fluorine-containing alkylene group;
p is an integer from 1 to 10;
Each B ′ is independently B ^{a ′} or B ^{b ′} ;
B ^{a ′} is independently —CH ₂ —CHX′—CO—O—adamantane—O—CO—CHX′—CH ₂ —; —CH ₂ —CHX′—CH ₂ —O—adamantane—O—. CH ₂ —CHX′—CH ₂ —;
B ^{b 'are} each independently, -CH = CH-CO-O- adamantane -O-CO-CH = CH - ; - CH = CH-CH 2 -O- adamantane _-O-CH 2 -CH = CH -Is:
Provided that at least one ^{Ba ′} is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CH ₂ O—, —C (O) —, —C (O) —O— or —C (O) —NR ^9. -Is;
R ³ represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —OCH ₂ —, —C (O) —, —O—C (O) — or —NR ⁹ —C (O) —. Is;
Each R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ is independently a single bond or an alkylene group having 1 to 6 carbon atoms;
Each R ⁸ is independently a single bond, an oxyalkylene group having 1 to 6 carbon atoms or an alkylenedioxy group having 1 to 6 carbon atoms;
Each R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
X ′ is a halogen atom:
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom, a chlorine atom or an organic group;
R ¹⁹ is a hydrogen atom, a halogen atom or an organic group;
k is an arbitrary integer;
x is each independently an integer of 1 to 5 in units enclosed in parentheses with n;
n is an arbitrary integer. ]
The polymer represented by these is also provided.

Production Example 1: Polyaddition of dihalide and diene

In a Pyrex tube, 1,4-butanediol diacrylate (87.9 mg, 0.4 mmol) was dissolved in CH ₂ Cl ₂ (6 ml), and I (CF ₂ ) ₆ I (220.5 mg) and aqueous sodium thiosulfate solution. (314.9 mg, 2 ml) was added and stirred while irradiating with ultraviolet light for 16 hours using a 400 W high-pressure mercury lamp while keeping the temperature of the reaction system constant. After completion of the reaction, the product was purified by reprecipitation, and the polymer 2 (139.2 mg, yield 53%, Mn = 6.2 × 10 ³ , Mw = 9.3 × 10 ³ , Mw / Mn = 1.5) was obtained. Obtained.

¹ H NMR (400 MHz, CDCl ₃ )
δ = 6.70 (dd, CF ₂ C H = CH, J ₁ = 125.2 Hz, J ₂ = 15.6 Hz), 6.42 (dm, CF ₂ CH = C H , J = 352.4 Hz), 4.61 (dd, CF ₂ CH ₂ C H I, J ₁ = 10.4 Hz, J ₂ = 3.2 Hz), 4.54-3.90 (m, COOC H ₂ ), 3.41-3.22 (m, CF ₂ C H HCHI), 2.79-2.61 (m, CF ₂ CH H CHI), 1.87-1.53 (m, COOCH ₂ C ₂ H ₄ )
¹⁹ F NMR (376 MHz, CDCl ₃ ); -59.5, -113.1 (dt, x), δ-113.6 (s, y), -122.2 (s, x, y), -123.6 (s, y),- 124.1 (s, x)

Example 1

Polymer 2 obtained in Production Example 1 (73.3 mg, Mn = 6.2 × 10 ³ , Mw = 9.5 × 10 ³ , Mw / Mn = 1.6), N-vinylpyrrolidone 3 (0.11 mL) ) And benzoyl peroxide (7.6 mg) were weighed and added to the reaction vessel, and then toluene (2.5 mL) was added and dissolved. After replacing the inside of the reaction system with an inert gas, the mixture was heated and stirred for 2 hours under reflux conditions. After completion of the reaction, the product was purified by reprecipitation to obtain the target graft polymer 4 (60.6 mg, Mn = 5.5 × 10 ³ , Mw = 8.2 × 10 ³ , Mw / Mn = 1.5). .

