JP4776303B2 - Method for producing fluorine-containing compound, fluorine-containing compound, fluorine-containing polymer, and optical material or electric material using fluorine-containing polymer - Google Patents

Description

  The present invention relates to a novel method for producing a fluorine-containing compound, a fluorine-containing polymer obtained from the fluorine-containing compound, and an optical material or an electric material using the fluorine-containing polymer.

A fluorine-containing polymer is a useful substance that is used as an optical member such as a plastic optical fiber or an exposure member, or as a surface modifier, and is used in a wide range of fields. However, the process for synthesizing the fluoropolymer is complicated and costly.
The fluorine-containing polymer can be obtained by polymerizing a fluorine-containing compound having a polymerizable unsaturated group. As one of the fluorine-containing compounds, 1,3-dioxolane derivatives and the like have been proposed (see, for example, Patent Documents 1 and 2 and Non-Patent Documents 1 and 2).

  However, conventionally known 1,3-dioxolane derivatives include compounds represented by the following chemical formula (A) (for example, see Patent Document 3) and compounds represented by the chemical formula (B) (for example, Patent Document). 4), and only specific substituents could be arranged at specific positions on the 5-membered ring of dioxolane.

In formula (B), R _f ^{1 ′} and R _f ^{2 ′} are each independently a C 1-7 polyfluoroalkyl group.

  These structural limitations are due to the synthesis method. For example, in the conventional method for synthesizing the chemical formula (A), only one fluorine-containing group can be arranged on the 1,3-oxolane ring. In the conventional method for synthesizing the chemical formula (B), the number of polyfluoroalkyl groups that can be introduced into the 1,3-oxolane ring is always limited to two, one at the 4,5-position. . Furthermore, the raw material for synthesizing the fluorine-containing compound of the chemical formula (B) is the following chemical formula (C), and it was difficult to synthesize this compound.

On the other hand, it has an amorphous copolymer of perfluoro 2,2-dimethyl-1,3-dioxole having perfluoro (butenyl vinyl ether) and perfluoro-2-methylene-4-methyl-1,3-dioxolane An amorphous copolymer of perfluoro 2,2-dialkyl-1,3-dioxole is also disclosed (see, for example, Patent Document 5 and Patent Document 6).
However, since these perfluoromonomers are very expensive, it is desired to provide more economical compounds. There is also a desire to provide fluoropolymers that exhibit better optical, thermal and solubility characteristics.
U.S. Pat. No. 3,308,107 US Pat. No. 3,450,716 US Pat. No. 3,978,030 JP-A-5-339255 US Pat. No. 5,276,121 US Pat. No. 5,408,020 Izvestiya Akademii Nank SSSR, Seriya Khimicheskaya, “VIBRATIONAL SPECTROSCOPY”, February 1988, p.392-395 Yuminov et al, “VIBRATIONAL SPECTROSCOPY”, April 1989, p.938

  Therefore, the problems to be solved by the invention are a method for producing a fluorine-containing compound which is a dioxane monomer excellent in flexibility and miscibility, a fluorine-containing compound, a fluorine-containing polymer, and an optical material or an electric material using the fluorine-containing polymer. Is to provide.

In consideration of the above situation, in order to further improve the flexibility and miscibility of the dioxane monomer, the present inventors have attempted to design and synthesize perfluoro-1,3-dioxolane containing an ether substituent. These synthetic routes involve the step of direct fluorination of the hydrocarbon precursor.
Moreover, a homopolymer can be obtained by polymerizing the obtained perfluoro-1,3-dioxolane containing an ether substituent in a bulk state or in a solution. Furthermore, a copolymer is obtained by copolymerizing the perfluoro-1,3-dioxolane and other unsaturated fluorine-containing compounds.

  That is, the present invention is as follows.

<1> A condensate is obtained by reacting one or more compounds represented by the following chemical formula (1) or one or more compounds represented by the following chemical formula (3) with one or more compounds represented by the following chemical formula (3). The manufacturing method of the fluorine-containing compound represented by following Chemical formula (4) which has a process and the process of fluorinating this condensate in a fluorine-type solution in fluorine gas atmosphere.

Wherein, X represents a hydrogen atom or a fluorine atom, Y represents an alkyl group having 1 to 7 carbon atoms, Z is represents a hydroxyl group, x represents an integer of 1-3.

<2> One or more compounds represented by the following chemical formula (1) or one represented by the following chemical formula (5) are reacted with one or more compounds represented by the following chemical formula (5) to obtain a condensate. The manufacturing method of the fluorine-containing compound represented by following Chemical formula (6) which has a process and the process of fluorinating this condensate in a fluorine-type solution in fluorine gas atmosphere.

