WO2006095790A1 - Novel polymer having fluorospiroketal structure - Google Patents

Abstract

A novel polymer having a fluorospiroketal structure. There is provided a process for producing a polymer containing the following unit (D), comprising polymerizing CH2=CHR and carbon monoxide to thereby obtain a polymer containing the following unit (E) and fluorinating the polymer. (E) (D) In the formulae, RF is a perfluoro monovalent saturated organic group, and R is the same group as represented by RF or a polyfluoro monovalent organic group that becomes RF through fluorination.

Description

 Polymer having novel fluorospiroketal structure

 Technical field

 [0001] The present invention relates to a novel polymer having a fluorospiroketal structure, a method for producing the polymer, a method for producing a cured product for curing the polymer, the cured product, and use as an optical material thereof About.

 Background art

 [0002] As a fluorine-containing polymer having a spiroketal structure, the formula CH = CH (CH) C F

 2 2 y 2y

A fluorine-containing polymer containing a repeating unit represented by the following formula (Z) obtained by polymerizing a compound represented by + 1 and carbon monoxide and carbon monoxide is known (where X is 1 is an integer of 1 to 5, and y is an integer of 1 to 10. (See Patent Document 1).

特許文献 1：特開 2002— 265595号公報 [0003] [Chemical 1]

Patent Document 1: Japanese Patent Laid-Open No. 2002-265595

 Disclosure of the invention

 Problems to be solved by the invention

[0004] However, a polymer in which a hydrogen atom bonded to a carbon atom forming a spiroketal skeleton is substituted with a fluorine atom has not been known. Further, there has been no known fluorinated polymer having a spiroketal structure and a curable polymer.

 Means for solving the problem

[0005] The present inventors have found a novel polymer having a fluorospiroketal structure.

 Furthermore, it was found that a cured product having a low refractive index, high transparency and high hardness can be obtained by introducing a cured site into the polymer and curing it.

That is, the gist of the present invention is as follows.

[1]: A compound represented by the following formula (F) and carbon monoxide carbon are polymerized to repeat the process represented by the following formula (Ε). A method for producing a polymer containing a repeating unit represented by the following formula (D), characterized in that a polymer containing a repeating unit is obtained and then fluorinated: (wherein R ^F is perfluoro a monovalent saturated organic group, R is Porifuruoro monovalent organic group is the same group or fluorinated and R ^F becomes R ^F. forth.) o

 CH = CH-R (F)

 [0007]

[0008] [2]: The compound represented by the formula (F) is represented by the formula CH = CH—QCH OC (0) R ^f

 twenty two

The repeating unit represented by the formula (E) is a repeating unit represented by the following formula (e), and the repeating unit represented by the formula (D) is represented by the following formula (d): The method for producing the polymer according to [1], wherein Q is the same group as Q ^F or a divalent organic group that is fluorinated to Q ^F , and Q ^F is a single bond Or a perfluorinated divalent saturated organic group, and R ^f is a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoro (etheric oxygen atom-containing alkyl) group having 2 to 20 carbon atoms.

[0009] [Chemical 3]

[0010] [3]: A compound represented by the formula CH = CH—QCH OC (0) R ^f is polymerized with carbon monoxide.

 twenty two

To obtain a polymer containing a repeating unit represented by the formula (e), and then fluorinate the polymer to obtain a polymer containing a repeating unit represented by the formula (d). The polymer is subjected to chemical conversion to obtain a polymer containing a repeating unit represented by the following formula (b), and then the polymer is reacted with a compound represented by the formula CX ² X ^ C COY. A method for producing a polymer containing a repeating unit represented by the following formula (a), wherein Q is the same group or fluorinated group as Q ^F Q ^F is a divalent organic group that becomes Q ^F , Q ^F is a single bond or a perfluoro divalent saturated organic group, and R ^f is a perfluoroalkyl group having 1 to 20 carbon atoms or a C 2 to 20 carbon atoms. It is a perfluoro (etheric oxygen atom-containing alkyl) group. Y is a halogen atom, and X ¹ , X ^: and X ³ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group. The same shall apply hereinafter. ).

 [0011]

[4]: A polymer containing a repeating unit represented by the formula (b).

[5]: A polymer containing a repeating unit represented by the following formula (bl) (wherein Q ^F1 is a perfluoroalkylene group having 1 to 10 carbon atoms; the same shall apply hereinafter).

[0013] [Chemical 5]

[0014] [6]: The polymer according to [4] or [5], wherein the polymer has a weight average molecular weight of 10 ³ to 10 °.

 [7]: A polymer containing a repeating unit represented by the formula (a).

[8]: a polymer containing a repeating unit represented by the following formula (al) (where Q ^F1 is a perfluoroalkylene group having 1 to 10 carbon atoms, and X ¹¹ is a hydrogen atom or a methyl group) The same shall apply hereinafter.)

[0015] [Chemical 6]

[0016] [9] :前記重合体の重量平均分子量が、 10³〜10⁶である [7]または [8]に記載の 重合体。

[9] The polymer according to [7] or [8], wherein the polymer has a weight average molecular weight of 10 ³ to 10 ⁶ .

 [10]: A method for producing a cured product, comprising curing a polymer containing a repeating unit represented by the formula (a).

 [11]: A method for producing a cured product, comprising curing a polymer containing a repeating unit represented by the formula (al).

 [12]: An optical material comprising the cured product according to [10] or [11] as an active ingredient. The invention's effect

 [0017] The present invention provides a novel polymer having a fluorospiroketal structure and a method for producing the same. When the polymer of the present invention is a polymer having a curable group in its side chain, the polymer is cured to obtain optical properties (high transparency, low refractive index, etc.) and mechanical properties. A cured product excellent in (hardness etc.) can be obtained. The cured product is useful as an active ingredient of an optical material.

