JP5358115B2 - Polymer having alicyclic structure and perfluorocyclobutyl ether structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent material capable of canceling various problems generated when being used in a part accompanying heat generation and a part to which a stress load is intermittently or continuously applied and improving transparency and heat resistance especially in a UV region. <P>SOLUTION: A polymer has an alicyclic structure and a perfluoro cyclobutyl ether structure and is represented by formula (1) (in the formula, R denotes a bivalent group by which an alicyclic group is formed). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a polymer having an alicyclic structure and a perfluorocyclobutyl ether structure. More specifically, the present invention relates to a polymer excellent in transparency and moldability, a transparent material comprising the polymer, and a molded body thereof.

Engineering plastics that are transparent and have excellent mechanical properties are widely used as optical materials. For example, polymethyl methacrylate and polycarbonate are used as optical materials for CDs, DVDs, lenses, etc., and for transparent parts of automobiles. Has been.
However, polymethyl methacrylate is excellent in transparency, but has a problem of high hygroscopicity and poor shape stability. Polycarbonate has high heat resistance and excellent transparency, but has problems such as poor flowability and increased birefringence of the molded product. Therefore, neither polymethylmethacrylate nor polycarbonate was sufficiently satisfactory as an optical material.

  In recent years, optical materials have been widely used in various optical information processing devices such as optical lenses, optical fibers, optical waveguides, and photonic crystals, and display devices such as flat panel displays (FPD). With the expansion of applications, further improvement in transparency in the ultraviolet region has been demanded from the demand for the most basic improvement in transparency as an optical material, particularly the improvement in information processing speed as an optical information processing apparatus. In addition, the optical material is thin film, film, fiber, and is often used in parts that generate heat, or parts that are intermittently or continuously stressed. Mechanical strength was sought.

Non-Patent Document 1 discloses a polymer containing an aromatic structure and a perfluorocyclobutyl ether structure having excellent transparency, water absorption, strength and heat resistance. However, when this polymer is used in thin film, film, or fiber forms where heat generation occurs, or where stress is applied intermittently or continuously, the optical material made of this polymer is Since the content of the aromatic ring structure is high, the transparency in the ultraviolet region is not sufficient, and the heat resistance is not sufficient.
In addition to transparency, there has been no material having particularly high heat resistance and high strength that can withstand the heat load generated by continuous transmission of high-intensity light.
Macromolecules, 37, 5724 (2004)

  The object of the present invention is to eliminate various problems that occur when optical materials are used in thin film, film, and fiber forms in parts that generate heat and parts that are intermittently or continuously stressed. Furthermore, it is to provide a transparent material having improved transparency and heat resistance, particularly in the ultraviolet region, among properties such as transparency, water absorption, strength and heat resistance.

（式中、Ｒは、炭素数５〜５０の置換又は非置換の２価の脂環式基、又は炭素数６〜１０の２価の芳香族基、炭素数１〜２０の置換又は非置換の２価の直鎖状脂肪族基、炭素数１〜２０の置換又は非置換の２価の分岐状脂肪族基、炭素数５〜５０の置換又は非置換の２価の脂環式基からなる群から選択される１以上の２価の基及び炭素数５〜５０の置換又は非置換の２価の脂環式基が結合して形成される２価の基であり、
ｎは１０以上１００００以下の整数である。）
２．前記炭素数５〜５０の置換又は非置換の２価の脂環式基が、アダマンタン構造、ビアダマンタン構造、ジアマンタン構造又はトリアマンタン構造を含む１に記載のポリマー。
３．前記式（１）で表されるポリマーが、下記式（２）又は（３）で表されるポリマーである１又は２に記載のポリマー。

（式中、Ｒ’は上記アダマンタン部位構造又はアリーレン部位に置換している置換基であって、Ｒ’はハロゲン元素、炭素数６〜３０の置換又は非置換の芳香族置換基、炭素数１〜２０の置換又は非置換の直鎖状脂肪族置換基、炭素数１〜２０の置換又は非置換の分岐状脂肪族置換基又は炭素数５〜５０の置換又は非置換の脂環式置換基であり、
ｍは０以上１４以下の整数であり、ｍが２以上の場合、複数のＲ’はそれぞれ同一でも異なってもよい）
４．下記式（４）で表されるモノマー。

（式中、Ｒは式（１）のＲと同様である。）
５．４に記載の一般式（４）で表されるモノマーを付加環化反応する１〜３のいずれかに記載のポリマーの製造方法。
６．１〜３のいずれかに記載のポリマー、又は５に記載のポリマーの製造方法により得られるポリマーを含む透明材料。
７．１〜３のいずれかに記載のポリマー、又は５に記載のポリマーの製造方法により得られるポリマーを有機溶媒に溶解させた塗料。
８．７に記載の塗料を用いて形成される薄膜。
９．６に記載の透明材料からなる部材。
１０．９に記載の部材を備える装置。 According to the present invention, the following polymers and the like are provided.
1. A polymer represented by the following formula (1) having an alicyclic structure and a perfluorocyclobutyl ether structure.