¹ H NMR (400 MHz, CDCl ₃ )
δ = 6.70 (dm, CF ₂ C H = CH, J = 125.2 Hz), 6.42 (dm, CF ₂ CH = C H , J = 352.4 Hz), 4.90 (m, CF ₂ CH ₂ CH ₂ C H I) , 4.54-3.80 (m, COOC H ₂ ), 3.58-3.49 (m, NC H ₂ CH ₂ ), 2.85-2.73 (m, CF ₂ C H HCHI), 2.33-2.20 (m, CF ₂ CH H CHI) , 1.87-1.53 (m, COOCH ₂ C ₂ H ₄ )
¹⁹ F NMR (376 MHz, CDCl ₃ ); -113.7 (dt, x), δ-115.3 (s, y), -121.5 (s, y), -122.2 (s, x, y), -124.2 (s , x)

Example 2

Polymer 2 obtained in Production Example 1 (73.3 mg, Mn = 5.9 × 10 ³ , Mw = 9.5 × 10 ³ , Mw / Mn = 1.6), N, N-dimethyl-5-hexene -1-yl ester 5 (20.4 mg) and benzoyl peroxide (7.8 mg) were weighed and added to the reaction vessel, then 1,2-dichloroethane (2.5 mL) was added and dissolved. After replacing the inside of the reaction system with an inert gas, the mixture was heated and stirred for 2 hours under reflux conditions. After completion of the reaction, the product was purified by reprecipitation to obtain the desired graft polymer 6 (82.0 mg, Mn = 8.3 × 10 ³ , Mw = 1.5 × 10 ⁴ , Mw / Mn = 1.8). .

¹ H NMR (400 MHz, CDCl ₃ )
δ = 6.91-6.79 (m, CF ₂ C H = CH), 6.57-6.50 (m, CF ₂ CH = C H ), 4.60-3.90 (m, COOC H ₂ ), 4.02-3.04 (m, I H ) 2.75-2.10 (m, CF ₂ C H H), 1.90-1.62 (m, COOCH ₂ C ₂ H ₄ ), 1.46-1.14 (m, CHIC ₇ H ₁₄ )
¹⁹ F NMR (471 MHz, CDCl ₃ ); -113.6 (dt, x), δ-113.7 (s, y), -121.4 (s, y), -122.1 (s, x, y), -124.1 (s , x)

Production Example 2

In a Pyrex tube, 1,7-octadiene (0.4 mmol) was dissolved in CH ₂ Cl ₂ (6 ml), and I (CF ₂ ) ₆ I (0.4 mmol) and an aqueous sodium thiosulfate solution (2.0 mmol, 1 ml aqueous solution). ) And irradiated with ultraviolet light for 16 hours using a 450 W high pressure mercury lamp while keeping the temperature of the reaction system constant. After completion of the reaction, the product was purified by reprecipitation to obtain polymer 8 (184.2 mg, Mn = 1.1 × 10 ⁴ , Mw = 3.4 × 10 ⁴ , Mw / Mn = 3.2).

Example 3

Raw material polymer 8 (60.0 mg, Mn = 1.1 × 10 ⁴ , Mw = 3.4 × 10 ⁴ , Mw / Mn = 3.2), N-vinylpyrrolidone (0.11 mL) and peroxide in the reaction vessel Benzoyl (7.9 mg) was weighed and added to the reaction vessel, and then toluene (2.5 mL) was added and dissolved. After replacing the inside of the reaction system with an inert gas, the mixture was heated and stirred for 2 hours under reflux conditions. After completion of the reaction, purification is performed by reprecipitation to obtain the target graft polymer 9 (40.6 mg, Mn = 1.2 × 10 ⁴ , Mw = 4.9 × 10 ⁴ , Mw / Mn = 4.0). It was.

Production Example 3

To a mixed solution of Compound 10 (868.7 mg) in acetonitrile / water (1.9 ml / 1.9 ml), I (CF ₂ ) ₆ I (2.09 g), sodium dithionite (33.5 mg), and carbonic acid Sodium hydrogen (16.8 mg) was added, and the reaction system was replaced with an inert gas, followed by stirring at 45 ° C. for 16 hours. As a result of performing extraction operation and reprecipitation after the reaction, the target compound 11 was obtained in a yield of 59% (1.76 g, Mn = 7.4 × 10 ³ , Mw = 1.3 × 10 ⁴ , Mw / Mn = 1.8).

In the above table, MMA means methyl methacrylate, St means styrene, and EA means ethyl acrylate.

Example 4 (Entry 1)
In a Pyrex tube, compound 11 (235.2 mg) in dimethyl sulfoxide (DMSO) solution (1 ml), methyl methacrylate (608.5 mg), sodium dithionite (158.1 mg), and sodium bicarbonate (76. 2 mg) was added and the inside of the reaction system was replaced with an inert gas, followed by stirring at 60 ° C. for 17 hours. As a result of performing extraction operation and reprecipitation after the reaction, the target compound 12a was obtained in a yield of 90% (757.6 mg, Mn = 1.4 × 10 ⁴ , Mw = 3.5 × 10 ⁴ , Mw / Mn = 2.5).