 BEST MODE FOR CARRYING OUT THE INVENTION

In the present specification, a compound represented by the formula (1) is referred to as a compound (1), and a repeating unit represented by the formula (A) is referred to as a unit (A). The same applies to compounds represented by other formulas and repeating units.

The present invention provides a polymer containing the following unit (D) by polymerizing the following compound (F) and carbon monoxide to obtain the following unit (E), and then fluorinating the polymer: Provide a method. However, the definitions of R ^F and R are as described above.

 CH = CH-R (F)

 2

 [0019] [Chemical 7]

R ^F is a group selected from a perfluoroalkyl group and a perfluoro (hetero atom-containing alkyl) group, and an ester bond between the carbon atom and carbon atom bond of the selected group May be inserted. The fluorine atom in R ^F may be substituted with SO F.

 2

Yes. The carbon number of R ^F is 1 to 42, more preferably 1 to 22. The direction of the ester bond is not particularly limited. The heteroatom is particularly preferably an etheric oxygen atom or an etheric oxygen atom, preferably a thioetheric sulfur atom.

[0021] R ^F is a carbon atom of a perfluoroalkyl group, a group in which an ester bond is inserted between carbon atom bonds, or a carbon atom-carbon atom of a perfluoroalkyl group containing an etheric oxygen atom A group in which an ester bond is inserted between the bonds is preferable. Alternatively, a group selected from a perfluoroalkyl group and a perfluoroalkyl group containing an etheric oxygen atom, or a group in which the fluorine atom of the selected group is substituted with SO F is preferable.

 2

Preferable specific examples of the former group (R ^F ) include groups in the compound (F-1) described later. Preferable specific examples of the latter group () include groups in the compound (F-2) described later.

[0022] R is a group corresponding to R ^F, a group wherein one or more became hydrogen atoms of fluorine atoms fluorinated in the R ^F Porifuruoro monovalent saturated organic group is preferred instrument R ^F Particularly preferred.

 [0023] Examples of R include a group selected from a polyfluoroalkyl group having a hydrogen atom and a polyfluoro (heteroatom-containing alkyl) group having a hydrogen atom. An ester bond may be inserted between the carbon atom and carbon atom bond of the selected group. The fluorine atom in R may be substituted with —SO 2 F. R carbon number and preferred

 2

The terror atom is the same as R ^F.

[0024] Furthermore, R is a carbon atom of a polyfluoroalkyl group having a hydrogen atom, a group in which an ester bond is inserted between carbon atom bonds, or a carbon atom of a polyfluoro (hetero atom-containing alkyl) group having a hydrogen atom. A group S in which an ester bond is inserted between atomic bonds S is particularly preferable. In addition, R is a polyfluoroalkyl group having a hydrogen atom and a polyfluoroalkyl group having a hydrogen atom and an etheric oxygen atom, or a fluorine atom of the selected group is substituted with SO F It may be a group.

 2

 [0025] A preferred embodiment of the former group (R) is a compound represented by the formula CH OC (

 2

0) A group represented by R ^f is mentioned. A preferred embodiment of the latter group (R) is a group (R ^f ) in the compound (F-2) described later. In the present invention, the compound (F) and carbon monoxide are polymerized to obtain a polymer containing the unit (E). The compound (F) is preferably the following compound (F-1) or the following compound (F-2). However, Q and R ^f have the same meaning as described above.

CH = CH-QCH OC (0) R ^f (F— 1).

 twenty two

CH = CH-R ^f '(F— 2).

 2

R ^f ′ is a polyfluoroalkyl group having a hydrogen atom and a polyfluoroalkyl group having a hydrogen atom and an etheric oxygen atom, or a fluorine atom of the selected group is substituted with —SOF A group having 1 to 20 carbon atoms.

 2

[0027] When Q is a single bond, a group represented by the formula CH OC (0) R ^f and a bull group are directly bonded.

 2

Means that An example of when Q and Q ^F are the same is when Q is a perfluorinated divalent organic group.

[0028] Q is a fluorinated becomes Q ^F are divalent organic groups preferred instrument etheric oxygen atom-containing § alkylene group or more preferably tool alkylene group alkylene group, is particularly preferred. The carbon number of Q is preferably 1-20, and particularly preferably L0. When Q is a divalent organic group, Q is preferably a straight chain structure, which may be a straight chain structure, a branched structure, a ring structure, or a structure having a partial ring structure. The same applies to Q ^F.

[0029] As a specific example of R ^f ,-(CF) F (s represents an integer of 1 to 20, and an integer of 2 to 10 is preferred.

 2 s

 Yes. ), CF (CF) 0 (CF) F CF (CF) OCF CF (CF) 0 (CF) F, etc.

 3 2 3 3 2 3 2 3

 It is.

[0030] As specific examples of the compound (F-l), CH = CH (CH) OC (0) R ^f , CH = CH (CH

 2 2 a 2 2

) C (0) OR ^f etc. (where R ^f has the same meaning as above. A and b are b

 Each is independently an integer from 1 to 10. ) o

[0031] R ¹ in the compound (F-2) is a polyfluoroalkyl group, a polyfluoro (alkoxyalkyl) group, a polyfluoroalkyl group having a fluorosulfol group, or a polyfluoro (alkoxy) having a fluorosulfol group. Alkyl) groups are preferred. The carbon number of R ^f ′ is preferably 1-20, and particularly preferably 1-10.

[0032] Specific examples of the compound (F-2) include CH = CH (CF) CF, CH = CH (CF) CF

 2 2 3 3 2 2 7 3

, CH = CHCH OCF CF SO F, CH = CHCH OCH CF CF H, CH = CHC H 2 OCH CF CF, CH 2 = CHCH 2 OCH 2 CH 2 (CF 3) CF, and the like.

 2 2 2 3 2 2 2 2 2 5 3

 The polymerization reaction of the compound (F) with carbon monoxide is preferably performed in the presence of a catalyst.