(In the formula, R is a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms, or a divalent aromatic group having 6 to 10 carbon atoms, substituted or unsubstituted having 1 to 20 carbon atoms. A divalent linear aliphatic group, a substituted or unsubstituted divalent branched aliphatic group having 1 to 20 carbon atoms, and a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms. A divalent group formed by combining one or more divalent groups selected from the group consisting of and a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms;
n is an integer of 10 or more and 10,000 or less. )
2. 2. The polymer according to 1, wherein the substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms includes an adamantane structure, a biadamantane structure, a diamantane structure, or a triamantane structure.
3. The polymer according to 1 or 2, wherein the polymer represented by the formula (1) is a polymer represented by the following formula (2) or (3).

Wherein R ′ is a substituent substituted on the adamantane moiety structure or arylene moiety, and R ′ is a halogen element, a substituted or unsubstituted aromatic substituent having 6 to 30 carbon atoms, or 1 carbon atom. -20 substituted or unsubstituted linear aliphatic substituent, 1 to 20 carbon substituted or unsubstituted branched aliphatic substituent, or 5 to 50 carbon substituted or unsubstituted alicyclic substituent And
m is an integer of 0 or more and 14 or less, and when m is 2 or more, a plurality of R ′ may be the same or different)
4). A monomer represented by the following formula (4).

(In the formula, R is the same as R in formula (1).)
The manufacturing method of the polymer in any one of 1-3 which carries out cycloaddition reaction of the monomer represented by General formula (4) as described in 5.4.
6. A transparent material containing the polymer according to any one of items 1 to 3 or the polymer obtained by the method for producing a polymer according to 5.
7. A paint obtained by dissolving the polymer according to any one of 1 to 3 or the polymer obtained by the method for producing a polymer according to 5 in an organic solvent.
A thin film formed using the paint according to 8.7.
A member made of the transparent material according to 9.6.
An apparatus comprising the member according to 10.9.

  According to the present invention, it is possible to eliminate various problems that occur when an optical material is used in the form of a thin film, a film, or a fiber in a part that generates heat and a part that is intermittently or continuously stressed. Furthermore, among the properties such as transparency, water absorption, strength and heat resistance, it is possible to provide a transparent material with improved transparency and heat resistance particularly in the ultraviolet region.

（式中、Ｒは、炭素数５〜５０の置換又は非置換の２価の脂環式基、又は炭素数６〜１０の２価の芳香族基、炭素数１〜２０の置換又は非置換の２価の直鎖状脂肪族基、炭素数１〜２０の置換又は非置換の２価の分岐状脂肪族基、炭素数５〜５０の置換又は非置換の２価の脂環式基からなる群から選択される１以上の２価の基及び炭素数５〜５０の置換又は非置換の２価の脂環式基が結合して形成される２価の基を表し、
Ｒには、フッ素、塩素、臭素等のハロゲン元素、炭素数６〜３０の置換又は非置換の芳香族置換基、炭素数１〜２０の置換又は非置換の直鎖状脂肪族置換基、炭素数１〜２０の置換又は非置換の分岐状脂肪族置換基、炭素数５〜５０の置換又は非置換の脂環式置換基が置換していてもよく、
前記炭素数５〜５０の置換又は非置換の２価の脂環式基は、その一部がエーテル結合、エステル結合、炭酸エステル結合、チオエーテル結合、チオエステル結合からなる群から選択される２価の基にさらにヘテロ原子が含まれる２価の基が存在していてもよい。
ｎは１０以上１００００以下の整数である。） The polymer of the present invention has an alicyclic structure and a perfluorocyclobutyl ether structure, and is represented by the following formula (1).

