JPWO2018038132A1 - Fluorinated polymer - Google Patents

Abstract

Polymer represented by formula (I). -(AB) n-(I) wherein each symbol is as defined in the specification.

Description

  The present invention relates to a fluorine-containing polymer.

  Many fluorine resins are used in various fields because of their high heat resistance and chemical resistance. As such a fluorine resin, for example, an alternating copolymer of a fluorine-containing alkylene and a non-fluorine alkylene is known (Non-patent Document 1).

Macromolecules 1997, 30, 645-648

  The copolymer as described above is obtained by the polyaddition of a bis-olefin and a fluorine-containing alkylene oxide, but since the raw material to be polyadded is limited, the design that can be designed is limited. Therefore, it has been difficult to give such a polymer a desired function.

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

  As a result of intensive investigations, the present inventors focused attention on the introduction of a halogen atom on the main chain as a result of a polyaddition reaction in the above-mentioned copolymer, and various grafts were made at the place where this halogen atom is present. It has been found that the introduction of a chain can impart to the copolymer properties according to the structure of the graft chain.

That is, in the first aspect of the present invention,
The following formula (I):
-(A-B) _n- (I)
[In the formula:
A is -R ¹¹ _p- ;
Each R ¹¹ independently represents a fluorine-containing alkylene group;
p is an integer of 1 to 10;
Each B is independently B ^a or B ^b ;
Each B ^a is independently -CHR ⁵ -CR ⁶ XR ² -R ¹ -R ³ -CR ⁶ X-CHR ^5- ;
Each B ^b is independently -CR ⁵ = CR ⁶ -R ² -R ¹ -R ³ -CR ⁶ = CR ^5- :
With the proviso that at least one B ^a 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 is 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 -And
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)- And
Each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ independently represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁸ each independently represents 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 independently represents 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) be k ^{-R 19:}
In the formula, at least one ^- is _{^{(CR 15 R 16 -CR 17 R}} 18) k -R 19 are 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 any integer;
n is an arbitrary integer. ]
To provide a polymer represented by

The present invention is, in a second aspect,
The following formula (I '):
-(AB _x ) _n- (I ')
[In the formula:
A is -R ¹¹ _p- ;
Each R ¹¹ independently represents a fluorine-containing alkylene group;
p is an integer of 1 to 10;
Each B is independently B ^a or B ^b ;
Each B ^a is independently -CHR ⁵ -CR ⁶ XR ² -R ¹ -R ³ -CR ⁶ X-CHR ^5- ;
Each B ^b is independently -CR ⁵ = CR ⁶ -R ² -R ¹ -R ³ -CR ⁶ = CR ^5- :
With the proviso that at least one B ^a is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² is 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 -And
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)- And
Each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ independently represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁸ each independently represents 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 independently represents 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) be k ^{-R 19:}
In the formula, at least one ^- is _{^{(CR 15 R 16 -CR 17 R}} 18) k -R 19 are 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 any integer;
x is each independently an integer of 1 to 5 in the unit enclosed in parentheses with n added;
n is an arbitrary integer. ]
To provide a polymer represented by

  According to the present invention, a polymer having various properties 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 comprising unit A and unit B.

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

In said formula, R < ¹¹ > is respectively independently a fluorine-containing alkylene group, p is an integer of 1-10. Such a fluorine-containing alkylene group may be linear or branched, and may have one or more substituents.

  The above-mentioned fluorine-containing alkylene group is preferably a fluorine-containing alkylene group having 1 to 10 carbon atoms, more preferably a fluorine-containing alkylene group having 2 to 6 carbon atoms. In a preferred embodiment, the fluorine-containing alkylene group may be linear.

  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 by a fluorine atom, or a hydrogen atom on the main chain carbon atom of the alkylene group is It may be a group substituted with all fluorine atoms (so-called perfluoroalkylene group).

In one aspect, R ¹¹ is a group represented by -R ¹³ _q -R ¹² -R ¹³ _r- .

Wherein, R ¹² is a perfluoroalkylene group having 1 to 8 carbon atoms, preferably perfluoro methylene or perfluoro ethylene.

In the formulae, each R ¹³ is independently CH ₂ or CHF. In one aspect, R ¹³ is CH ₂ .

  In the formula, q and r are each independently 0 or 1. In one aspect, q and r are zero. 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 B ^a or B ^b .