[0033] The catalyst may be a Pd complex having a bidentate phosphine ligand, a Pd cation having a ligand preferred by an organometallic complex, and a metal phosphine ligand having a counter-on force being more preferred. Pd complexes with dentate phosphite ligands are particularly preferred! /. The bidentate phosphine ligand and the bidentate phosphite ligand are preferably optically active ligands.

[0034] The catalyst is preferably a compound represented by the following formula (ca-1) or a compound represented by the following formula (ca-2).

[0035] [Chemical 8]

 (ca-1) (ca-2)

[0036] G is a bidentate ligand coordinated to Pd. G is particularly preferably a phosphite having an optically active aliphatic group, which is preferred by an optically active phosphite, or a phosphite having an optically active aromatic group.

 D— is against. D— is p-tolyl SO—, CF COO_, CF SO—, BF—,

 3 3 3 3 4

PF- or BAr_ (Ar is an aryl group which may have a substituent) is preferable.

6 4

Solv is a solvent molecule that coordinates to Pd. Solv is preferably acetonitrile, methanol, or halogenated hydrocarbon. The line extending from Solv to Pd means the coordination bond formed between Solv and Pd.

 T is a halogen atom, an alkyl group, an aryl group, or a hydrogen atom. In the alkyl group, c (o) o, 1 OC (O) —, or 1 O may be inserted.

[0037] Specific examples of the catalyst include the catalysts described in Examples and the catalyst described in JP-A-2002-265595.

The catalyst is preferably used in an amount of 1 mmol to 1 mol with respect to 1 mol of compound (F). The polymerization reaction is preferably carried out by dissolving the catalyst and compound (F) in a solvent, introducing carbon monoxide, and applying pressure. The polymerization temperature is preferably 20 to 80 ° C. The polymerization pressure is preferably from 1.0 MPa to 5. OMPa (gauge pressure).

 [0038] In the polymerization reaction of the compound (F) and carbon monoxide, a polymer containing the unit (E) is produced.

および R^f'は前記と同じ意味を示す。 The unit (E) is the following unit (e) generated when the compound (F-1) is used as the compound (F), or when the compound (F-2) is used as the compound (F). The unit (e ′) shown below is preferred. Q,

And R ^f ′ has the same meaning as described above.

 [0039] [Chemical 9]

単位 ）の具体例としては、下記単位が挙げられる

Specific examples of unit) include the following units:

単位 (e' )の具体例としては、下記単位が挙げられる。 [0040] [Chemical Formula 10]) CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) 0 (CF ₂ ) ₃ F

Specific examples of the unit (e ′) include the following units.

 [0041] [Chemical 11]

[0042] The fluorine content of the polymer containing the unit (E) is preferably 35% by mass or more, particularly preferably 50% by mass or more. The upper limit of the fluorine content of the polymer containing the unit (E) is preferably 65% by mass or less. When a polymer having a fluorine content in the above range is subjected to liquid phase fluorination described later, there is an advantage that the fluorination reaction proceeds efficiently.

The weight average molecular weight of the polymer containing the unit (E) is preferably 1000 or more and 10 ³ to 10 ⁶ Particularly preferred. In this range, since the vaporization of the polymer is suppressed, the polymer can be efficiently fluorinated.

 Next, in the present invention, the polymer containing the unit (E) obtained by the above method is fluorinated. Fluorination means a reaction in which substantially all of the hydrogen atoms bonded to the carbon atoms of the unit (E) are replaced with fluorine atoms. In the fluorination according to the present invention, the ratio of the number of hydrogen atoms replaced by fluorine atoms (also referred to as fluorination rate) out of the total number of hydrogen atoms in the polymer containing the unit (E) is 95% or more. The preferred range is 95-100%. The product of the fluorination reaction may contain a product having a fluorination rate of less than 100%.

 [0044] The fluorination can be carried out in a uniform state where fluorination using a cobalt fluorination method, an electrochemical fluorination method, or a liquid phase fluorination method is preferred, and the reaction yield is high. Fluorination using the fluorination method is particularly preferred.

 The liquid phase fluorination method is a method in which a polymer containing the unit (E) is brought into contact with fluorine gas in a state where the polymer is dissolved in a liquid reaction solvent. The state dissolved in the reaction solvent means a state in which the polymer containing the unit (E) is dissolved in an amount of 0.1% by mass or more (preferably 0.5% by mass or more) with respect to the reaction solvent. The liquid phase fluorination method is preferably carried out according to the method described in the pamphlet of International Publication No. 02Z79294.

 [0046] The reaction solvent is a solvent capable of dissolving the polymer containing the unit (E) and fluorine gas, and C

 A solvent containing no H bond is preferred. Specific examples of the reaction solvent include perfluoroalkanes, perfluoroethers, perfluoropolyethers, chlorofluorocarbons, chlorofluoropolyethers, perfluoroalkyla. Min, an inert fluid, and the like.

[0047] The amount of the reaction solvent is preferably 5 times or more, more preferably 10 to 100 times the mass of the polymer containing the unit). The viscosity of the solution in which the polymer containing the unit (E) is dissolved in the reaction solvent is preferably 5 X 10 ^{_4 to} 0. lPa 's, and 5 X 10 ^{_4 to} 5 X 10 ^_3 Pa' s is particularly preferable. Yes.

[0048] The fluorine gas in the liquid phase fluorination method may be used as it is or diluted with an inert gas. In the case of using diluted fluorine gas, the fluorine gas concentration is preferably 10% by volume or more, particularly preferably 20% by volume or more. The amount of fluorine gas is the weight including the unit (E). It is preferable to make the amount of fluorine gas equivalent to an excess equivalent to the hydrogen atom in the coalescence. In addition, it is preferable to continue introducing fluorine gas into the reaction system so that an excessive amount is maintained.