Wherein, X represents a hydrogen atom or a fluorine atom, Y represents an alkyl group having 1 to 7 carbon atoms, Z is represents a hydroxyl group, an integer of 1 to 3 x and y are each independently To express.

<3> A condensate obtained by reacting at least one compound represented by the following chemical formula (1) or at least one compound represented by the following chemical formula (7) with one or more compounds represented by the following chemical formula (7): And a step of fluorinating the condensate in a fluorine-containing solution in a fluorine gas atmosphere. A method for producing a fluorine-containing compound represented by the following chemical formula (8):

Wherein, X represents a hydrogen atom or a fluorine atom, Y represents an alkyl group having 1 to 7 carbon atoms, Z is represents a hydroxyl group, n1 and n2 each integer of independently 1 to 3 To express.

<4> lower hear Science formula (6) or the fluorine-containing compound represented by the chemical formula (8).


In the formula, x and y each independently represent any integer of 1 to 3, and n1 and n2 each independently represent any integer of 1 to 3.

<5> A fluorine-containing homopolymer obtained by polymerization of the fluorine-containing compound according to <4>.

<6> A fluorine-containing copolymer obtained by copolymerization of the fluorine-containing compound according to <4> and an unsaturated fluorine-containing compound other than the fluorine-containing compound.

<7> An optical member or an electrical member containing at least one of the fluorine-containing homopolymer according to <5> and the fluorine-containing copolymer according to <6>.

<8> The optical member or electrical member according to <7>, wherein the optical member or electrical member is an optical fiber, an optical waveguide, a photomask, or a coating material.

  ADVANTAGE OF THE INVENTION According to this invention, the optical material or electrical material using the manufacturing method of a fluorine-containing compound which is a dioxane monomer excellent in the softness | flexibility and miscibility, a fluorine-containing compound, a fluorine-containing polymer, and a fluorine-containing polymer can be provided.

1. Method for Producing Fluorine-Containing Compound A method for producing a fluorine-containing compound which is an ether derivative of perfluoro-1,3-dioxolane of the present invention will be described.

<1> Method for Producing Fluorine-Containing Compound Represented by Chemical Formula (4) In the method for producing an ether derivative of 1,3-dioxolane represented by Chemical Formula (4), the first aspect is represented by Chemical Formula (1) And a compound represented by the chemical formula (3). Although this reaction scheme is illustrated below, this invention is not limited to this.

  When the manufacturing process of the present invention is roughly divided, it is preferable to include at least the following four processes.

(1) A step of generating a condensate by dehydrating the compound represented by the chemical formula (1) and the compound represented by the chemical formula (3).
(2) A step of fluorinating the condensate produced in the step (1) in a fluorine-containing solution in a fluorine atmosphere.
(3) A step of generating a carboxylate with a base.
(4) A step of heating to decarboxylate the carboxylate.
Hereinafter, the four steps (1) to (4) will be described.

Step (1) In the method for producing an ether derivative of 1,3-dioxolane represented by chemical formula (4), the compound represented by chemical formula (1) and the compound represented by chemical formula (3) are: The reaction is preferably carried out equimolarly. Here, the compound represented by the chemical formula (1) may be used alone or in combination. The compound represented by the chemical formula (3) may be used alone or in combination. In the chemical formula (3), x represents an integer of 1 to 3, and is preferably 1.
Moreover, since it is exothermic reaction, it is preferable to make it react, cooling. In addition, there is no restriction | limiting in particular about reaction conditions, It is also preferable to add purification processes, such as distillation, before the process of following (2).

  In chemical formula (1), X represents a hydrogen atom or a fluorine atom. X is preferably a hydrogen atom because of its availability. Y represents an alkyl group having 1 to 7 carbon atoms. Y is preferably an alkyl group having 1 to 3 carbon atoms.

In the chemical formula (3), Z represents a hydroxyl group. x represents an integer of 1 to 3, and is preferably 1.

Step (2) In this step, all the hydrogen atoms in the compound produced in (1) are replaced with fluorine atoms. As the method, direct fluorination in a fluorinated solution is preferred. For such direct fluorination, see Synthetic Fluorine Chemistry, Eds by G. et al. A. Olah, R.A. D. Chambers and G.C. K. S. Prakash, J. et al. Wiley and Sons. Inc. New York (1992). J. et al. Lagow, T .; R. Bierschenk, T.W. J. et al. Juhlke and H.C. Reference can be made to the method of polyether synthesis in Kawa, Chapter 5.
Although there is no restriction | limiting in particular as a fluorine-type solution, For example, a 1,1, 2- trichlorotrifluoroethane, polyfluorobenzene etc. are preferable, Specifically, Fluorinert FC-75, FC-77, FC-88 (3M For example).
The present invention is carried out in a fluorine solution in a fluorine gas atmosphere, and the intermediate product obtained in the step (1) is fluorinated with the fluorine gas. The fluorine gas may be diluted with nitrogen gas.