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

Each B ^b is independently a group represented by —CR ⁵ CRCR ⁶ RR ² RR ¹ RR ³ CRCR ⁶ CRCR ⁵ −.

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

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

In another aspect, some B's in the _formula- (A-B) _n- are B ^a and the remaining B's are B ^b . That is,-(A-B) _{n- is-} (A- ^Ba ) _{n '} -(A- ^Bb ) _{n "} -(wherein, n' and n" are each independently an arbitrary integer. There is no limitation on the order in which repeating units with n ′ or n ′ ′ are present.

In said formula, R < ¹ > is an alkylene group, -R < ⁷ > -arylene-R < ⁷ >-, or -R < ⁷ >-(poly) oxyalkylene -R < ⁸ >-.

  The above "alkylene group" may be linear, branched or cyclic. In one aspect, the alkylene group is linear or branched. In one preferred embodiment, the alkylene group is linear. In this aspect, the alkylene group may be preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and still more preferably an alkylene group having 3 to 8 carbon atoms. In another preferred embodiment, the alkylene group is cyclic alkylene. In this aspect, 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 still more preferably Is 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. In addition, the bond to another group may be any position of cyclic, for example, when the above "arylene" is phenylene, the bond to another group is in ortho position, meta position or para position. It may be in any place. Preferably, arylene is a phenylene group. Also preferably, the phenylene group is a paraphenylene group.

  The above “(poly) oxyalkylene group” is a single oxyalkylene group (so-called, oxyalkylene group) and a group in which one or more oxyalkylene groups are linked to each other (so-called, polyoxyalkylene group) Encompass both. Preferably, it may be a group in which one or more oxyalkylene groups are linked.

The (poly) oxyalkylene group, _{preferably, - (OC l H 2l)} m - is. In the formula, C ₁ H _{2 l} 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 _{2 l} ” to which m is attached in the (poly) oxyalkylene group is not necessarily the same in the (poly) oxyalkylene group, and may be different. For example, (poly) oxyalkylene _{group, - (OCH 2) - (} OCH 2 CH 2) - it may be like. In a preferred embodiment, the units “OC ₁ H _{2 l} ” to which m is attached are identical in the formula. In a preferred embodiment, l is an integer of 2 to 4.

  In formula, m is an integer of 1-10, Preferably it is an integer of 2-6.

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 to 6) Yes).

Said R < ⁷ > is respectively independently a single bond or a C1-C6 alkylene group. The said C1-C6 alkylene group is preferably a C1-C3 alkylene group, more preferably a C1-C2 alkylene group.

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. The said C1-C6 oxyalkylene group is preferably a C1-C3 oxyalkylene group, More preferably, a C1-C2 oxyalkylene group. The C1-C6 alkylenedioxy is preferably a C1-C3 alkylenedioxy, more preferably a C1-C2 alkylenedioxy.

In the above formulae, 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, for example, 1 or 2 carbon atoms), —O—, —CH ₂ O—, -C (O)-, -C (O) -O- or -C (O) -NR < ⁹ >-.

In the above formulae, 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)-.

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

In the above formulae, each R ⁵ 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 formulas, 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 formulas, X ^{is, - (CR 15 R 16 -CR} 17 R 18) is a k ^{-R 19.}

The above R ^{15 to} R ¹⁸ may be any structure depending on the compound used when introducing the X group in the above formula.

The 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 aspect, each of R ^{15 to} R ¹⁸ is independently a hydrogen atom, a chlorine atom or an organic group.

  The organic group means a group containing a carbon atom. The organic group is not particularly limited, but may be a group in which a hydrogen atom is eliminated from a hydrocarbon group. The above "hydrocarbon group" means a group containing a carbon atom and a hydrogen atom. Such a 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, for example, an aliphatic hydrocarbon group, Aromatic hydrocarbon groups and the like can be mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. In such a hydrocarbon group, a hydrogen atom may be substituted by a halogen atom, and one or more N, O, S, Si, amides, sulfonyls, siloxanes in the terminal or molecular chain thereof. , Carbonyl, carbonyloxy and the like.

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

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

  The halogen atom may be 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 still more preferably iodine.

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

  The above k are each independently an arbitrary integer. In a preferred embodiment, k is an integer of 1 to 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} is an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably methyl or ethyl) hydrogen atom or 1 to 6 carbon atoms is.