 [0049] The reaction temperature in the liquid phase fluorination method is such that 50 ° C to 0 ° C is a particularly preferred fluorination rate from the viewpoint of suppressing the carbon atom-carbon atom bond cleavage reaction of the polymer. For this reason, it is particularly preferable that the liquid phase fluorine method is started at −50 ° C. to 0 ° C. and gradually heated to 10 ° C. to 50 ° C. Further, it is particularly preferable to pressurize the reaction system, which is preferably pressurized during heating, to 0.1 to 0.3 MPa (gauge pressure).

 [0050] In the liquid phase fluorination method, HF is by-produced. Therefore, HF scavenger in the reaction system

 (NaF is preferred) or HF scavenger and outlet gas are preferably contacted at the reactor gas outlet.

 [0051] In order to increase the fluorination rate of the polymer containing the unit (E) in the liquid phase fluorination method, an aromatic hydrocarbon compound (benzene, toluene, etc.) is added to the reaction system, or ultraviolet rays are added. Irradiation is preferred. The addition amount of the aromatic hydrocarbon compound is preferably from 0.1 to 10 mol%, particularly preferably from 0.1 to 5 mol%, based on the total number of hydrogen atoms in the polymer containing the unit (E). The reaction type in the liquid phase fluorination reaction may be a batch method or a continuous method.

[0052] In the fluorination of the polymer containing the unit (E), a polymer containing the unit (D) is formed. For example, a polymer containing the following unit (d) is produced in the fluorination reaction of the polymer containing the unit (e), and a polymer containing the following unit (d ′) is produced in the fluorination reaction of the unit (e ′). Generate. However, QF and R ^f have the same meaning as described above.

 [0053] [Chemical 12]

Q ^F is a single bond when the group represented by the formula —CF OC (0) R ^f and the CF of the spiroketal ring

 2

And are directly connected. Q ^F is perfluoro (containing etheric oxygen atoms). An alkylene group) or a perfluoroalkylene group. Q ^F has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.

[0055] R ^F is a group selected from a perfluoroalkyl group having a perfluoroalkyl group and an etheric oxygen atom, or a fluorine atom of the selected group is substituted with SO F.

 2

A group having 1 to 20 carbon atoms. The number of carbon atoms in R ^F ′ is preferably 1 to: L0. R ^F ′ is preferably a perfluoroalkyl group, a perfluoro (alkoxyalkyl) group, a perfluoroalkyl group having a fluorosulfonyl group, or a perfluoro (alkoxyalkyl) group having a fluorosulfol group. ,.

 [0056] Specific examples of the unit (d) include the following units.

単位 (d' )の具体例としては、下記単位が挙げられる。 [0057] [Chemical 13] CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) 0 (CF ₂ ) ₃ F

Specific examples of the unit (d ′) include the following units.

 [0058] [Chemical 14]

[0059] The polymer containing the unit (D) of the present invention may contain units other than the unit (D) (hereinafter referred to as other units). However, as other units, a group selected from the fluorine atom and R ^F group of the unit (D) (however, the group includes an atom), a fluorine atom and a group other than And a unit substituted in the above group). The other group is preferably a hydrogen atom or a perchloroalkyl group.

 [0060] In the other unit, the polymer in which the fluorine atom of the unit (D) is a unit substituted with a hydrogen atom, the fluorination rate in the fluorination reaction of the polymer containing the unit) is 95% or more. A polymer in the case of less than% is mentioned.

As another polymer, a polymer in which R ^F of the unit (D) is a unit substituted with another group In the polymerization of the compound (F) and carbon monoxide and carbon, a polymer produced when a compound having a different R portion of the compound (F) is used together with the compound (F).

 [0061] When the polymer containing the unit (D) has only the unit (D), the arrangement of the units (D) is not particularly limited, and examples thereof include the following arrangement.

 [0062] [Chemical 15]

[0063] Polymer Strength of Unit (D) In the case of a polymer containing the unit (D) and other units, the units may be arranged in a block shape or a random shape.

[0064] The polymer containing the following unit (d) obtained by the production method of the present invention includes a unit of —Q ^F CF

 2

It is a useful polymer that can be derived into other polymers by chemical conversion of the OC (0) R ^f moiety. For example, a polymer containing the following unit (b) is obtained from a polymer containing the unit (d), and then the polymer and the formula. Χ ² Χ ³ =. A polymer containing the following unit (a) can be produced by reacting with a compound represented by Χ ^ ΟΥ. However, X ¹ , X ² , X ³ and Y have the same meaning as described above.

[0065] [Chemical 16]

[0066] X ¹ , X ² and X ³ are each independently preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a perfluoroalkyl group having 1 to 3 carbon atoms. X ¹ is particularly preferably a hydrogen atom or a methyl group. X ² and X ³ are particularly preferably hydrogen atoms. Y is preferably a chlorine atom or a bromine atom.

 [0067] As a method for chemically converting the polymer containing the unit (d) to the polymer containing the unit (b), the following [Method 1] or the following [Method 2] is preferred.

[Method 1] Polymer containing unit (c-1) by thermal decomposition reaction of polymer containing unit (d) And then producing a polymer containing the unit (b) by reducing the polymer.

[0068] [Chemical 17]

[0069] The thermal decomposition reaction is preferably performed in the presence of an alkali metal fluoride. The alkali metal fluoride is preferably NaF, CsF or KF. The reaction conditions in the thermal decomposition reaction are preferably those described in International Publication 02Z79274 Pamphlet. For example, when the polymer containing the liquid unit (d) is subjected to a thermal decomposition reaction, the polymer is preferably thermally decomposed by heating in the presence of an alkali metal fluoride in the absence of a solvent. When the polymer containing the solid unit (d) is subjected to a thermal decomposition reaction, the solution composition obtained by dissolving the polymer in a solvent is heated in the presence of an alkali metal fluoride. It is preferred to thermally decompose the polymer.