(In the formula, R is a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms, or a divalent aromatic group having 6 to 10 carbon atoms, substituted or unsubstituted having 1 to 20 carbon atoms. A divalent linear aliphatic group, a substituted or unsubstituted divalent branched aliphatic group having 1 to 20 carbon atoms, and a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms. Represents a divalent group formed by combining one or more divalent groups selected from the group consisting of and a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms;
R includes halogen elements such as fluorine, chlorine and bromine, substituted or unsubstituted aromatic substituents having 6 to 30 carbon atoms, substituted or unsubstituted linear aliphatic substituents having 1 to 20 carbon atoms, carbon A substituted or unsubstituted branched aliphatic substituent having 1 to 20 carbon atoms, a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms may be substituted,
The substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms is a divalent selected from the group consisting of an ether bond, an ester bond, a carbonate ester bond, a thioether bond, and a thioester bond. A divalent group in which a hetero atom is further contained in the group may be present.
n is an integer of 10 or more and 10,000 or less. )

In the formula (1), R is a divalent group of (i) or (ii).
(I) a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms (ii) a divalent aromatic group having 6 to 10 carbon atoms, a substituted or unsubstituted divalent group having 1 to 20 carbon atoms From a group consisting of a linear aliphatic group, a substituted or unsubstituted divalent branched aliphatic group having 1 to 20 carbon atoms, and a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms. A divalent group formed by combining one or more selected divalent groups and a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms

Examples of the substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms include a cyclopentane structure , a cyclohexane structure, a cycloheptane structure, or a ring having a hetero atom in place of one carbon constituting the cycloalkane structure. Examples thereof include a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms including a structure, and preferably a substituted or substituted carbon atom having 5 to 50 carbon atoms including an adamantane structure, a biadamantan structure, a diamantane structure, or a triamantane structure. An unsubstituted divalent alicyclic group, more preferably an adamantane structure, a biadamantane structure, a diamantane structure, or a triamantane structure.

  The substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms is a divalent group partially selected from the group consisting of an ether bond, an ester bond, a carbonate ester bond, a thioether bond, and a thioester bond. Further, a divalent group containing a hetero atom may be present.

  Examples of the divalent aromatic group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group.

  Examples of the substituted or unsubstituted divalent linear aliphatic group having 1 to 20 carbon atoms include a methylene group, an ethylene group, and a propylene group.

  Examples of the substituted or unsubstituted divalent branched aliphatic group having 1 to 20 carbon atoms include a methylmethylene group, a trifluoromethylmethylene group, a dimethylmethylene group, and a bis (trifluoromethyl) methylene group.

  The substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms is composed of an adamantane structure, biadamantane structure, diamantane structure, triamantane structure, cyclopentane structure, cyclohexane structure, cycloheptane structure or norbornene structure And a divalent alicyclic group composed of an adamantane structure, a biadamantane structure, a diamantane structure or a triamantane structure is preferable.

  R is a halogen element such as fluorine, chlorine or bromine, a substituted or unsubstituted aromatic substituent having 6 to 30 carbon atoms, a substituted or unsubstituted linear aliphatic substituent having 1 to 20 carbon atoms, A substituted or unsubstituted branched aliphatic substituent having 1 to 20 carbon atoms and a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms may be substituted.

  Examples of the substituted or unsubstituted aromatic substituent having 6 to 30 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a terphenyl group.

  A substituted or unsubstituted linear aliphatic substituent having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic substituent having 1 to 20 carbon atoms, and a substituted or unsubstituted alicyclic ring having 5 to 50 carbon atoms The formula substituent is, for example, a substituent in which each divalent group described in R is monovalent.

  In the formula (1), n represents the degree of polymerization, and n is an integer of 10 or more and 10,000 or less. When n is less than 10, the polymer characteristics may not be obtained. On the other hand, when n is more than 10,000, the solubility of the polymer decreases, the increase in the polymerization degree during the polymerization reaction is suppressed, and there is a possibility that a polymer solution for forming a thin film cannot be prepared.

（式中、Ｒ’は上記アダマンタン部位構造又はアリーレン部位に置換している置換基であって、Ｒ’はハロゲン元素、炭素数６〜３０の置換又は非置換の芳香族置換基、炭素数１〜２０の置換又は非置換の直鎖状脂肪族置換基、炭素数１〜２０の置換又は非置換の分岐状脂肪族置換基又は炭素数５〜５０の置換又は非置換の脂環式置換基であり、
ｍは０以上１４以下の整数である。） The polymer represented by the formula (1) is preferably a polymer represented by the following formula (2) or (3).

