JP4604726B2 - Novel fluorine-containing epoxy compound and polymer thereof - Google Patents
Novel fluorine-containing epoxy compound and polymer thereof Download PDFInfo
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本発明は、短波長光に対して高い透明性を有する重合体、および該重合体の原料等として有用な新規な含フッ素エポキシ化合物に関する。 The present invention relates to a polymer having high transparency to short wavelength light, and a novel fluorine-containing epoxy compound useful as a raw material for the polymer.
半導体等の製造工程に用いるフォトリソグラフィ（露光処理）において、フォトマスクやレチクル（以下、これらをマスクパターン面という。）への異物付着を防止するために、ペリクルが用いられる。ペリクルとは、透明薄膜が接着剤を介して枠体に設置されたマスクパターン面上に一定の距離をおいて装着される光学物品である。 In photolithography (exposure processing) used in a manufacturing process of a semiconductor or the like, a pellicle is used to prevent foreign matter from adhering to a photomask or a reticle (hereinafter referred to as a mask pattern surface). A pellicle is an optical article in which a transparent thin film is mounted at a certain distance on a mask pattern surface placed on a frame body via an adhesive.
半導体の配線や配線間隔が微細化するに伴い、フォトリソグラフィにおける露光光源に発振波長が２００ｎｍ以下のエキシマレーザー光（たとえば、発振波長が１９３ｎｍのＡｒＦエキシマレーザー光や発振波長が１５７ｎｍのＦ２エキシマレーザー光等。）の使用が検討されている。 As semiconductor wiring and wiring spacing become finer, excimer laser light with an oscillation wavelength of 200 nm or less (for example, ArF excimer laser light with an oscillation wavelength of 193 nm or F 2 excimer laser with an oscillation wavelength of 157 nm) is used as an exposure light source in photolithography The use of light etc.) is under consideration.
該エキシマレーザー光を用いたフォトリソグラフィ用ペリクルの材料として、主鎖にエーテル性酸素原子を含み環構造を含まない含フッ素重合体（Ｑ）が提案されている。含フッ素重合体（Ｑ）としては、主鎖に式−ＯＣＦ２ＣＦ２−で表される繰返し単位と式−ＣＦ２Ｏ−で表される繰返し単位を含み、他の主鎖部分に環構造を含まない含フッ素重合体（Ｑ１）が提案されている（特許文献１参照。）。含フッ素重合体（Ｑ１）は、ＣＦ２＝ＣＦ２を酸素と光酸化反応させて得られる（特許文献２参照。）。 As a material for a pellicle for photolithography using the excimer laser light, a fluorine-containing polymer (Q) having an etheric oxygen atom in the main chain and no ring structure has been proposed. The fluoropolymer (Q) includes a repeating unit represented by the formula —OCF 2 CF 2 — and a repeating unit represented by the formula —CF 2 O— in the main chain, and a ring structure in the other main chain portion. A fluorine-containing polymer (Q1) that does not contain is proposed (see Patent Document 1). The fluoropolymer (Q1) can be obtained by photooxidizing CF 2 = CF 2 with oxygen (see Patent Document 2).
含フッ素重合体（Ｑ１）中の繰返し単位は、ＣＦ２＝ＣＦ２の重合により形成されたモノマー単位ではなく、ＣＦ２＝ＣＦ２の酸化分解により形成される単位であると考えられた。そして含フッ素重合体（Ｑ１）中の繰返し単位の、割合および組み合せは限定されていた。また他の繰返し単位を含む含フッ素重合体（Ｑ）を得ようとしても、原料となる化合物の入手が困難であり得られる含フッ素重合体（Ｑ）の種類は限定されていた。 Repeat units in the fluoropolymer (Q1) is not a monomer unit formed by polymerization of CF 2 = CF 2, it was considered to be units formed by oxidative decomposition of CF 2 = CF 2. And the ratio and combination of the repeating units in the fluoropolymer (Q1) were limited. Moreover, even if it was going to obtain the fluoropolymer (Q) containing another repeating unit, the acquisition of the compound used as a raw material was difficult, and the kind of fluoropolymer (Q) which can be obtained was limited.