 [0070] The reduction reaction is preferably performed in the presence of a reducing agent. The reducing agent is NaBH, LiAlH

 4 4 or Li ((CH) CHCH) A1H is preferred. In addition, the unit in the polymer containing the unit (c-1)

 3 2 2 2

 It is preferable to react 1 to 50 molecules of the reducing agent with respect to the number of units of the position (c 1). 5 ~ 2

The power of reacting five molecules is more preferable.

[0071] [Method 2] A polymer containing the unit (d) is reacted with a compound represented by the formula R—OH to obtain a polymer containing the following unit (c 2). A method for producing a polymer containing the unit (b) by reduction reaction (where R is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group, and so on).

[0072] [Chemical 18]

The reaction conditions for the polymer containing the unit (d) and the compound represented by the formula R—OH are preferably the reaction conditions described in WO 02Z79274. Next unit (c-2) The reduction reaction of the containing polymer is preferably carried out in the same manner as the reduction reaction of the polymer containing the unit (c 1).

[0074] The polymer containing the unit (b), which is a production intermediate of the polymer containing the unit (a), is a novel polymer. The weight average molecular weight of the polymer containing the unit (b) is preferably 10 ³ 10 ⁶ . A preferred embodiment of the polymer containing the unit (b) is a polymer containing the following unit (bl) (wherein QF ¹ has the same meaning as described above).

 [0075] [Chemical 19]

 Specific examples of the unit (b) include the following units.

単位 (b)を含む重合体が、単位 (b)のみカゝらなる重合体である場合、単位 (b) :、 び方は、特に限定されず、たとえば下記の並び方が挙げられる。 [0076] [Chemical 20]

When the polymer containing the unit (b) is a polymer comprising only the unit (b), the unit (b): and the way are not particularly limited, and examples thereof include the following arrangement.

[0077] [Chemical 21]

The reaction between the polymer containing unit (b) and the compound represented by the formula CX ^^ C COY has the formula ΟΧ ² Χ ³ = ΟΧ ^ に 対 し て for one unit (b) in the polymer. It is preferable to react the compound represented by the formula (1) or more, particularly preferably 15 molecules.

[0078] As a specific example of a compound represented by the formula ΟΧ ² Χ ³ = ΟΧ ^ ΟΥ, CH = CHCOCl CH

 2

 = CHCOBr CH = C (CH) COCl CH = C (CH) COBr CH = CFCOCl

2 2 3 2 3 2

CH = C (CF) COCl CF = CFCOCl CF = CHCOCl CHF = CFCOCl etc. Can be mentioned.

[0079] The polymer containing the unit (a) is a novel polymer. The weight average molecular weight of the polymer containing the unit (a) is preferably from 10 ³ to 10 ⁶ .

 [0080] The polymer containing the unit (a) may be one or more of the units (a) and may be one or more of the units (a), and the unit (a It may be a polymer that has the strength of one or more of other units other than). Other units include a group in which the fluorine atom of unit (a) is replaced by a hydrogen atom, a unit selected from unit (b) and unit (e ′), and a fluorine atom in the selected unit as a hydrogen atom. Examples include substituted units.

 [0081] When the polymer containing the unit (a) is a polymer having only the unit (a), the arrangement of the units (a) is not particularly limited, and examples thereof include the following arrangement.

 [0082] [Chemical 22]

A preferred embodiment of the polymer containing the unit (a) includes a polymer containing the following unit (al) (wherein Q ^F1 and X ¹¹ have the same meaning as described above).

単位 (a)の具体例としては、下記単位が挙げられる。 [0084] [Chemical 23] (0) CX ¹¹ = CH ₂

Specific examples of the unit (a) include the following units.

[0085] [Chemical 24] C (0> C (CH ₃ ) = CH ₂

[0086] The polymer containing the unit (a) is useful as a curable polymer. That is, the polymer A cured product can be obtained by curing the unsaturated group (radically polymerizable group) therein. The present invention provides a method for producing a cured product in which a polymer containing the unit (a) is cured. In the curing of the polymer, the polymer containing the unit (a) that may be cured by polymerizing only the polymer containing the unit (a) is reacted with another compound capable of reacting with the polymer. And may be cured. Other compounds include other curable compounds that copolymerize with the polymer containing unit (a).

 [0087] The polymer containing the unit (a) is preferably cured in the presence of a curing initiator (radical generator). Examples of the curing initiator include a heat-sensitive curing initiator and a light-sensitive curing initiator. The curing initiator is preferably used in an amount of 0.01 to 5% by mass, particularly preferably 0.5 to 2.5% by mass, based on the polymer (a).

 [0088] The polymer containing the unit (a) may be cured as it is, and may be cured after preparing a solution composition obtained by dissolving and dispersing the polymer in a solvent. From the viewpoint of the latter, the latter is preferable. The solvent in the solution composition is particularly preferably 10 to 500% by mass, preferably 1 to 1000% by mass, based on the polymer containing the unit (a).

 [0089] Examples of the solvent include perfluoroalkylamines such as perfluorotripropylamine, perfluorotributylamine, fluorinate (trade name, manufactured by 3M), Vertrel (trade name, DuPont). And other organic solvents (hydrocarbons, alcohols, ketones, ethers, esters and chlorinated hydrocarbons).

 [0090] The solution composition is useful as a surface treating agent for imparting the physical properties of the cured product of the present invention to the substrate surface. For example, the solution composition is applied to the substrate surface, the solvent is then volatilized to form a thin film containing a polymer containing the unit (a) on the substrate surface, and then the unit (a) is contained. By forming a thin film comprising a cured product obtained by curing a polymer on the surface of the substrate, the physical properties of the cured product of the present invention can be imparted to the substrate surface.

[0091] Examples of the coating method include a roll coating method, a casting method, a dip coating method, a spin coating method, a water casting method, a die coating method, a Langmuir projet method, and a vacuum deposition method. Examples of the curing method include a method using heating and a method using light irradiation. [0092] A cured product obtained by curing the polymer containing the unit (a), or a cured product obtained by curing the polymer containing the unit (a) and another curable compound has an optical property (high It is particularly useful as an active ingredient in optical materials because of its excellent transparency, low refractive index, etc.) and mechanical properties (hardness, etc.).