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

In a preferred ^{embodiment, R 18} is an alkyl group, an aryl group, pyrrolidonyl _{^{group, -R 21 - (O-C}} a H 2a) b -OR 22, -R 21 -NR 22, -R 21 -OH, -R 21 It may be -COOR ²² or ^-R 21 -OCOR ^22,.

R ²¹ is a single bond or an alkylene group having 1 to 6 carbon atoms (preferably, 1 to 3 carbon atoms, more preferably -CH ₂ -or -CH ₂ CH _2- , more preferably -CH _2- ), It is 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 may be branched. _{Preferably, - (O-C a H} 2a) b - are straight-chain. The above a is independently an integer of 1 to 5, preferably an integer of 2 to 4, for example, 2 for each unit to which b is attached. That is, the units “OC _a H _2a ” to which b is attached may be the same as or different from each other in — (O—C _a H _2a ) _b —. In a preferred embodiment, the units “OC _a H _2a ” to which b is attached are identical in the formula.

In one ^{embodiment, CR 15 R 16 -CR 17 R} 18 is, styrenes, may have a repeating structure methacrylates or acrylates as a monomer unit.

In one ^{embodiment, CR 15 R 16 -CR 17 R} 18 may be less hydrophilic groups.

［式中、Ｒ^２５は、それぞれ独立して、水素原子またはメチル基であり、
ｋは、任意の整数、好ましくは１〜２０の整数であり、
ｎは、任意の整数、好ましくは１〜２０の整数である。］

[Wherein, each R ²⁵ independently represents a hydrogen atom or a methyl group,
k is any integer, preferably an integer of 1 to 20,
n is any integer, preferably an integer of 1 to 20. ]

^{Preferably, CR 15 R 16 -CR 17 R} 18 may be the following groups.

More ^{preferably, CR 15 R 16 -CR 17 R} 18 may be the following groups.

［式中、Ｒ^２６は、それぞれ独立して、炭素数１〜６のアルキル基、好ましくは炭素数１〜３のアルキル基、より好ましくはメチル基であり、
ｋは、任意の整数、好ましくは１〜２０の整数である。］In another ^{embodiment, CR 15 R 16 -CR 17 R} 18 may be less hydrophobic groups.

[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 any integer, preferably an integer of 1 to 20. ]

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

であり得る。このような組み合わせでは、Ｂ^ａの主鎖が疎水性、Ｘが親水性であることから、Ｘ基の種類および量を調節することにより、得られる重合体の親水性および疎水性を調節することができる。In one aspect, B ^a is
-CH ₂ -CHX- alkylene -CHX-CH ₂ -, or _-CH 2 -CHX-CO-O- alkylene _{-O-CO-CHX-CH 2} -;
And CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ is

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

であり得る。このような組み合わせでは、Ｂ^ａの主鎖が親水性、Ｘが疎水性であることから、Ｘ基の種類および量を調節することにより、得られる重合体の親水性および疎水性を調節することができる。In another embodiment, B ^a is
-CH ₂ -CHX-CH ₂ - polyoxyalkylene _{-O-CH 2 -CHX-CH 2} -
And CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ is

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

  In the above formula, n may 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 depending on the raw material or terminator used for the synthesis.

The average molecular weight of the polymer represented _by- (A-B) _n -is not particularly limited, and can be appropriately set according to the purpose of use and the like. For example, in one embodiment, the weight average molecular weight of the polymer of the present invention is 5 × 10 ^{2 to} 5 × 10 ⁶ , preferably 1 × 10 ^{3 to} 3 × 10 ⁶ , for example, 5 × 10 ² And 1 × 10 ⁵ , preferably 1 × 10 ^{3 to} 3 × 10 ⁴ .

  In one aspect, 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 polymer has a lower viscosity, and the distribution of the crosslinked structure at the time of crosslinking becomes uniform, and the mechanical strength is increased. In addition, it is also advantageous when the polymer is further subjected to modification reaction, polymerization, crosslinking reaction, surface treatment and the like even after completion of the polymerization.