Step (3) A carboxylate is produced from the fluorine compound obtained in step (2) with a base. As the base, potassium hydroxide, sodium hydroxide, cesium hydroxide and the like are preferable, and potassium hydroxide is more preferable.

Step (4) The obtained carboxylate is heated to decarboxylate. The heating temperature is preferably 250 ° C to 320 ° C, and more preferably 270 ° C to 290 ° C.

  In the manufacturing method of this invention, it can also manufacture by adding processes other than the process of said (1)-(4).

  Further, as a second embodiment in the method for producing an ether derivative of 1,3-dioxolane represented by the chemical formula (4), as shown in the following scheme, instead of the compound represented by the chemical formula (1), A compound represented by the following chemical formula (2) may be used.

Even when the compound represented by the chemical formula (2) is used as a raw material, it preferably includes at least four steps (1) to (4). In this case, the above (1) to (4) In the process of), “compound represented by chemical formula (1)” is read as “compound represented by chemical formula (2)”.
Moreover, you may add a process suitably other than the said four processes. Moreover, even if it is a case where the compound represented by Chemical formula (2) is used for a raw material, it is the same about the suitable conditions in each process of said (1)-(4).
Furthermore, X and Y in the chemical formula (2) have the same meanings as X and Y in the chemical formula (1), and the preferred ranges are also the same.

<2> Method for Producing Fluorine-Containing Compound Represented by Chemical Formula (6) The ether derivative of 1,3-dioxolane represented by Chemical Formula (6) has been described in the method for producing a fluorine-containing compound represented by Chemical Formula (4) above. It can be prepared according to the following two schemes similar to the method.

Also in the manufacturing method of the fluorine-containing compound of Chemical formula (6), it is preferable to include at least four steps (1) to (4) described in the method of manufacturing the fluorine-containing compound of Chemical Formula (4). You may add a process suitably other than one process. The same applies to suitable conditions in the steps (1) to (4).
In the chemical formulas in the above scheme, chemical formulas (1) and (2) have the same meanings as those described in the method for producing a fluorine-containing compound of the above chemical formula (4), and preferred ranges are also the same. Moreover, x and y in Chemical Formula (5) and Chemical Formula (6) each independently represent an integer of 1 to 3, and x and y may be the same or different.

<3> Method for Producing Fluorine-Containing Compound Represented by Chemical Formula (8) The ether derivative of 1,3-dioxolane represented by Chemical Formula (8) has been described in the method for producing a fluorine-containing compound represented by Chemical Formula (4) above. It can be prepared according to the following two schemes similar to the method.

Also in the manufacturing method of the fluorine-containing compound of Chemical formula (8), it is preferable to include at least four steps (1) to (4) described in the manufacturing method of the fluorine-containing compound of Chemical Formula (4). You may add a process suitably other than one process. The same applies to suitable conditions in the steps (1) to (4).
In the chemical formulas in the above two schemes, the chemical formulas (1) and (2) have the same meanings as those described in the method for producing the fluorine-containing compound of the chemical formula (4), and the preferred ranges are also the same. N1 and n2 in Chemical Formula (7) and Chemical Formula (8) each independently represent an integer of 1 to 3, and n1 and n2 may be the same or different.

2. Fluorine-containing compound The fluorine-containing compounds of the chemical formulas (4), (6) and (8) obtained by the production method of the present invention are perfluoro-1,3-dioxolane derivatives and have an ether group. Since these 1,3-dioxolane derivatives have a feature that they are easily polymerized, it is easy to produce a copolymer by copolymerization with homopolymers or other types of perfluorovinyl monomers.

3. Production method of fluorine-containing polymer The above-mentioned fluorine-containing compound can be radically polymerized by a conventional method to produce a fluorine-containing polymer. As the radical catalyst, it is preferable to use a peroxide, but a perfluoroperoxide is used so that the fluorine atom of the fluorine compound is not replaced with a hydrogen atom.
Here, when only one of the fluorine-containing compounds represented by the chemical formulas (4), (6), and (8) is used as a monomer raw material for radical polymerization, a homopolymer can be obtained.
On the other hand, a copolymer can be obtained by radical polymerization using at least two of the fluorine-containing compounds represented by the chemical formulas (4), (6) and (8). Further, a copolymer is produced by polymerization of at least one fluorine-containing compound represented by the above chemical formulas (4), (6) and (8) with another fluorine-containing unsaturated compound or a hydrocarbon-based unsaturated compound. can do.