 Example

 [0093] The present invention will be described by way of examples, but the present invention is not limited thereto.

 In the following, tetramethylsilane is TMS, dichloropentafluoropropane is R — 225, 1, 1, 2—trichlorophlotriethane is R — 113, (+) — (R) — 2— Diphen yiphosphmo ― 1, 1 ― omaphthalene― 2 —— yl (S 1 1, 丄 —— Dinaphtalene—— 2, 2 '-diyl phosphite (R, S) —BINAPHOS (compound (ca—ll) below), number average The molecular weight is M and the weight average molecular weight is M. B [3,5- (CF 3) CH] is tetrakis nw 3 2 6 3 4

 (3,5-bis (trifluoromethyl) phenol) borate is shown.

[0094] (R, S) — BINAPHOS is described in J. Orgmet. Chem., 576, 248 (1999), J. Am. Chem. Soc., 119, 12779 (1997), J. Am. Chem. Soc. 115, 7033 (1993) and the like.

[0095] M and M were measured using the GPC method described in JP-A-2001-208736.

. In other words, a mixed solvent of R-225Z hexafluoroisopropyl alcohol was used as the mobile phase, and two PLgel MIXED-E columns (manufactured by Polymer Laboratories) were connected in series as the column. Used an evaporative light scattering detector. The yield of the reaction was determined from ¹⁹ F-NMR (internal standard: 1,3-bis (trifluoromethyl) benzene) or ¹ H—NMR. The refractive index of the cured film was measured using spectroscopic ellipsometry (JA Woollam Co., Inc. WVASE32).

[0096] [Example 1] Production example of polymer (E-11)

 Dehydrated methylene chloride (lmL) containing Pd (CH) (CI) [(R, S) -BINAPHOS] (10 mg)

Three

 Dehydrated acetonitrile (0.5 mL) containing Na [B [3,5- (CF) C H]] (lOmg) in solution

 3 2 6 3 4

 The solution was added and stirred at 25 ° C for 1 hour. The solvent was removed under reduced pressure and [Pd (CH) (CH C

 3 3

N) [(R, S)-BINAPHOS]] ⁺ -[B [3, 5— (CF) CH]

 3 2 6 3 4 Γ (the following compound (ca—11)

. Hereinafter referred to as a catalyst. ) [0097] [Chemical 25]

触媒に脱水塩化メチレン（2mL)と CH =CH(CH ) OC(0)CF(CF )OCF CF

Dehydrated methylene chloride (2 mL) and CH = CH (CH) OC (0) CF (CF) OCF CF

 2 2 4 3 2

(CF) 0 (CF) F (3. Og) are mixed in order, freeze degassed and autoclay

3 2 3

 Into the flask (internal volume 50 mL).

[0098] Carbon monoxide was injected into the autoclave until the internal pressure reached 2. OMPa (gauge pressure).

 The autoclave was immersed in a 50 ° C oil bath, and polymerization was carried out for 138 hours while stirring the autoclave. Then, the internal pressure was changed to atmospheric pressure, and dehydrated methanol (0.5 mL) was removed.

 [0099] Further, carbon monoxide and carbon were injected into the autoclave until the internal pressure reached 2. OMPa (gauge pressure), and the inside of the autoclave was stirred at 25 ° C for 1 hour. The autoclave contents were filtered and the filtrate collected was distilled off under reduced pressure to obtain a solid. The solid was purified by a reprecipitation method using a mixed solution of R-225 and methanol as a developing solvent and referred to as polymer (1.7 g, yield 54%) (hereinafter referred to as polymer (E-11)). ) As a result of analyzing the polymer (E-11) by NMR and IR, the polymer (E-11) was a polymer containing the following unit (E-11). M of the polymer (E-11) was 19700, and M was 25500.

 n w

 [0100] 'H-NMROOO.4MHZ, solvent: R—113, standard: TMS) δ (ppm): 1.00-3.50

 (brm, 9Η), 4.43 (brs, 2H).

[0101] ¹⁹ F-NMR (282.7 MHz, solvent: R—113, standard: CFC1) δ (ppm): — 80.8 (3F

 Three

), -81.5 (3F), -82.6 (3F), —78.6 to — 85.2 (4F), —129.6 (2F), —12 7.5 to 1 131.3 (IF), —144.9 (1F). [0102] IR (neat): 1148, 1238, 1716, 1785, 2946cm

 [0103] [Chemical 26]

[0104] [Example 2] Production example of polymer (D-11)

 R-113 (312 g) was added to an autoclave (internal volume 500 mL, made of nickel), and the mixture was stirred and kept at 25 ° C. At the autoclave gas outlet, a cooler maintained at 20 ° C, a packed bed of NaF pellets, and a cooler maintained at -20 ° C were installed in series. In addition, from the cooler maintained at −20 ° C., a liquid return line for returning the agglomerated liquid to the autoclave was installed. After nitrogen gas was blown for 1.0 hour, fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was blown for 1 hour at a flow rate of 12.97 LZh.

 Next, a solution obtained by dissolving polymer (E-11) (14.9 g) obtained in the same manner as in Example 1 in R-113 (147 g) while blowing 20% fluorine gas at the same flow rate was used. Infused over 7 hours. Next, while blowing 20% fluorine gas at the same flow rate, the internal pressure of the reactor was increased to 0.15 MPa (gauge pressure), and a solution of benzene (0.5 g) dissolved in R-113 (50 mL) (9 mL) The reaction was continued for 10 minutes. Further, the solution (6 mL) was injected, and the operation of continuing the reaction was repeated 4 times, and then nitrogen gas was blown for 1.0 hour.