Example 5 (Entry 2)
To a DMSO solution (1 ml) of compound 11 (230.9 mg), styrene (0.69 ml), sodium dithionite (159.0 mg), and sodium hydrogen carbonate (75.3 mg) were added, and the reaction was carried out at room temperature. After replacing the inside of the system with an inert gas, the mixture was stirred at 150 ° C. for 4 hours. As a result of performing extraction operation and reprecipitation purification after the reaction, the target compound 12b was obtained in a yield of 54% (462.6 mg, Mn = 1.5 × 10 ⁴ , Mw = 4.8 × 10 ⁴ , Mw / Obtained by Mn = 3.3).

Example 6
To a solution of compound 11 (133.3 mg) in DMSO (0.6 mL) was added ethyl acrylate (342.0 mg,), sodium dithionite (88.3 mg), and sodium bicarbonate (43.8 mg). After replacing the interior of the reaction system with an inert gas at room temperature, the mixture was stirred at 60 ° C. for 16 hours. After the reaction, extraction with dichloromethane / water was performed, followed by purification by reprecipitation using hexane. As a result, the target compound 12c was obtained in a yield of 52% (247.3 mg).

Production Example 4

An aqueous solution (25 ml) of I (CF ₂ ) ₆ I (2.68 g) and Na ₂ S ₂ O ₃ (3.95 g) against a dichloroethane solution (80 ml) of diacrylate compound (13) (1.38 g) And was irradiated with light by a high-pressure mercury lamp for 28 hours. After the reaction, purification by extraction operation and reprecipitation resulted in a yield of 42% (1.60 g, Mn = 3.8 × 10 ³ , Mw = 7.2 × 10 ³ , Mw / Obtained with Mn = 1.9).

Example 7 (Entry 1)
Compound 14 (77.2 mg, Mn = 3.8 × 10 ³ , Mw = 7.2 × 10 ³ , Mw / Mn = 1.9), methyl methacrylate (319.7 mg, 20 equivalents), tetrabutyl Ammonium iodide (57.7 mg, 1 equivalent) and toluene (0.08 ml) were added, and nitrogen bubbling was performed at room temperature for 30 minutes, followed by stirring at 110 ° C. for 2.5 hours. As a result of purification by reprecipitation using methanol after the reaction, the target compound 15a was obtained in a yield of 34% (136.7 mg, Mn = 1.3 × 10 ⁴ , Mw = 7.8 × 10 ⁴ , Mw /Mn=6.0).

Example 8 (Entry 2)
For compound 14 (77.3 mg, Mn = 3.8 × 10 ³ , Mw = 7.2 × 10 ³ , Mw / Mn = 1.9), acrylic acid (224.4 mg), tetrabutylammonium iodide ( 59.7 mg) and toluene (0.05 mL) were added, and the reaction system was replaced with an inert gas at room temperature, followed by stirring at 110 ° C. for 16 hours. As a result of purification by reprecipitation using methanol after the reaction, the target compound 15b was obtained in a yield of 10% (30.0 mg, Mn = 4.4 × 10 ³ , Mw = 6.1 × 10 ³ , Mw /Mn=1.4).

Example 9 (Entry 3)
Compound 14 (76.4 mg, Mw = 7.2 × 10 ³ , Mn = 3.8 × 10 ³ , Mw / Mn = 1.9) against 2-hydroxyethyl methacrylate (396.8 mg), N— Iodosuccinimide (NIS) (1.2 mg), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V70) (12.5 mg), and toluene (0.1 mL) were added, After replacing the interior of the reaction system with an inert gas at room temperature, the mixture was stirred at 40 ° C. for 7 hours. As a result of reprecipitation using hexane after the reaction, the target compound 17c was obtained in a yield of 17% (82.1 mg, Mn = 6.2 × 10 ³ , Mw = 9.3 × 10 ³ , Mw / Mn = 1.5).

Example 10 (Evaluation of hydrophilicity of polymer)
Sample preparation Polymers combined in the above production examples 1 and 4, Examples 1, 2, 5, 6, 7 and 9, and polystyrene (manufactured by Aldrich, Mn = 3.5 × 10 ⁴ , product number: 331655-1G) ) Were dissolved in dichloromethane so as to have a concentration of 0.1 wt% to prepare a polymer solution. The polymer solution was dropped on a cover glass and air-dried in a draft for 1 hour to prepare a polymer film.
-Measuring method The contact angle immediately after dropping deionized water (2 microliters) on the polymer film | membrane obtained above was measured.