Wherein R ′ is a substituent substituted on the adamantane moiety structure or arylene moiety, and R ′ is a halogen element, a substituted or unsubstituted aromatic substituent having 6 to 30 carbon atoms, or 1 carbon atom. -20 substituted or unsubstituted linear aliphatic substituent, 1 to 20 carbon substituted or unsubstituted branched aliphatic substituent, or 5 to 50 carbon substituted or unsubstituted alicyclic substituent And
m is an integer of 0 or more and 14 or less. )

Particularly preferred specific examples of R ′ include fluorine, phenyl group, naphthyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group. , Heptyl group, octyl group, nonyl group, decyl group, cyclopentyl group, cyclobutyl group, cyclohexyl group, norbornyl group, adamantyl group, biadamantyl group, dimethylbiadamantyl group, dibutylbiadamantyl group, diamantyl group, triamantyl group, and these The substituent which combines 2 or more among substituents is mentioned.
When R ′ is other than the above-described substituents, the heat resistance and strength of the polymer may be reduced due to molecular motion or thermal decomposition of the substituents themselves.

Specific examples of the polymer of the present invention are shown below.

（式中、Ｒは式（１）のＲと同様である。） The polymer having an alicyclic structure and a perfluorocyclobutyl ether structure of the present invention is selected, for example, by subjecting a monomer represented by the following formula (4) to a cycloaddition reaction using heat, ultraviolet rays, electron beams, plasma, or the like. It can be manufactured with good rate and yield. Moreover, it can manufacture also by making it mix and copolymerize the monomer represented by several Formula (4).

(In the formula, R is the same as R in formula (1).)

The preferred polymerization conditions vary depending on the monomer used and the desired physical properties of the resulting polymer, but in the case of a cycloaddition reaction by heat, the monomer is cycloadditionally reacted by heating at a temperature in the range of 50 ° C to 300 ° C. be able to.

The monomer represented by the formula (4) can be produced by a conventionally known method (for example, Macromolecules, 37, 5724 (2004)).
Specific production conditions vary depending on the desired structure of the monomer, but can be controlled by the reactants, catalyst, concentration and addition ratio of raw materials, amount of solvent added, reaction temperature, reaction time, post-reaction treatment method, etc. It is.

The produced monomer is preferably used after purification. By using the purified monomer, stability can be improved in addition to the transparency, heat resistance and strength of the polymer of the present invention.
Examples of monomer purification methods include ion exchange resin treatment, reprecipitation, recrystallization, microfiltration, drying, and the like. Fe ³⁺ , Cl ⁻ , Na ⁺ , K ⁺ , Ca ^{2+ and the} like contained in the monomer by these purification methods. Ionic impurities, reaction solvent, post-treatment solvent, moisture and the like can be removed.

  In addition, when the polymer of the present invention is produced by adding a catalyst or a reactant, the obtained polymer is purified using the above-described purification method, thereby adding to the transparency, heat resistance and strength of the polymer of the present invention. Stability can be improved.

  A conventional polymer containing an aromatic ring structure and a perfluorocyclobutyl ether structure has a high content of the aromatic ring structure and is not sufficiently transparent in the ultraviolet region. Therefore, the polymer is improved by substitution with an aliphatic structure. On the other hand, in the present invention, the aliphatic structure is a cycloaliphatic structure, in particular, among the compounds composed of carbon, a structure such as adamantane common to diamond having the highest strength and high stability on the earth. The free rotation of the ether bond in the inside can be restricted, and the heat resistance and strength of the polymer can be dramatically improved.

The transparent material containing a polymer having an alicyclic structure and a perfluorocyclobutyl ether structure according to the present invention is used in various optical information processing devices such as optical lenses, optical fibers, optical waveguides, photonic crystals, and display devices such as flat panel displays. Performance and durability can be dramatically improved. In addition, the transparent material containing the polymer of the present invention has characteristics such as high transparency in the ultraviolet light region, low water absorption, high strength, high heat resistance and the like.
The transparent material of the present invention may contain various additives used in the resin molding field in addition to the polymer of the present invention.

The transparent material of the present invention can produce various molded products (thin films, films, thin plates, fibers, etc. formed on a substrate such as a silicon wafer) by a known molding method.
Examples of the molding method include injection molding method, injection compression molding method, extrusion molding method, blow molding method, pressure molding method, transfer molding method, spin coating method, spray coating method, casting method, CVD method, etc. A molding method can be appropriately selected according to the form and performance of a desired product.
In addition, molding is performed using a monomer or a low molecular weight polymer (oligomer) having a prepolymerization of n to 2 to 25, and the resulting molded body is cured by heat, ultraviolet light, electron beam, plasma, etc. (cyclization addition) Reaction).