本発明は、以下の発明を提供する。
＜１＞：下式（１）で表される化合物（ただし、ＲＦ１およびＲＦ２は、それぞれ独立に、フッ素原子または炭素数１〜３のペルフルオロアルキル基を示す。）。
The present invention provides the following inventions.
<1>: Compound represented by the following formula (1) (wherein R F1 and R F2 each independently represents a fluorine atom or a C 1 to C 3 perfluoroalkyl group).
＜２＞：下式（２）で表される化合物をエポキシ化反応させる式（１）で表される化合物の製造方法。
ＣＦ２＝ＣＦＣＲＦ１ＲＦ２ＯＣＦ２ＣＦ＝ＣＦ２ （２）
＜３＞：式（１）で表される化合物を重合させた重合体。
＜４＞：重量平均分子量が５００〜１００００００である＜３＞の重合体。
<2>: A method for producing a compound represented by the formula (1) in which a compound represented by the following formula (2) is epoxidized.
CF 2 = CFCR F1 R F2 OCF 2 CF = CF 2 (2)
<3>: A polymer obtained by polymerizing the compound represented by formula (1).
<4>: The polymer of <3> having a weight average molecular weight of 500 to 1,000,000.
本発明によれば、新規な含フッ素エポキシ化合物が提供される。本発明の含フッ素エポキシ化合物は、１分子内に２個のエポキシ構造を有する特徴的な化合物である。本発明の含フッ素エポキシ化合物を重合させた重合体は、重合体の主鎖にエーテル性酸素原子を含み、２００ｎｍ以下の波長光に対して高い透明性を有する。 According to the present invention, a novel fluorine-containing epoxy compound is provided. The fluorine-containing epoxy compound of the present invention is a characteristic compound having two epoxy structures in one molecule. The polymer obtained by polymerizing the fluorine-containing epoxy compound of the present invention contains an etheric oxygen atom in the main chain of the polymer and has high transparency with respect to light having a wavelength of 200 nm or less.
本明細書において、式（１）で表される化合物を化合物（１）とも記す。他の式で表される化合物においても同様に記す。また、式（Ａ）で表わされるモノマー単位を単位（Ａ）と記す。モノマー単位とは、モノマーの重合により形成されるモノマーに由来する最大の繰り返し単位を意味する。 In the present specification, the compound represented by the formula (1) is also referred to as a compound (1). The same applies to compounds represented by other formulas. The monomer unit represented by the formula (A) is referred to as a unit (A). A monomer unit means the largest repeating unit derived from the monomer formed by superposition | polymerization of a monomer.
本発明は、下記化合物（１）を提供する（ただし、ＲＦ１およびＲＦ２は、前記と同じ意味を示す。以下同じ。）。 The present invention provides the following compound (1) (provided that R F1 and R F2 have the same meaning as described above; the same applies hereinafter).
ＲＦ１およびＲＦ２は、同一であっても異なっていてもよい。炭素数１〜３のペルフルオロアルキル基であるＲＦ１およびＲＦ２としては、トリフルオロメチル基が好ましい。ＲＦ１およびＲＦ２は、いずれもフッ素原子であるのが好ましい。 R F1 and R F2 may be the same or different. As R < F1> and R <F2 > which are C1-C3 perfluoroalkyl groups, a trifluoromethyl group is preferable. Both R F1 and R F2 are preferably fluorine atoms.
化合物（１）の具体例としては下記の化合物が挙げられる。 Specific examples of the compound (1) include the following compounds.