From the above results, the use of the polymer 4 or 6 having a hydrophilic skeleton introduced after graft polymerization is more hydrophilic than the case of using the polymer 2 having no hydrophilic skeleton introduced. It was confirmed to be high. Further, it was confirmed that the graft polymer 12b having a hydrophilic skeleton has higher hydrophilicity than polystyrene which is a polymer of the graft chain. Further, when the polymer 15a or 15c having a hydrophilic skeleton introduced after graft polymerization is used, the polymer 15a or 15c may have higher hydrophilicity than the case of using the polymer 14 having no hydrophilic skeleton introduced. confirmed.

Since the polymer of the present invention can have various properties, it can be used in a wide range of applications.

Claims (13)

1. The following formula (I):
   -(AB) _n- (I)
   [Where:
   A is —R ¹¹ _p —;
   Each of R ¹¹ is independently a fluorine-containing alkylene group;
   p is an integer from 1 to 10;
   Each B is independently B ^a or B ^b ;
   B ^a is ^{independently, -CHR 5 -CR 6 X-R} 2 -R 1 -R 3 -CR 6 X-CHR 5 - is and;
   B ^b is independently —CR ⁵ ═CR ⁶ —R ² —R ¹ —R ³ —CR ⁶ ═CR ⁵ —:
   Provided that at least one ^Ba is present;
   R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
   R ² represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CH ₂ O—, —C (O) —, —C (O) —O— or —C (O) —NR ^9. -Is;
   R ³ represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —OCH ₂ —, —C (O) —, —O—C (O) — or —NR ⁹ —C (O) —. Is;
   Each R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
   Each R ⁶ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
   Each R ⁷ is independently a single bond or an alkylene group having 1 to 6 carbon atoms;
   Each R ⁸ is independently a single bond, an oxyalkylene group having 1 to 6 carbon atoms or an alkylenedioxy group having 1 to 6 carbon atoms;
   Each R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
   X is a halogen atom or — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ :
   Provided that at least one — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ is present;
   R ¹⁵ to R ¹⁸ are each independently a hydrogen atom, a chlorine atom or an organic group;
   R ¹⁹ is a hydrogen atom, a halogen atom or an organic group;
   k is an arbitrary integer;
   n is an arbitrary integer. ]
   A polymer represented by
2. Formula (I ′) below:
   − (A−B _x ) _n − (I ′)
   [Where:
   A is —R ¹¹ _p —;
   Each of R ¹¹ is independently a fluorine-containing alkylene group;
   p is an integer from 1 to 10;
   Each B is independently B ^a or B ^b ;
   B ^a is ^{independently, -CHR 5 -CR 6 X-R} 2 -R 1 -R 3 -CR 6 X-CHR 5 - is and;
   B ^b is independently —CR ⁵ ═CR ⁶ —R ² —R ¹ —R ³ —CR ⁶ ═CR ⁵ —:
   Provided that at least one ^Ba is present;
   R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
   R ² represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CH ₂ O—, —C (O) —, —C (O) —O— or —C (O) —NR ^9. -Is;
   R ³ represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —OCH ₂ —, —C (O) —, —O—C (O) — or —NR ⁹ —C (O) —. Is;
   Each R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
   Each R ⁶ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
   Each R ⁷ is independently a single bond or an alkylene group having 1 to 6 carbon atoms;
   Each R ⁸ is independently a single bond, an oxyalkylene group having 1 to 6 carbon atoms or an alkylenedioxy group having 1 to 6 carbon atoms;
   Each R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
   X is a halogen atom or — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ :
   Provided that at least one — (CR ¹⁵ R ¹⁶ —CR ¹⁷ R ¹⁸ ) _k —R ¹⁹ is present;
   R ¹⁵ to R ¹⁸ are each independently a hydrogen atom, a chlorine atom or an organic group;
   R ¹⁹ is a hydrogen atom, a halogen atom or an organic group;
   k is an arbitrary integer;
   x is each independently an integer of 1 to 5 in units enclosed in parentheses with n;
   n is an arbitrary integer. ]
   A polymer represented by
3. B
   —CH ₂ —CHX-alkylene-CHX—CH ₂ —;
   —CH ₂ —CHX—CO—O-alkylene-O—CO—CHX—CH ₂ —;
   —CH ₂ —CHX—CO—NR ⁹ -alkylene-NR ⁹ —CO—CHX—CH ₂ —;
   —CH ₂ —CHX—CO—O—adamantane—O—CO—CHX—CH ₂ —;
   —CH ₂ —CHX—CH ₂ —O-adamantane—O—CH ₂ —CHX—CH ₂ —;
   —CH ₂ —CHX-phenylene-CHX—CH ₂ —; or —CH ₂ —CHX—CH ₂ —polyoxyalkylene—O—CH ₂ —CHX—CH ₂ —
   Wherein X and R ⁹ are as defined in claim 1. ]
   The polymer of Claim 1 or 2 which is group represented by these.
4. B
   —CH ₂ —CHX-alkylene-CHX—CH ₂ —;
   —CH ₂ —CHX—CO—O-alkylene-O—CO—CHX—CH ₂ —; or —CH ₂ —CHX—CH ₂ —polyoxyalkylene—O—CH ₂ —CHX—CH ₂ —
   Wherein X and R ⁹ are as defined in claim 1. ]
   The polymer according to any one of claims 1 to 3, which is a group represented by:
5. B
   -CH ₂ -CHX-alkylene-CHX-CH _2- ; or -CH ₂ -CHX-CO-O-alkylene-O-CO-CHX-CH _2-
   Wherein X and R ⁹ are as defined in claim 1. ]
   The polymer according to any one of claims 1 to 4, which is a group represented by:
6. The polymer according to any one of claims 1 to 5, wherein CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ has a repeating structure having styrenes, methacrylates, or acrylates as monomer units.
7. CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ is:
   