When the transparent material of the present invention is formed into a thin film by a spin coating method or the like, a paint in which the transparent material of the present invention is dissolved in an organic solvent can be used.
Organic solvents include chloroform, dichloromethane, 1,1,2,2-tetrachloroethane, dichloroethane, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, DMF, NMP, dimethylacetamide, DMSO, anisole, acetophenone, benzonitrile, nitrobenzene, propylene Examples include glycol methyl ether acetate, propylene glycol monomethyl ether, THF, cyclohexanone, methyl ethyl ketone, and acetone.

The concentration of the transparent material of the present invention in the paint may be appropriately adjusted in consideration of the viscosity of the paint and the molding method.
The thickness of the thin film is not particularly limited, but generally a thickness of about 10 nm to 10 μm is preferably used.

  The film made of the transparent material of the present invention has a thickness of about 1 μm to 1 mm, and the thin plate has a thickness of about 1 mm to 1 cm.

  The transparent material of the present invention can be used as a member using a known transparent material. Specific examples include a transparent film such as an FPD protective film, a transparent thin plate such as a light diffusing plate and a light reflecting plate, a linear transparent member such as an optical fiber and an optical waveguide, and an optical information processing member such as a photonic crystal. The above-described member can be used as a constituent member of the device, and for example, can be used as a constituent member of a display device such as an optical information processing device or FPD.

The transparent material of the present invention has high transparency particularly in the ultraviolet region. In addition, having transparency means that it transmits without absorbing part or all of light.
In the transparent material of the present invention, the maximum non-transmission light wavelength (λ _cutoff ) that is an index of transparency is preferably in the range of 150 nm or more and 325 nm or less. If the maximum non-transmission light wavelength exceeds 325 nm, there is a risk of yellowing.
The transparent material of the present invention, also the index a is the transmittance of 80% at a wavelength of transparency (lambda ₈₀₎ is preferably less than 380 nm. This is because coloring may be observed when the wavelength of 80% transmittance is in the visible light region. Preferably, it is less than 360 nm. From the viewpoint of transparency, the shorter the transmittance 80% wavelength, the better. Examples of the shortest wavelength include a lower limit value of the maximum non-transmitted light wavelength.
The maximum non-transmission light wavelength and the transmittance of 80% wavelength can be adjusted by adjusting the number m of substitutions in the above formula (2) or (3), for example.
The maximum non-transmitted light wavelength and the transmittance of 80% wavelength can be determined by measuring the transmission spectrum of the film-like sample with an ultraviolet-visible spectrometer.

The glass transition temperature (T _g ), which is an index of heat resistance, is preferably in the range of 150 ° C. or higher and 400 ° C. or lower. The 10% weight loss temperature (T _d10 ) is preferably in the range of 400 ° C. or more and 600 ° C. or less.
The glass transition temperature can be measured with a differential scanning calorimeter, and the 10% weight loss temperature can be measured with a differential thermothermal gravimetric simultaneous measurement apparatus in a nitrogen atmosphere.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. The starting materials and reagents used in the following synthesis examples and examples are all commercially available compounds or compounds prepared by known methods.

Example 1
In a 500 ml flask, a mixture of sodium hydride (3.1 g, 127 mmol) and dimethyl sulfoxide (200 ml) was added to 1,3-bis (4-hydroxyphenyl) adamantane (20.4 g) under a nitrogen atmosphere. , 63.6 mmol) in dimethyl sulfoxide (200 ml) was added dropwise, heated to 80 ° C. and stirred for 12 hours. Next, the reaction solution was cooled in an ice bath and 1,2-dibromotetrafluoroethane (49.6 g, 191 mmol) was added dropwise so that the temperature did not exceed 30 ° C., and then at room temperature for 12 hours and further at 50 ° C. Stir for 12 hours. The reaction solution was cooled, poured into 2 liters of distilled water, stirred for a while, and the precipitate was collected by filtration. The obtained precipitate was dried under reduced pressure at 100 ° C. for 12 hours and purified by silica gel column chromatography using hexane to obtain a synthetic intermediate represented by the following formula (5) as white crystals (19.9 g). Yield 46%). The melting point of the compound represented by the formula (5) was 107 ° C.