  The polymer mentioned above polyadditions a dihalide corresponding to the A structure and a diene corresponding to the B structure, and then the obtained polymer is reacted with a monomer corresponding to X to introduce an X group. It can be obtained by

In particular,
(Step 1) 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 are as defined 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) Then, the compound represented by the formula (C1) is represented by the following formula (D1) corresponding to X:
CR ¹⁵ R ¹⁶ = CR ¹⁷ R ¹⁸ (D1)
By grafting a compound represented by
-(A-B) _n- (I)
[Wherein, A and B are as defined above. ]
You can get

(Step 1)
The conditions for the above-mentioned polyaddition are not particularly limited, and can be appropriately selected by those skilled in the art according to the raw material to be used and the desired product. For example, it can carry out like a nonpatent literature 1 statement.

  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, and more preferably an iodine atom.

  The polyaddition in step 1 is preferably initiated by generating radicals by ultraviolet 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 light source of ultraviolet light is not limited as long as it emits ultraviolet light, and examples thereof include a mercury lamp, a xenon lamp, a UV lamp, a halogen lamp, and an LED, and preferably a high pressure mercury lamp is used. .

Examples of the photoredox catalyst include Rhodamine B, Esion Y, [Ru (bpy) ₃ ] ⁺ analogue, [Ir (bpy) ₃ ] ⁺ analogue 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, Triethylamine, tributylamine, ascorbic acid, ascorbic acid salt and the like are mentioned, preferably sodium dithionite, copper (I) iodide, copper (I) bromide, and particularly preferably sodium dithionite.

  Examples of the radical generator include organic peroxides, inorganic peroxides, organic azo compounds and the like, and preferably organic peroxides. The organic peroxides include, but are not limited to, benzoyl peroxide as the organic peroxide, potassium persulphite as the inorganic peroxide, and AIBN as the organic azo compound.

(Step 2)
The conditions of the grafting reaction in step 2 are not particularly limited, and can be appropriately selected by those skilled in the art according to the raw materials to be used and the desired product.

  The grafting reaction of 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 as a mixture of two or more.

  In one embodiment, the grafting reaction of step 2 is carried out 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 grafting reaction of step 2 is carried out using a combination of two or more of the above radical generator and a polymerization catalyst.

  As the above-mentioned radical generator, the above-mentioned organic peroxide, inorganic peroxide, organic azo compound etc. 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 above-mentioned polymerization catalyst include phenols such as BHT, vitamin E and vitamin C (ascorbic acid and salts thereof), cyclohexadiene, diethoxyhydrophosphonium oxide, tetraalkylphosphonium iodide, tetraalkylammonium iodide, N -Iodosuccinimide, or sodium iodide etc. can be used.

Formula (D1):
CR ¹⁵ R ¹⁶ = CR ¹⁷ R ¹⁸ (D1)
The compounds represented by are so-called graft monomers and have ethylenic double bonds.

  The compound represented by the formula (D1) is, for example, vinyl pyrrolidone, α-alkyl olefin, vinyl ether, allyl ether, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, styrene, vinyl acetate, etc. It may be a derivative.

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

［式中、Ｒ^２５は、それぞれ独立して、水素原子またはメチル基であり、
Ｒ^２６は、それぞれ独立して、炭素数１〜６のアルキル基、好ましくは炭素数１〜３のアルキル基、より好ましくはメチル基であり、
ｎは、任意の整数、好ましくは１〜２０の整数である。］

[Wherein, each R ²⁵ independently represents a hydrogen atom or a methyl group,
R ²⁶ is each independently 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 any integer, preferably an integer of 1 to 20. ]

In step 1 above, preferably, A and B polymerize alternately. However, in step 1, a portion in which B is continuously polymerized may occur. Specifically, _'(wherein, x -A-' is a is integer from 2 to 5) -A-B _x may occur structure represented by. The present invention relates to such a polymer, that is, the following formula (I '):
-(AB _x ) _n- (I ')
[In the formula:
A is -R ¹¹ _p- ;
Each R ¹¹ independently represents a fluorine-containing alkylene group;
p is an integer of 1 to 10;
Each B is independently B ^a or B ^b ;
Each B ^a is independently -CHR ⁵ -CR ⁶ XR ² -R ¹ -R ³ -CR ⁶ X-CHR ^5- ;
Each B ^b is independently -CR ⁵ = CR ⁶ -R ² -R ¹ -R ³ -CR ⁶ = CR ^5- :
With the proviso that at least one B ^a is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² is 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 -And
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)- And
Each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ independently represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁸ each independently represents 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 independently represents 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) be k ^{-R 19:}
In the formula, at least one ^- is _{^{(CR 15 R 16 -CR 17 R}} 18) k -R 19 are 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 any integer;
x is each independently an integer of 1 to 5 in the unit enclosed in parentheses with n added;
n is an arbitrary integer. ]
To provide a polymer represented by