   

   

   [In the formula, each R ²⁵ independently represents a hydrogen atom or a methyl group;
   k is an integer from 1 to 20,
   n is an arbitrary integer. ]
   The polymer according to any one of claims 1 to 6, which is a group represented by:
8. CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ is:
   

   

   [Wherein, each R ²⁶ independently represents an alkyl group having 1 to 6 carbon atoms,
   k is an integer of 1 to 20. ]
   The polymer according to any one of claims 1 to 6, which is a group represented by:
9. The polymer according to any one of claims 1 to 8, wherein at least one R ¹⁹ is an iodine atom.
10. The polymer according to any one of claims 1 to 9, wherein the content of iodine atoms is 15% by weight or less.
11. The polymer according to any one of claims 1 to 10, having a weight average molecular weight of 5.0 x 10 ³ to 5.0 x 10 ⁴ .
12. The polymer according to any one of claims 1 to 11, having a molecular weight distribution of 1.3 to 3.0.
13. The following formula (Ia):
    -(AB _x ') _n- (Ia)
    [Where:
    A is —R ¹¹ _p —;
    Each of R ¹¹ is independently a fluorine-containing alkylene group;
    p is an integer from 1 to 10;
    Each B ′ is independently B ^{a ′} or B ^{b ′} ;
    B ^{a ′} is independently —CH ₂ —CHX′—CO—O—adamantane—O—CO—CHX′—CH ₂ —; —CH ₂ —CHX′—CH ₂ —O—adamantane—O—. CH ₂ —CHX′—CH ₂ —;
    B ^{b 'are} each independently, -CH = CH-CO-O- adamantane -O-CO-CH = CH - ; - CH = CH-CH 2 -O- adamantane _-O-CH 2 -CH = CH -Is:
    Provided that at least one ^{Ba ′} is present;
    R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
    R ² represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CH ₂ O—, —C (O) —, —C (O) —O— or —C (O) —NR ^9. -Is;
    R ³ represents a single bond, an alkylene group having 1 to 6 carbon atoms, —O—, —OCH ₂ —, —C (O) —, —O—C (O) — or —NR ⁹ —C (O) —. Is;
    Each R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
    Each R ⁶ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
    Each R ⁷ is independently a single bond or an alkylene group having 1 to 6 carbon atoms;
    Each R ⁸ is independently a single bond, an oxyalkylene group having 1 to 6 carbon atoms or an alkylenedioxy group having 1 to 6 carbon atoms;
    Each R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
    X ′ is a halogen atom:
    R ¹⁵ to R ¹⁸ are each independently a hydrogen atom, a chlorine atom or an organic group;
    R ¹⁹ is a hydrogen atom, a halogen atom or an organic group;
    k is an arbitrary integer;
    x is each independently an integer of 1 to 5 in units enclosed in parentheses with n;
    n is an arbitrary integer. ]
    A polymer represented by