4). Use of fluorinated polymer The fluorinated homopolymer and the fluorinated copolymer of the present invention have a high glass transition temperature, are amorphous substances, and are excellent in heat resistance, light resistance and the like. Utilizing such properties, it can be suitably used for optical materials and electrical materials.
Preferable uses of the fluorine-containing polymer of the present invention include, for example, plastic optical fibers, optical waveguides, optical lenses, prisms, photomasks, special paints and the like.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to this.

[Example 1]
<Synthesis of perfluoro 2-methylene-4- (methoxymethyl) -1,3-dioxane (fluorine-containing compound where x = 1 in chemical formula (3))>
Dehydration stops for a mixture of 2.0 mol 3-methoxy-1,2-propanediol, 2.0 mol methyl pyruvate, 10 g ion exchange resin (H form, DOWEX®) and 1 L anhydrous benzene. To reflux in a flask equipped with a Dean-Stark trap. The resulting methyl-4- (methoxymethyl-2--2-methyl-1,3-dioxane-2-carboxylate was purified by fractional distillation.

The yield of the obtained purified product was 55%, and the boiling point was 80 ° C./1.0 mmHg. Moreover, the analysis result by < ¹ > H NMR was as follows.
¹ H NMR (CDCl ₃ ) δ (ppm): 1.60 (d, 3H, —CH ₃ ), 4.28-4.50 (m, 1H, —OCH—), 4.12-4.25 and _{3.80-3.90 (m, 2H, OCH 2} -), 3.76 (d, 3H, -COOCH 3), 3.41-3.60 (m, 2H, -OCH 2 -), 3. _{39 (d, 3H, -OCH 3} ).

650 g of the purified methyl 4- (methoxymethyl-methyl-1,3-dioxane-2-carboxylate) was fluorinated in a fluorinated solvent Flurinert FC-75 under a fluorine gas atmosphere diluted with nitrogen.
After the reaction stopped, the mixture was treated with aqueous potassium hydroxide to form an organic phase and an aqueous phase. The product in the aqueous phase was separated and a portion of the water was removed under reduced pressure. The obtained product was filtered to obtain a potassium salt of perfluoro 4- (methoxymethyl) -2-methyl-1,3-dioxane-2-carboxylate. The yield was 95%. The results of ¹ H NMR and ¹⁹ F NMR of the obtained potassium salt are shown below.

¹ H NMR (DMSO) δ (ppm): None.
¹⁹ F NMR (DMSO) δ (ppm): −55.11 (dt, 3F, —OCF ₃ ), −79.71 (d, 3F, —CF ₃ ), 76.59 (m, 1F) and − 81.00 (m, 1F) (2F _{total, OCF 2 -), - 85.35} (m, 2F, -OCF 2 -), - 120.67 (dm, 1F, -OCF-).

100 g (0.243 mol) of the above potassium salt was decomposed at 250 ° C. in an argon atmosphere, and the product was collected in a trap cooled to −78 ° C. The product was purified by fractional distillation to give perfluoro 2-methylene-4- (methoxymethyl) -1,3-dioxane. The yield was 81% (61 g, 0.19 mol). The results of ¹ H NMR, ¹⁹ F NMR and GC-MS of the obtained target product are shown below.

^-1 H NMR (CDCl ₃ ) δ (ppm); none.
¹⁹ F NMR (CDCl ₃ ) δ (ppm): −55.56 (3F, —OCF ₃ ), −82.54 (1F) and −87.40 (1F) (2F in total, —OCF ₂ —) , −85.28 (m, 2F, —OCF ₂ —), −126.06 (2F, 4 line pattern, ═CF ₂ ), −128.44 (1F, —OCF—).
GC-MS: m / e 310 (M ⁺ ) and had the expected pattern.

  The outline of the synthesis scheme of Example 1 is shown below.

[Example 2]
<Free radical polymerization of perfluoro-2-methylene-4- (methoxymethyl) -1,3-dioxane>
2 g of perfluoro-2-methylene-4- (methoxymethyl) -1,3-dioxane and 8.8 mg of perfluorobenzoyl peroxide are charged into a glass tube, which is then subjected to 3 vacuum-thaw cycles. Degassed and refilled with argon. The tube was sealed under vacuum and heated at 60 ° C. for 24 hours to obtain a perfluoro-2-methylene-4- (methoxymethyl) -1,3-dioxane homopolymer as a solid rod.
The homopolymer was dissolved in hexafluorobenzene, precipitated into chloroform and dried in vacuo to a constant weight (1.8 g). The yield was 90% and the glass transition temperature Tg was 101 ° C.
The results of FTIR, ¹ H NMR, ¹⁹ F NMR, and ¹³ C NMR are shown below.