  In one embodiment, in the polymer represented by the above formula (I ′), the abundance ratio of unit A to unit B 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-mentioned 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 polymeric materials. The method of hydrophilization is not particularly limited, and examples thereof include a method in which the polymer material is mixed with another polymer material and then molding, or a method in which a polymer material is molded and the polymer of the present invention is applied to the surface thereof. The polymer of the present invention is suitably used particularly as a hydrophilizing agent for a polymeric porous membrane formed from a polymeric material.

  Thus, the present invention also provides a blend of the polymer of the present invention and other polymeric materials.

  In one aspect, the polymer represented by the above-mentioned formula (I) of the present invention can be used as a paint itself or as an additive to a paint. The polymers of the formula (I) according to the invention can have different functions, for example, because they can have the desired hydrophilicity and hydrophobicity, they can be used as coatings for various substrates and applications. be able to.

Further, the present invention is an intermediate compound before introducing a graft chain, which is represented by the following formula (Ia):
-(AB _x ') _n- (Ia)
[In the formula:
A is -R ¹¹ _p- ;
Each R ¹¹ independently represents a fluorine-containing alkylene group;
p is an integer of 1 to 10;
B 'is each independently B ^a' or B ^{b '} ;
Each of B ^{a ′} independently represents —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 ′} each independently represents —CH = CH—CO—O-adamantane —O—CO—CH = CH—; —CH = CH—CH ₂ —O—adamantane —O—CH ₂ —CH = CH -And:
With the proviso that at least one B ^{a ′} is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² is 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 -And
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)- And
Each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ independently represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁸ each independently represents 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 independently represents 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 any integer;
x is each independently an integer of 1 to 5 in the unit enclosed in parentheses with n added;
n is an arbitrary integer. ]
It also provides a polymer represented by

Preparation Example 1: Polyaddition of dihalide with diene

During pyrex tube, 1,4-butanediol diacrylate (87.9 mg, 0.4 mmol) was dissolved in _{CH 2 Cl 2 (6ml),} I (CF 2) 6 I (220.5mg) and aqueous sodium thiosulfate (314.9 mg, 2 ml) was added, and the mixture was stirred while being irradiated 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 reaction product was purified by reprecipitation to obtain Polymer 2 (139.2 mg, yield 53%, Mn = 6.2 × 10 ³ , Mw = 9.3 × 10 ³ , Mw / Mn = 1.5). 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 (73.3 mg, Mn = 6.2 × 10 ³ , Mw = 9.5 × 10 ³ , Mw / Mn = 1.6) obtained in Production Example 1, N-vinylpyrrolidone 3 (0.11 mL) ) And benzoyl peroxide (7.6 mg) were weighed and added to the reaction vessel, then toluene (2.5 mL) was added to dissolve. The reaction system was replaced with an inert gas, and the mixture was heated and stirred under reflux conditions for 2 hours. After completion of the reaction, purification was conducted by reprecipitation to obtain the objective 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. The reaction system was replaced with an inert gas, and the mixture was heated and stirred under reflux conditions for 2 hours. After completion of the reaction, purification was conducted by reprecipitation to obtain the target 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

Dissolve 1,7-octadiene (0.4 mmol) in CH ₂ Cl ₂ (6 ml) in a Pyrex tube, I (CF ₂ ) ₆ I (0.4 mmol) and aqueous sodium thiosulfate solution (2.0 mmol, 1 ml aqueous solution ) Was added and ultraviolet light was irradiated 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, purification was conducted 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 a reaction vessel Benzoyl (7.9 mg) was weighed and added to the reaction vessel, then toluene (2.5 mL) was added to dissolve. The reaction system was replaced with an inert gas, and the mixture was heated and stirred under reflux conditions for 2 hours. After completion of the reaction, purification is carried out 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). The

Production Example 3

Acetonitrile / water compound 10 (868.7mg) to (1.9 ml / 1.9 ml) mixed _{solution, I (CF 2) 6 I} (2.09g), sodium dithionite (33.5 mg), and carbonate After adding hydrogen sodium (16.8 mg) and replacing the inside of the reaction system with an inert gas, stirring was performed at 45 ° C. for 16 hours. After the reaction, as a result of purification by extraction operation and reprecipitation, 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 / It obtained by 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, methyl methacrylate (608.5 mg), sodium dithionite (158.1 mg), and sodium hydrogen carbonate (76. 2 mg) to a solution of compound 11 (235.2 mg) in dimethyl sulfoxide (DMSO) (1 ml). 2 mg) was added, and after replacing the reaction system with an inert gas, stirring was performed at 60 ° C. for 17 hours. After the reaction, as a result of purification by extraction operation and reprecipitation, 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 / It obtained by Mn = 2.5).