Next, after preparing a solution of white crystals (19.9 g, 29.4 mmol) represented by the formula (5) obtained in acetonitrile (100 ml) in a 500 ml flask, zinc powder (3. 9 g, 58.8 mmol) was added, heated to 80 ° C. under a nitrogen atmosphere and stirred for 30 hours. Then, after cooling the reaction solution, acetonitrile was distilled off under reduced pressure, and the remaining solid was fractionated by silica gel column chromatography with hexane. The obtained solid was purified by distillation under reduced pressure (180 ° C., 0.02 Torr) to obtain a monomer represented by the following formula (6) as white crystals (12.3 g, yield 87%). The melting point of the monomer represented by the formula (6) was 51 ° C.

The structure of the synthesized compound represented by formula (6) was confirmed by IR measurement, NMR measurement and elemental analysis. The measurement results are shown below.
FT-IR (KBr, cm ^-1 ): 2911 (CH ₂ ), 1833 (CF = CF ₂ ), 1507 (CH = CH), 1272 (CF), 1135 (CF)
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.78 (t, 2H, adamantane), 1.93 (d, 8H, adamantane), 1.97 (s, 2H, adamantane), 2.32 (m, 2H, adamantane) , 7.05 (d, 4H, o-Ar-H), 7.37 (d, 4H, m-Ar-H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 29.4, 35.6, 37.0, 42.3, 49.2, 115.6, 126.4, 147.2, 153.1
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-120.9 (dd, 1F), -127.8 (dd, 1F), -134.4 (dd, 1F)
Elemental analysis: C ₂₆ H ₂₂ F ₆ O ₂
Theoretical value (%) C: 65.00 H: 4.61 N: 0.00
Actual value (%) C: 64.64 H: 4.58 N: 0.00

Example 2
In Example 1, except that 2,2-bis (4-hydroxyphenyl) adamantane was used in place of 1,3-bis (4-hydroxyphenyl) adamantane, the same as the synthesis intermediate as in Example 1, the following formula White crystals (15.7 g, yield 36%) represented by (7) were obtained. Next, the same procedure as in Example 1 was performed except that the synthetic intermediate represented by formula (7) was used instead of the synthetic intermediate represented by formula (5) and vacuum distillation was performed at 150 ° C. and 0.02 Torr. Thus, a monomer represented by the following formula (8) was obtained as white crystals (8.9 g, yield 80%). The melting point of the monomer represented by the formula (8) was 128 ° C.

The structure of the synthesized compound represented by the formula (8) was confirmed by IR measurement, NMR measurement and elemental analysis. The measurement results are shown below.
FT-IR (KBr, cm ^-1 ): 2909 (CH ₂ ), 1833 (CF = CF ₂ ), 1504 (CH = CH), 1272 (CF), 1139 (CF)
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ1.71-1.73 (4H, adamantane), 1.76 (2H, adamantane), 1.82 (2H, adamantane), 1.97-2.00 (4H, adamantane), 3.19 (2H , Adamantane), 6.96 (d, 4H, o-Ar-H), 7.37 (d, 4H, m-Ar-H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 27.4, 32.2, 33.2, 37.8, 49.9, 116.0, 127.3, 144.9, 152.3
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-120.9 (dd, 1F), -127.6 (dd, 1F), -134.3 (dd, 1F)
Elemental analysis: C ₂₆ H ₂₂ F ₆ O ₂
Theoretical value (%) C: 65.00 H: 4.61 N: 0.00
Actual value (%) C: 64.79 H: 4.68 N: 0.00

Example 3
In a 100 ml flask, the monomer (6) synthesized in Example 1 (0.50 g) was heated at 180 ° C. for 9 hours under a nitrogen atmosphere, and further heated at 220 ° C. for 3 hours to obtain a solid polymer. Obtained. The obtained polymer was dissolved in tetrahydrofuran and reprecipitated in methanol to obtain a polymer containing an alicyclic structure and a perfluorocyclobutyl ether structure of the following formula (9) as a white solid (0.46 g, yield). 92%).