FTIR: no carbonyl absorption.
¹ H NMR (C ₆ F ₆ / CDCl ₃ ) δ (ppm): None.
¹⁹ F NMR (C ₆ F ₆ / CDCl ₃ ) δ (ppm): −58.32 (3F, —OCF ₃ ), −79.40 (2F, —OCF ₂ —), −85.8 (2F, _{-OCF 2 -), - 109.05 (} 2F, -CF 2 on the backbone -), 121.80 (on the side chain OCF-).
_{^{· 13 C NMR (C 6 F}} 6 / CDCl 3) δ (ppm): carbonyl carbon peaks no.

[Example 3]
<Synthesis of perfluoro-2-methylene-4,5-dimethoxymethyl-1,3-dioxane (fluorine-containing compound where x = 1 and y = 1 in chemical formula (5))>
Perfluoro-2-methylene-4,5-dimethoxymethyl-1,3-dioxane is a condensate obtained by dehydrating a diol compound and 2-dioxopropyl acetate according to the following schematic scheme, as in Example 1. Was obtained by fluorination in a fluorine solution in a fluorine gas atmosphere.

  1,4-Dimethylmethoxy-2,3-butyldiol was obtained by a condensation reaction of tartaric acid and dimethylmethoxypropane according to the description of Helvetica Chimica Acta 60, 031 (1977) Dieter Seebath et al.

Methyl-4,5-dimethoxydimethyl-1,3-dioxane-2-carboxylate was obtained using diol and 2-dioxopropyl acetate in a benzene solvent and p-toluenesulfonic acid as a catalyst. The purified compound had a boiling point of 150 ° C./8 Torr. The result of ¹ H NMR is shown below.

¹ H NMR (CDCl ₃ ) δ (ppm): 4.0-4.2 (m, 2H, in —CH ₂ OC (═O) —, 2-CH—, 4H), 3.56 (m, − _{CH 2 O-, 4H), 3.4} (m, -OCH 3, 6H), 2.11 (s, -C (= O) CH 3, 3H), 1.42 (s, -CCH 3, 3H ).

1,000 g (4.95 mol) of the purified methyl carboxylate was fluorinated in a fluorinated solvent Flurinert FC-75 under a fluorine gas atmosphere reduced with nitrogen.
After the reaction stopped, the mixture was treated with aqueous potassium hydroxide to form an organic phase and an aqueous phase. The product in the aqueous phase was separated and a portion of the water was removed under reduced pressure. The obtained product was filtered to obtain a potassium salt. This salt was further dried at 80 ° C. under reduced pressure to obtain 1295 g (3.46 mol).
The results of ¹ H NMR and ¹⁹ F NMR of the obtained potassium salt are shown below.

¹ H NMR (in d ₆ -DMSO) δ (ppm): None.
¹⁹ F NMR (in d ₆ -DMSO) δ (ppm): −82, −80.05 (3F, —CF ₃ ), −78.57, −79.92, −81.58, −91.32 _{(4F, -OCF 2 -),} - 129.57, -130.79 (m, 2F, -CFO-).

The potassium salt was decomposed at 250 ° C. under a Calgon atmosphere, and the product was collected in a trap cooled to −78 ° C. The product was purified by fractional distillation to give perfluoro-2-methylene-4,5-dimethoxymethyl-1,3-dioxane. The yield was 50%. The results of ¹ H NMR and ¹⁹ F NMR of the obtained target product are shown below.

^-1 H NMR (in CDCl ₃ ) δ (ppm); none.
_{^{· 19 F NMR (in CDCl 3}} ) δ (ppm): - 56 (m, CF 3 O-, 6F), - 84 (-CF 2 O-, 4F), - 126 (2F, = CF 2), - 138 (m, 2F, -CFO).