Example 5 (Entry 2)
Styrene (0.69 ml), sodium dithionite (159.0 mg), and sodium hydrogen carbonate (75.3 mg) were added to a DMSO solution (1 ml) of compound 11 (230.9 mg) and reacted at room temperature After replacing the inside of the system with an inert gas, stirring was performed at 150 ° C. for 4 hours. After the reaction, as a result of purification by extraction operation and reprecipitation, 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 / It obtained by Mn = 3.3).

Example 6
Ethyl acrylate (342.0 mg), sodium dithionite (88.3 mg), and sodium hydrogen carbonate (43.8 mg) were added to a DMSO solution (0.6 mL) of compound 11 (133.3 mg). After replacing the reaction system with an inert gas at room temperature, stirring was performed at 60 ° C. for 16 hours. After the reaction, extraction with dichloromethane / water was carried out, and purification by reprecipitation with hexane was carried out to obtain the target compound 12c in a yield of 52% (247.3 mg).

Production Example 4

Diacrylate compounds (13) relative to dichloroethane (80 ml) of _{(1.38g), I (CF 2} ) 6 I (2.68g), and _Na 2 _S 2 _O 3 aqueous solution (3.95 g) (25 ml) Were added, and light irradiation with a high pressure mercury lamp was performed for 28 hours. After the reaction, as a result of purification by extraction operation and reprecipitation, the target compound 14 was obtained in a yield of 42% (1.60 g, Mn = 3.8 × 10 ³ , Mw = 7.2 × 10 ³ , Mw / It obtained by Mn = 1.9).

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

Example 8 (Entry 2)
Acrylic acid (224.4 mg) relative to compound 14 (77.3 mg, Mn = 3.8 × 10 ³ , Mw = 7.2 × 10 ³ , Mw / Mn = 1.9), tetrabutylammonium iodide ( 59.7 mg) and toluene (0.05 mL) were added, and after replacing the reaction system with an inert gas at room temperature, stirring was performed at 110 ° C. for 16 hours. After the reaction, as a result of purification by reprecipitation using methanol, 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)
To compound 14 (76.4 mg, Mw = 7.2 × 10 ³ , Mn = 3.8 × 10 ³ , Mw / Mn = 1.9), 2-hydroxyethyl methacrylate (396.8 mg), N— Add iodosuccinimide (NIS) (1.2 mg), 2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile) (V70) (12.5 mg), and toluene (0.1 mL), After displacing the reaction system with an inert gas at room temperature, stirring was performed at 40 ° C. for 7 hours. After the reaction, reprecipitation with hexane was carried out, and as a result, 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 (hydrophilicity evaluation of polymer)
Sample Preparation The polymers combined in the above Preparation Examples 1 and 4 and Examples 1, 2, 5, 6, 7 and 9, and polystyrene (manufactured by Aldrich, Mn = 3.5 × 10 ⁴ , product number: 331651-25G The polymer solution was prepared by dissolving each of the above in dichloromethane so as to give a concentration of 0.1 wt%. The polymer solution was dropped onto a cover glass and air dried in a draft for 1 hour to prepare a polymer film.
Measurement Method The contact angle immediately after dropping deionized water (2 μL) on the polymer membrane obtained above was measured.

  From the above results, when polymer 4 or 6 in which a hydrophilic skeleton is introduced after graft polymerization is used, it is more hydrophilic than in the case where polymer 2 in which a hydrophilic skeleton is not introduced is used It was confirmed to be high. Moreover, it was confirmed that the graft polymer 12b having a hydrophilic skeleton is more hydrophilic than polystyrene, which is a polymer of its graft chain. Furthermore, when the polymer 15a or 15c into which the hydrophilic skeleton is introduced after graft polymerization is used, the hydrophilicity is higher than when the polymer 14 into which the hydrophilic skeleton is not introduced is used. confirmed.