 [0106] After completion of the reaction, the contents of the autoclave were concentrated and further vacuum-dried (60 ° C, 6. Oh, lkPa) to give a viscous polymer (19. Og) at 25 ° C Polymer (D-11)) was obtained. As a result of analyzing the polymer (D-11) by NMR, it was found that the polymer (D-11) had the following units (9-9 mol% of hydrogen atoms in the polymer (E-11) substituted with fluorine atoms): It was a polymer containing D-11). M of the polymer (D-11) was 5850, and M was 9400.

 n w

[0107] ¹⁹ F-NMR (282.7 MHz, solvent: R—113, standard: CFC1) δ (ppm): — 77.5-

 Three

 -86. 0 (7F), -89. 5 (5F), -90. 0 ~-95. 0 (3F), -105. 0 ~-129.5 (8 F),-120. 0 ~-139 0 (3F), —142. 0 to — 146.0 (1F), —178. 0 to — 20.0 (1F).

[0108] [Chemical 27]

[Example 3] Production example of polymer (K 20)

 Place the polymer (D-11) (10g), NaF (2.2g) and R-225 (50mL) in a round bottom flask (made of fluorocarbon resin) and stir at 25 ° C with methanol (2 7g) was slowly added and stirred at 25 ° C for 10-12 hours. Next, the filtrate collected by pressure filtration of the flask was concentrated to obtain a white polymer (3. Og, yield 58%) (hereinafter referred to as polymer (K-20)). As a result of analyzing the polymer (K-20) by NMR and IR, the polymer (K-20) was a polymer containing the following unit (K20).

[0109] ¹⁹ F-NMR (282.7 MHz, solvent: acetone-d, standard: CFC1) δ (ppm): — 105.

 6 3

 0 to-129.5 (8F),-178. 0 to-200.0 (1F).

 'H -NMR OOO. 4MHZ, Solvent: Acetone — d, Standard: TMS) δ (ppm): 4.1 (3 1)

 6

IR (neat): 1150, 1200, 1440, 1785cm ^_1 ₀

[0110] [Chemical 28]

[0111] [Example 4] Production example of polymer (Β-11)

 In a flask equipped with a dropping funnel with a nitrogen gas atmosphere in an ice bath, add NaBH (1.08 g),

 Four

 Lahydrofuran (50 mL) and methanol (20 mL) were added and stirred. Next, a solution obtained by dissolving the polymer (K-20) (2.4 g) obtained in Example 3 in tetrahydrofuran (30 mL) was slowly added dropwise while maintaining the flask internal temperature at 10 ° C. or lower. The internal temperature was maintained at 25 ° C and the mixture was stirred for a while. Further, the temperature inside the flask was kept at 70 ° C. and stirred for 2 hours.

[0112] After the solution in the flask was cooled, 2 mol ZL of HC1 aqueous solution (250 mL) was slowly added dropwise while maintaining the temperature in the flask at 30 ° C or lower. Next, R-225 was further added to the solution in the flask, and the resulting organic layer was recovered and dried over magnesium sulfate. Filter the organic layer further Then, the obtained filtrate was dried under reduced pressure to obtain a polymer (B-11).

[0113] The polymer (B-11) was slightly dissolved in tetrahydrofuran and methanol. Also polymer (B

 -11) was analyzed by IR. As a result, the polymer (B-11) was a polymer containing the following unit (B-11) in which the COOC H structure in the polymer (K-20) was converted into a CHOH structure. there were.

 3 2

IR (neat): 1180, 3250cm ^_1 .

[0114] [Chemical 29]

[0115] [Example 5] Production example of polymer (A-11)

 In a flask equipped with a dropping funnel with a nitrogen gas atmosphere in an ice bath, the polymer (B-11) (1. Og), hydroquinone (0. Olg), triethylamine (0.5 g), and jetyl ether ( 20 mL) was added and stirred. Next, CH = CHCOC1 (0.5 g) was added to tetrahydrofuran.

 2

 The solution dissolved in (8 mL) was slowly added dropwise with the flask internal temperature kept at 5 ° C or lower, and the power was kept at 25 ° C and stirred for a while.

[0116] R-225 and water were added to the solution in the flask, and the resulting pale yellow solid was collected and dried under reduced pressure to obtain polymer (A-11) (1.05 g). The polymer (A-11) was dissolved in methanol, isopropanol V-dimethyl and dimethylformamide, respectively. As a result of analyzing the polymer (A-11) by NMR and IR, the polymer (A-11) was found to be CH OH in the polymer (B-11).

 2 Polymerization containing the following units (A-11) whose structure is converted to CH OC (0) CH = CH structure

 twenty two

 Body (A-11).

[0117] ¹⁹ F-NMR (282.7 MHz, solvent: CD OD, standard: CFC1) δ (ppm): 110.0 ~

 3 3

 -130. 0 (8F), -180. 0 to-200. 0 (1F).

 'H-NMROOO.4MHZ, Solvent: CD OD, Criteria: TMS) δ (ppm): 3.0-4.0 (2

 Three

 H), 6.0-6.5 (3H).

IR (neat): 1179, 1634, 1747, 2960, 3300 cm ^_1 .

[0118] [Chemical 30]

[Example 6] Example of production of cured product 1

 Polymer (A-11) (0.1 lg), dimethylformamide (0.7 g), photocuring initiator (Ciba 'Specialty' Chemicals, trade name: Irgacure 907) (10 mg) and 4, 4 , -Jetylaminobenzophenone (3.5 mg) was mixed to obtain a curable composition 1.

[0120] A thin film (film thickness: 50 to 200 nm) comprising the curable composition 1 by coating the curable composition 1 on a glass substrate by spin coating and then drying at 100 ° C for 5 minutes. ) Was formed. Next, glass with a cured film (thickness: 119 nm) formed by curing curable composition 1 by irradiating the glass substrate with 2. ljZcm ² ultraviolet rays (high pressure mercury lamp) at 25 ° C. A substrate was obtained. As a result of measuring the refractive index of the cured film by spectroscopic ellipsometry, it was 1.45 to L 48 in the visible range.