<Free radical polymerization of perfluoro-2-methylene-4,5-dimethoxymethyl-1,3-dioxane>
2 g perfluoro-2-methylene-4,5-dimethoxymethyl-1,3-dioxane and 8.8 mg perfluorobenzoyl peroxide are charged into a glass tube, which is then subjected to 3 vacuum drying-thawing cycles. And then backfilled with argon. The tube was sealed under vacuum and heated at 60 ° C. for 30 hours to obtain a perfluoro-2-methylene-4- (methoxymethyl) -1,3-dioxane homopolymer as a solid rod.
The homopolymer was dissolved in hexafluorobenzene, precipitated into chloroform and dried in vacuo to a constant weight (1.8 g). The yield was 90%, the glass transition temperature Tg was 88 ° C., and the minute rotation was 255 ° C. (nitrogen gas).
The results of FTIR, ¹ H NMR, ¹⁹ F NMR, and ¹³ C NMR are shown below.

FTIR: no carbonyl absorption.
¹ H NMR (in CDCl ₃ ) δ (ppm): None.
¹⁹ F NMR (in CDCl ₃ ) δ (ppm): −100 to 130 (4F, —CF and —CF ₂ in the main chain), −110 (4F, —CF ₂ —), −58 (6F, − OCF _{3).
^{· 13 C NMR (C 6 F}} 6 / CDCl 3) δ (ppm): carbonyl carbon peaks no.

[Example 4]
<Synthesis of ether ring-containing perfluorodioxane (compound in the case of n1 and n2 = 1 in chemical formula (7))>
A condensation reaction between 1,4-anhydroerythritol and pyruvate or 2-oxopropyl acetate was carried out. Hereinafter, the latter condensation reaction using 2-oxopropyl acetate will be described in detail, and an outline of a synthesis scheme using 2-oxopropyl acetate of Example 3 will be shown.

A mixture of 448 g of 1,4-anhydroerythritol, 500 g of 2-oxopropyl acetate and 30 g of p-toluene sulfate in 1 L of benzene was placed in a 2 L flask. The mixture was refluxed and 107 ml of water was distilled off. The product was treated with sodium carbonate and then washed with water. The product was directly fluorinated in a fluorinated solvent under a fluorine gas / nitrogen gas atmosphere.
After fluorination, the fluorinated solution was treated with an aqueous potassium hydroxide solution under cooling to obtain an organic phase and an aqueous phase. After separation of the product in the aqueous phase, a portion of the water was removed under reduced pressure. The isolated potassium salt was filtered. The yield was 70% and there was no melting point.
The results of ¹ H NMR and ¹⁹ F NMR are shown below.

-No ¹ H NMR (DMSO).
¹⁹ F NMR (DMSO) δ (ppm): 82, 82.05 (3F, CF ₃ ), −78.57 to 79.92, −83.58 to 93.32 (4F, —OCF ₂ —), -129.58, -130.79 (m, 2F, -CFO).

100 g of the obtained potassium salt was decomposed at 250 ° C., then cooled to −78 ° C. and collected in a trap. The obtained compound was purified by fractional distillation to obtain perfluoro-2-ether ring-substituted dioxane. The yield of the target product was 50%, and the boiling point was 74 ° C./760 mmHg.
The results of ¹ H NMR and ¹⁹ F NMR are shown below.

_{^{· 1 H NMR (CDCL 3)}} δ (ppm) None _{^{· 19 F NMR (CDCL 3)}} δ (ppm): - 78, -92 (4F, -OCF 2 -), - 136 (2F, -CF-), -126 (2F, = CF ₂₎
-GC-MS: m / e 272 (M ^<+> ).

[Example 5]
<Free radical polymerization of perfluoro-2-ether ring-substituted dioxane>
A glass tube was filled with 2 g of the monomer obtained in Example 4 (perfluoro-2-ether ring-substituted dioxane) and 8.8 mg of perfluorobenzoyl peroxide, which was then subjected to 3 vacuum-thaw cycles. And then backfilled with argon.
The tube was sealed under vacuum and heated at 60 ° C. for 1 day. A solid polymer rod was obtained. The polymer was dissolved in hexafluorobenzene, precipitated in chloroform, and dried in vacuum to a constant weight (1.8 g) to obtain the desired polymer. The yield was 90%.
The results of FTIR, DSC, and refractive index of the obtained polymer are shown below.

FTIR: no carbonyl absorption.
DSC: Tg = 164 ° C., TGA initial decomposition temperature is 350 ° C. under nitrogen atmosphere.
Refractive index: 1.3372 (532 nm), 1.3348 (632 nm), 1.3315 (839 nm); 1.3302 (1.544 nm).