  The polymers of the present invention can have various properties and can be used in a wide variety of applications.

Claims (13)

The following formula (I):
-(A-B) _n- (I)
[In the formula:
A is -R ¹¹ _p- ;
Each R ¹¹ independently represents a fluorine-containing alkylene group;
p is an integer of 1 to 10;
Each B is independently B ^a or B ^b ;
Each B ^a is independently -CHR ⁵ -CR ⁶ XR ² -R ¹ -R ³ -CR ⁶ X-CHR ^5- ;
Each B ^b is independently -CR ⁵ = CR ⁶ -R ² -R ¹ -R ³ -CR ⁶ = CR ^5- :
With the proviso that at least one B ^a is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² is 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 -And
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)- And
Each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ independently represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁸ each independently represents 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 independently represents 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) be k ^{-R 19:}
In the formula, at least one ^- is _{^{(CR 15 R 16 -CR 17 R}} 18) k -R 19 are 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 any integer;
n is an arbitrary integer. ]
A polymer represented by The following formula (I '):
-(AB _x ) _n- (I ')
[In the formula:
A is -R ¹¹ _p- ;
Each R ¹¹ independently represents a fluorine-containing alkylene group;
p is an integer of 1 to 10;
Each B is independently B ^a or B ^b ;
Each B ^a is independently -CHR ⁵ -CR ⁶ XR ² -R ¹ -R ³ -CR ⁶ X-CHR ^5- ;
Each B ^b is independently -CR ⁵ = CR ⁶ -R ² -R ¹ -R ³ -CR ⁶ = CR ^5- :
With the proviso that at least one B ^a is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² is 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 -And
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)- And
Each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ independently represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁸ each independently represents 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 independently represents 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) be k ^{-R 19:}
In the formula, at least one ^- is _{^{(CR 15 R 16 -CR 17 R}} 18) k -R 19 are 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 any integer;
x is each independently an integer of 1 to 5 in the unit enclosed in parentheses with n added;
n is an arbitrary integer. ]
A polymer represented by B 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} -
[Wherein, X and R ⁹ are as defined in claim 1. ]
The polymer according to claim 1 or 2, which is a group represented by B 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} -
[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 B is
-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 CR ¹⁵ R ¹⁶ -CR ¹⁷ R ¹⁸ is, styrenes, methacrylates, or having the repeating structure acrylates as a monomer unit, polymers according to any one of claims 1 to 5. CR ¹⁵ R ^16- CR ¹⁷ R ¹⁸ is:

[Wherein, each R ²⁵ independently represents a hydrogen atom or a methyl group,
k is an integer of 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 CR ¹⁵ R ^16- CR ¹⁷ R ¹⁸ is:

[Wherein, each R ²⁶ is independently 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 The polymer according to any one of claims 1 to 8, wherein at least one R ¹⁹ is an iodine atom.   The polymer according to any one of claims 1 to 9, wherein the content of iodine atoms is 15% by weight or less. The polymer according to any one of claims 1 to 10, which has a weight average molecular weight of 5.0 × 10 ³ to 5.0 × 10 ⁴ .   The polymer according to any one of claims 1 to 11, having a molecular weight distribution of 1.3 to 3.0. The following formula (Ia):
-(AB _x ') _n- (Ia)
[In the formula:
A is -R ¹¹ _p- ;
Each R ¹¹ independently represents a fluorine-containing alkylene group;
p is an integer of 1 to 10;
B 'is each independently B ^a' or B ^{b '} ;
Each of B ^{a ′} independently represents —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 ′} each independently represents —CH = CH—CO—O-adamantane —O—CO—CH = CH—; —CH = CH—CH ₂ —O—adamantane —O—CH ₂ —CH = CH -And:
With the proviso that at least one B ^{a ′} is present;
R ¹ is an alkylene group, -R ⁷ - arylene -R ⁷ -, or -R ⁷ - (poly) oxyalkylene -R ⁸ - a and;
R ² is 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 -And
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)- And
Each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
Each R ⁷ independently represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁸ each independently represents 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 independently represents 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 any integer;
x is each independently an integer of 1 to 5 in the unit enclosed in parentheses with n added;
n is an arbitrary integer. ]
A polymer represented by