 [0121] [Example 7] Production example of cured product 2

 Polymer (A-11) (2 parts), (CH 3) CHOH (97.82 parts), photocuring initiator (Ciba)

 3 2

 A curable composition 2 was obtained by mixing Charity Chemicals, trade name: Irgacure 907) (0.12 part) and 4,4, -jethylaminobenzophenone (0.06 part).

[0122] A curable composition 2 was coated on a polyethylene terephthalate film (hereinafter referred to as PET film! /) With a bar coater, and then dried at 100 ° C for 5 minutes. A thin film (film thickness 50 to 500 nm) made of the curable composition 2 was formed. Next, the PET film was irradiated with ultraviolet light (high pressure mercury lamp) of 1.2 j / cm ² at 25 ° C to obtain a PET film on which a cured film formed by curing of the curable composition 2 was formed. . The refractive index of the cured film estimated from the surface reflectance was 1.46.

 Industrial applicability

[0123] A cured product obtained by curing the polymer (a) of the present invention is useful as an optical material because of its excellent optical properties. For example, the cured product is composed of an optical fiber material (a core material and a cladding material of an optical fiber), an optical waveguide material (a core material and a cladding material of an optical path material), a pellicle material, a lens material (a spectacle lens, Optical lenses, optical cells, etc.), elements (Light-emitting elements, solar cell elements, etc.) Sealing materials, interlayer insulation films (for semiconductor elements, liquid crystal displays, multilayer wiring boards, etc.), high-frequency elements (RF circuit elements, GaAs elements, InP elements, etc.) It is useful as an anti-reflection filter for protective films and displays (PDP, LCD, CRT, LCD, etc.). In addition, since the polymer (a) has a high fluorine content and is excellent in releasability, it is useful as a surface modifier for breathable fabrics, an oil sealant for bearings in motor fluid bearing devices, and the like. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2005-67955 filed on March 10, 2005 are cited here as the disclosure of the specification of the present invention. Incorporate.

Claims

Claims [1] A compound containing a repeating unit represented by the following formula (E) is obtained by polymerizing a compound represented by the following formula (F) and carbon monoxide, and then the polymer: A method for producing a polymer containing a repeating unit represented by the following formula (D), wherein RF is a perfluoromonovalent saturated organic group, and R is the same group as fluorine or fluorine This is a polyfluoro monovalent organic group that is converted to RF.) CH = CH-R (F) 2  [Chemical 1]

[2] The compound represented by the formula (F) is a compound represented by the formula CH = CH—QCH OC (0) R ^f  twenty two The repeating unit represented by the formula (E) is a repeating unit represented by the following formula (e), and the repeating unit represented by the formula (D) is represented by the following formula (d): The method for producing a polymer according to claim 1, wherein Q is the same group as Q ^F or a divalent organic group that is fluorinated to form QF, and Q ^F is a single bond or perfluoro A divalent saturated organic group, and R ^f is a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoro (ether oxygen atom-containing alkyl) group having 2 to 20 carbon atoms.) O  [Chemical 2]

[3] A compound represented by the formula CH = CH-QCH OC (0) R ^f is polymerized with carbon monoxide.  twenty two A polymer containing a repeating unit represented by the formula (e) is obtained, and then the polymer is fluorinated to obtain a polymer containing a repeating unit represented by the following formula (d). The polymer is subjected to chemical conversion to obtain a polymer containing a repeating unit represented by the following formula (b), and then the polymer and the formula CX ² Χ ³ =. A method for producing a polymer containing a repeating unit represented by the following formula (a), characterized by reacting with a compound represented by Χ ^ ((where Q is the same group or fluorinated group as Q ^F Q ^F is a divalent organic group that becomes Q ^F , Q ^F is a single bond or a perfluoro divalent saturated organic group, and R ^f is a perfluoroalkyl group having 1 to 20 carbon atoms or a C 2 to 20 carbon atoms. A perfluoro (etheric oxygen atom-containing alkyl) group, Y is a halogen atom, and X ¹ , X ² and X ³ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group.) o [Chemical 3]

A polymer containing a repeating unit represented by the following formula (b) (wherein Q ^F is a single bond or a perfluoro divalent saturated organic group).

[5] A polymer containing a repeating unit represented by the following formula (bl) (wherein Q ^F1 is a perfluoroalkylene group having 1 to 10 carbon atoms).

[6] The polymerization according to claim 4 or 5, wherein the polymer has a weight average molecular weight of 10 ³ to 10 ^6. body. [7] A polymer containing a repeating unit represented by the following formula (a) (where Q ^F is a single bond or a perfluoro divalent saturated organic group, and X ¹ , X ² and X ³ are each independently , Hydrogen atom, fluorine atom or monovalent organic group.) O [Chemical 6]) CX ¹ = CX ² X ³

[8] A polymer containing a repeating unit represented by the following formula (al) (wherein is a fluoroalkylene group having 1 to 10 carbon atoms, and X ¹¹ is a hydrogen atom or a methyl group.) o  [Chemical 7]

[9] The polymer according to claim 7 or 8, wherein the polymer has a weight average molecular weight of 1 (量 to 10 ⁶ ). [10] A method for producing a cured product characterized by curing a polymer containing a repeating unit represented by the following formula (a) (where Q ^F is a single bond or a perfluoro divalent saturated organic group, X ¹ , X ² and X ³ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group. [Chemical 8]

[11] A method for producing a cured product, characterized by curing a polymer containing a repeating unit represented by the following formula (al) (where Q ^F1 is a perfluoroalkylene group having 1 to 10 carbon atoms: in and, X 1 ¹ is a hydrogen atom or a methyl group.) o [Chemical 9]

[12] An optical material comprising the cured product according to claim 10 or 11 as an active ingredient.