[Example 6]
<Copolymer of fluorine-containing compound produced in Example 1 (M ₁₎ and the fluorine-containing compound prepared in Example 4 (M _2)>
Glass polymerization of the fluorine-containing compound (M ₁ ) prepared in Example ₁ and the fluorine-containing compound (M ₂ ) prepared in Example 4 in various ratios together with perfluorodibenzoyl peroxide or perfluorodi-t-butyl peroxide. Placed in tube and degassed with argon in 3 vacuum-thaw cycles. The tube was sealed under vacuum and heated at 60-65 ° C. To determine monomer reactivity, the resulting copolymer was dissolved in hexafluoro-benzene and then precipitated into chloroform and dried to constant weight in vacuo to stop monomer conversion at about 10-15%. It was. The composition of the polymer produced was determined by measuring ¹⁹ F NMR.
For the typical copolymer obtained, data such as glass transition temperature and refractive index are shown in Table 1, FIG. 1, FIG. 2, and FIG.

The glass transition temperatures (Tg) of the fluorine-containing compound (M ₁ ) and the fluorine-containing compound (M ₂ ) were 110 ° C. and 168 ° C., respectively.

As an example of a copolymer of M ₁ and M ₂ , the following is a description of the case where the feed ratio of the fluorine-containing compound (M ₁ ) to the fluorine-containing compound (M ₂ ) is 20:80 and 40:60. Polymer production methods were described in detail and the dispersibility of these copolymers was evaluated.

(Copolymer [1] having a charge molar ratio of (M ₁ ) to (M ₂ ) of 20:80)
6.20 g (0.020 mol) of the fluorinated compound (M ₁ ) prepared in Example 1 and 2.18 g (0.80 mol) of the fluorinated compound (M ₂ ) prepared in Example 4 were placed in a glass polymerization tube. ) And 1.4 g of perfluorobenzoyl peroxide as a polymerization initiator.
The tube was degassed with argon in three vacuum-thaw cycles, then the tube was sealed in vacuo, heated gradually at 55-60 ° C. for 12 hours, and then further heated to 100 ° C. for 24 hours. The solid product was dissolved in hexafluorobenzene and then precipitated into chloroform. The yield was 92%, and the glass transition temperature (Tg) was 130 ° C. by DSC analysis.
The composition of the produced copolymer was determined by ¹⁹ F NMR measurement, and it was confirmed that the composition ratios of M ₁ and M ₂ were 16.5 and 83.5 mol%, respectively.
The copolymer melted without decomposition at 280-300 ° C. The refractive indexes were 1.3470 (532 nm), 1.3449 (633 nm), 1.3433 (839 nm) and 1.3405 (1544 nm).

(Copolymer [2] having a charge molar ratio of (M ₁ ) to (M ₂ ) of 40:60)
12.4 g (0.04 mol) of the fluorine-containing compound (M ₁ ) prepared in Example 1 and 16.30 g (0.06 mol) of the fluorine-containing compound (M ₂ ) prepared in Example 4 on a glass tube 1.4 g of perfluorobenzoyl peroxide was charged. The tube was degassed, sealed in vacuum and heated at 55-60 ° C. for 12 hours and further heated to 100 ° C. for 24 hours to complete the polymerization. The resulting copolymer was dissolved in hexafluorobenzene and then precipitated into chloroform. The yield was 92% and Tg was 120 ° C.
The composition of the copolymer was determined by ¹⁹ F NMR measurement, and it was confirmed that the composition ratio of M ₁ and M ₂ was 38 and 62, respectively.
The copolymer melted at 290-300 ° C. The refractive indexes were 1.3438 (532 nm), 1.3417 (633 nm), 1.3398 (839 nm) and 1.3345 (1544 nm).

  The material dispersibility of the copolymer [1] and the copolymer [2] was calculated by the following formula I.

Formula I; M (λ) = − λd ² n / cdλ ²
[Wherein n represents the refractive index of the polymer, λ represents the relevant wavelength, and c represents the speed of light in vacuum. ]

Further, d ² n / dλ ² was calculated by applying refractive index data as a function of wavelength to a three term sellmeier equation.

From the values of M (λ) and d ² n / dλ ² obtained by these calculations, it is clear that the material dispersibility of the copolymer [1] and the copolymer [2] is comparable to that of the perfluorinated polymer, CYTOP. became.

[Example 7]
<Copolymer of the fluorine-containing compound prepared in Example 4 and (M ₂₎ and heptafluoropropyl trifluorovinyl ether>
In a glass polymerization tube, 200 mol of CFC-113, 27.2 g (0.10 mol) of a fluorinated compound (M ₂ ), 9.7 g (0.12 mol) of heptafluoropropyl trifluorovinyl ether and 1.3 g of peroxidic peroxide. Filled with fluorodibenzoyl.
The tube was degassed and sealed and heated at 50 ° C. for 8 hours and then at 60 ° C. for 12 hours. The solvent excess monomer was then removed by evaporation and the resulting polymer was dried at 110 ° C. under vacuum for 16 hours. The product weighed 34 g and was compressed at 340 ° C. into a film.
When ¹⁹ F NMR of this copolymer was measured, it was found that it was composed of 58 mol% of a fluorine-containing compound (M ₂ ) and 42 mol% of vinyl ether. Moreover, when the obtained copolymer was analyzed by DSC, the glass transition temperature Tg was 90 degreeC.