The logarithmic viscosity, IR and NMR of the polymer represented by the formula (9) thus obtained were measured. The measurement results are shown below.
Logarithmic viscosity (η _inh ): 0.36 dL / g (measured at 0.5 ° C / deciliter chloroform solution at 30 ° C)
FT-IR (film, cm ^-1 ): 2905 (CH ₂ ), 1509 (CH = CH), 1317 (CF), 1204 (CF), 963 (CF)
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.75 (t, 2H, adamantane), 1.89 (d, 8H, adamantane), 1.93 (s, 2H, adamantane), 2.28 (m, 2H, adamantane) , 7.04 (d, 2H, o-Ar-H), 7.11 (d, 2H, o-Ar-H), 7.31 (dd, 4H, m-Ar-H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 29.4, 35.6, 36.9, 42.2, 49.1, 117.8, 126.1, 147.3, 150.4
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-127.7, -128.8, -129.2, -129.4, -129.8, -130.6, -131.2, -131.8, -132.1, -132.6

Example 4
In a flask with a capacity of 100 ml, the monomer (8) (0.5 g) synthesized in Example 2 was heated at 180 ° C. for 2 hours under a nitrogen atmosphere, and further heated at 220 ° C. for 3 hours to obtain a solid polymer. Obtained. The obtained polymer was dissolved in tetrahydrofuran and reprecipitated in methanol to obtain a polymer containing an alicyclic structure and a perfluorocyclobutyl ether structure of the following formula (10) as a white solid (0.47 g, yield). 94%).

The logarithmic viscosity, IR, and NMR of the polymer represented by the formula (10) thus obtained were measured. The measurement results are shown below.
Logarithmic viscosity (η _inh ): 0.20 dL / g (measured at 0.5 ° C / deciliter chloroform solution at 30 ° C)
FT-IR (film, cm ^-1 ): 2917 (CH ₂ ), 1506 (CH = CH), 1319 (CF), 1204 (CF), 962 (CF)
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.69-1.71 (6H, adamantane), 1.78 (2H, adamantane), 1.94 (4H, adamantane), 3.13 (2H, adamantane), 6.78 (d, 2H , O-Ar-H), 6.99 (d, 2H, o-Ar-H), 7.27 (dd, 4H, m-Ar-H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 27.4, 32.1, 33.1, 37.8, 49.9, 118.0, 127.0, 145.2, 149.5
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-127.7, -128.8, -129.1, -129.5, -130.0, -130.7, -131.2, -131.8, -132.7, -133.3

Synthesis example 1
As Example 1, except that bisphenol A was used in place of 1,3-bis (4-hydroxyphenyl) adamantane and extraction was performed with diethyl ether instead of silica gel chromatography, A colorless transparent oily substance (11.2 g, yield 30%) represented by the following formula (11) was obtained. Next, the same procedure as in Example 1 was performed except that the synthetic intermediate represented by formula (11) was used instead of the synthetic intermediate represented by formula (5) and vacuum distillation was performed at 150 ° C. and 0.02 Torr. Thus, a monomer represented by the following formula (12) was obtained as a colorless transparent oil (6.2 g, yield 84%).

The structure of the synthesized compound represented by the formula (12) was confirmed by IR measurement and NMR measurement. The measurement results are shown below.
FT-IR (KBr, cm ^-1 ): 2974 (CH ₃ ), 1833 (CF = CF ₂ ), 1504 (CH = CH), 1277 (CF), 1140 (CF)
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.65 (s, 6H, CH ₃ ), 6.99 (d, 4H, o-Ar—H), 7.20 (d, 4H, m-Ar—H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 30.9, 42.3, 115.5, 128.3, 147.0, 153.1
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-120.9 (dd, 1F), -127.7 (dd, 1F), -134.5 (dd, 1F)

Comparative Example 1
In a 100 ml flask, the monomer (12) (0.50 g) synthesized in Synthesis Example 1 was heated at 180 ° C. for 24 hours under a nitrogen atmosphere and then heated at 240 ° C. for 8 hours to obtain a solid polymer. It was. The obtained polymer was dissolved in chloroform and reprecipitated in methanol to obtain a polymer containing a perfluorocyclobutyl ether structure not containing an alicyclic structure represented by the following formula (13) as a white solid (0. 45 g, 90% yield).