[Example 8]
<Copolymer of the fluorine-containing compound prepared in Example 4 and (M ₂₎ and heptafluoropropyl trifluorovinyl ether>
A glass polymerization tube was filled with 27.2 g (0.10 mol) of a fluorine-containing compound (M ₂ ), 1.9 g (0.02 mol) of heptafluoropropyl trifluorovinyl ether, and 1.3 g of perfluorodibenzoyl peroxide. did.
After the tube was degassed and sealed, the tube was heated at 40 ° C. for 10 hours and then at 60 ° C. for 12 hours. Unreacted monomer was removed by evaporation and the resulting polymer was dried at 110 ° C. under vacuum for 16 hours. The polymer was dissolved in hexafluorobenzene and reprecipitated with chloroform.
When ¹⁹ F NMR of this copolymer was measured, it was found that it was composed of 92 mol% of a fluorine-containing compound (M ₂ ) and 8 mol% of vinyl ether. Moreover, when the obtained copolymer was analyzed by DSC, the glass transition temperature Tg was 122 degreeC.

In Example 6, the relationship (mol%) between the content (mol%) of the fluorine-containing compound (M ₁ ) in the raw material and the content of the structure due to the fluorine-containing compound (M ₁ ) in the produced polymer. FIG. It is a diagram showing the relationship between the content of the glass transition temperature (mol%) and the copolymer (Tg) of the fluorine-containing compound in the copolymer obtained in Example 5 (M _1). It is a diagram showing the relationship between content (mol%) and the refractive index of the copolymer of the fluorine-containing compound in the copolymer obtained in Example 5 (M _1).

Claims (8)

A step of obtaining a condensate by reacting one or more compounds represented by the following chemical formula (1) or one or more compounds represented by the following chemical formula (3) with one or more of the compounds represented by the following chemical formula (3): The manufacturing method of the fluorine-containing compound represented by following Chemical formula (4) which has the process of fluorinating this condensate in a fluorine-type solution in fluorine gas atmosphere.
[Wherein, X represents a hydrogen atom or a fluorine atom, Y represents an alkyl group having 1 to 7 carbon atoms, Z is represents a hydroxyl group, x represents an integer of 1-3. ] A step of obtaining a condensate by reacting one or more compounds represented by the following chemical formula (1) or one or more compounds represented by the following chemical formula (5) with one or more of the compounds represented by the following chemical formula (5): A method of producing a fluorine-containing compound represented by the following chemical formula (6), comprising: fluorinating the condensate in a fluorine-based solution in a fluorine gas atmosphere.
[Wherein, X represents a hydrogen atom or a fluorine atom, Y represents an alkyl group having 1 to 7 carbon atoms, Z is represents a hydroxyl group, x and y are each integer of independently 1 to 3 Represents. ] A step of obtaining a condensate by reacting one or more compounds represented by the following chemical formula (1) or one represented by the following chemical formula (7) with one or more compounds represented by the following chemical formula (7) And a step of fluorinating the condensate in a fluorine-based solution in a fluorine gas atmosphere. A method for producing a fluorine-containing compound represented by the following chemical formula (8):
[Wherein, X represents a hydrogen atom or a fluorine atom, Y represents an alkyl group having 1 to 7 carbon atoms, Z is represents a hydroxyl group, an integer of 1-3 each independently n1 and n2 Represents. ] Under hear Science formula (6) or the fluorine-containing compound represented by the chemical formula (8).


[Wherein, x and y each independently represents an integer of 1 to 3, and n1 and n2 each independently represents an integer of 1 to 3. ]   A fluorine-containing homopolymer obtained by polymerization of the fluorine-containing compound according to claim 4.   A fluorine-containing copolymer obtained by copolymerization of the fluorine-containing compound according to claim 4 and an unsaturated fluorine-containing compound other than the fluorine-containing compound. An optical member or an electrical member comprising at least one of the fluorine-containing homopolymer according to claim 5 and the fluorine-containing copolymer according to claim 6.   The optical member or electrical member according to claim 7, wherein the optical member or electrical member is an optical fiber, an optical waveguide, a photomask, or a coating material.