The logarithmic viscosity, IR and NMR of the polymer represented by the formula (13) thus obtained were measured. The measurement results are shown below.
Logarithmic viscosity (η _inh ): 0.30dL / g (measured at 0.5 ° C / deciliter concentration chloroform solution at 30 ° C)
FT-IR (film, cm ^-1 ): 2972 (CH ₃ ), 1507 (CH = CH), 1309 (CF), 1204 (CF), 963 (CF)
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.63 (s, 6 H, CH ₃ ), 6.98 (d, 2 H, o-Ar—H), 7.07 (d, 2 H, o-Ar—H) , 7.24 (m, 4H, m-Ar-H)
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 30.7, 42.2, 117.6, 128.0, 147.1, 150.5
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-127.7, -128.7, -129.2, -129.3, -129.8, -130.6, -131.1, -131.7, -132.2, -132.9

[Polymer evaluation]
The polymers produced in Examples 3 and 4 and Comparative Example 1 were evaluated as follows. The obtained results are shown in Table 1.
(1) Number average molecular weight and weight average molecular weight After making the polymer a dilute tetrahydrofuran solution, the number average molecular weight and the weight average molecular weight (polystyrene standard conversion) were measured by gel permeation chromatography (GPC).
(2) 10% weight loss temperature (T _d10 )
Under a nitrogen atmosphere, a 10% weight loss temperature (T _d10 ) was measured with a differential thermothermal gravimetric simultaneous measurement apparatus.
(3) Glass transition temperature (T _g )
The glass transition temperature (T _g ) was measured with a differential scanning calorimeter.
(4) Maximum non-transmission light wavelength (λ _cutoff ) and wavelength of transmittance 80% (λ ₈₀ )
Using the polymers produced in Examples 3 and 4 and Comparative Example 1, a transparent and colorless film having a thickness of 10 to 40 μm was produced. By measuring the ultraviolet-visible absorption spectrum (FIG. 1) of the produced film, the maximum wavelength (λ _cutoff ) of light that does not pass through and the wavelength (λ ₈₀ ) with a transmittance of 80% were measured.

  From the results in Table 1, the polymer containing the alicyclic structure and the perfluorocyclobutyl ether structure of the present invention is particularly useful as a transparent material because of its high transparency to ultraviolet light and high heat resistance. I understand.

The polymer of the present invention can be suitably used as a transparent material for optical devices such as optical fibers and optical lenses, and display devices such as flat panel displays.
The transparent material of the present invention is an optical information transmission device such as an optical fiber or an optical waveguide, a CMOS image sensor, a CCD image sensor, an optical information processing device such as a CD, a DVD, a Blu-ray disc, an optical computer, a liquid crystal display, a liquid crystal projector, or a plasma. It is suitable as a material for constituent members of display devices such as a display, an EL display, and an LED display.

It is a figure which shows the ultraviolet visible absorption spectrum of the film which consists of a polymer manufactured in Example 3 and 4 and the comparative example 1. FIG.

Claims (10)

A polymer represented by the following formula (1) having an alicyclic structure and a perfluorocyclobutyl ether structure.

(In the formula, R is a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms, or a divalent aromatic group having 6 to 10 carbon atoms, substituted or unsubstituted having 1 to 20 carbon atoms. A divalent linear aliphatic group, a substituted or unsubstituted divalent branched aliphatic group having 1 to 20 carbon atoms, and a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms. A divalent group formed by combining one or more divalent groups selected from the group consisting of and a substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms;
n is an integer of 10 or more and 10,000 or less. )   The polymer according to claim 1, wherein the substituted or unsubstituted divalent alicyclic group having 5 to 50 carbon atoms includes an adamantane structure, a biadamantane structure, a diamantane structure, or a triamantane structure. The polymer according to claim 1 or 2, wherein the polymer represented by the formula (1) is a polymer represented by the following formula (2) or (3).

Wherein R ′ is a substituent substituted on the adamantane moiety structure or arylene moiety, and R ′ is a halogen element, a substituted or unsubstituted aromatic substituent having 6 to 30 carbon atoms, or 1 carbon atom. -20 substituted or unsubstituted linear aliphatic substituent, 1 to 20 carbon substituted or unsubstituted branched aliphatic substituent, or 5 to 50 carbon substituted or unsubstituted alicyclic substituent And
m is an integer of 0 or more and 14 or less, and when m is 2 or more, a plurality of R ′ may be the same or different) A monomer represented by the following formula (4).

(In formula, it is the same as R of Claim 1. )   The method for producing a polymer according to any one of claims 1 to 3, wherein the monomer represented by the general formula (4) according to claim 4 is subjected to cycloaddition reaction.   The transparent material containing the polymer in any one of Claims 1-3, or the polymer obtained by the manufacturing method of the polymer of Claim 5.   The coating material which dissolved the polymer in any one of Claims 1-3, or the polymer obtained by the manufacturing method of the polymer of Claim 5 in the organic solvent.   A thin film formed using the paint according to claim 7.   A member made of the transparent material according to claim 6. An apparatus comprising the member according to claim 9.

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