本発明の化合物（１）は、新規化合物である。化合物（１）は、下記化合物（２）をエポキシ化反応させて得られる。
ＣＦ２＝ＣＦＣＲＦ１ＲＦ２ＯＣＦ２ＣＦ＝ＣＦ２ （２）
エポキシ化反応は、酸化剤の存在下に行うのが好ましい。酸化剤としては、有機系酸化剤（たとえば有機過酸化物等。）、無機系酸化剤（たとえば次亜塩素酸ソーダ、ＫＨＳＯ５等。）が挙げられる。
Compound (1) of the present invention is a novel compound. Compound (1) is obtained by epoxidizing the following compound (2).
CF 2 = CFCR F1 R F2 OCF 2 CF = CF 2 (2)
The epoxidation reaction is preferably performed in the presence of an oxidizing agent. Examples of the oxidizing agent include organic oxidizing agents (eg, organic peroxides) and inorganic oxidizing agents (eg, sodium hypochlorite, KHSO 5 etc.).
反応の温度は、−１０℃〜＋１０℃が好ましく、−５℃〜＋５℃が特に好ましい。
反応の圧力は、０〜２ＭＰａ（ゲージ圧）が好ましく、０〜１ＭＰａ（ゲージ圧）が特に好ましい。
The reaction temperature is preferably −10 ° C. to + 10 ° C., particularly preferably −5 ° C. to + 5 ° C.
The reaction pressure is preferably 0 to 2 MPa (gauge pressure), particularly preferably 0 to 1 MPa (gauge pressure).
反応は、２相系反応で行うのが好ましく、相間移動触媒を用いた２相系反応で行うのが特に好ましい。相間移動触媒としては、塩化トリオクチルメチルアンモニウム、臭化テトラブチルアンモニウム等が挙げられ、塩化トリオクチルメチルアンモニウムが好ましい。 The reaction is preferably carried out by a two-phase system reaction, particularly preferably a two-phase system reaction using a phase transfer catalyst. Examples of the phase transfer catalyst include trioctylmethylammonium chloride and tetrabutylammonium bromide, with trioctylmethylammonium chloride being preferred.
化合物（２）は、ＨＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨと下記化合物（９）をエーテル化反応させて下記化合物（８）を得て、該化合物（８）を式Ｒｆ−ＣＯＦで表される化合物とエステル化反応させて下記化合物（７）を得て、該化合物（７）をハロゲン化反応させて下記化合物（６）を得て、該化合物（６）をフッ素化反応させて下記化合物（５）を得て、該化合物（５）を熱分解反応させて下記化合物（４）を得て、該化合物（４）を熱分解反応させて下記化合物（３）を得て、該化合物（３）を脱ハロゲン化反応させる方法を用いて製造できる。
ＣＨ２＝ＣＨＣＲ１Ｒ２Ｘ （９）
ＣＨ２＝ＣＨＣＲ１Ｒ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨ （８）
ＣＨ２＝ＣＨＣＲ１Ｒ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＣ（Ｏ）Ｒｆ （７）
ＣＨ２ＺＣＨＺＣＲ１Ｒ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＣ（Ｏ）Ｒｆ （６）
ＣＦ２ＺＣＦＺＣＲＦ１ＲＦ２ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＯＣ（Ｏ）Ｒｆ （５）
ＣＦ２ＺＣＦＺＣＲＦ１ＲＦ２ＯＣＦ２ＣＦ２ＣＦ２ＣＯＦ （４）
ＣＦ２ＺＣＦＺＣＲＦ１ＲＦ２ＯＣＦ２ＣＦ＝ＣＦ２ （３）
ＣＦ２＝ＣＦＣＲＦ１ＲＦ２ＯＣＦ２ＣＦ＝ＣＦ２ （２）
ただし、Ｒ１およびＲ２は、それぞれＲＦ１とＲＦ２に対応する基であり、Ｒ１はＲＦ１と同一の基またはフッ素化反応によりＲＦ１となる基であり、Ｒ２はＲＦ２と同一の基またはフッ素化反応によりＲＦ２となる基である。Ｒ１およびＲ２は、それぞれ水素原子または炭素数１〜３のアルキル基が好ましく、水素原子が特に好ましい。
Compound (2) is obtained by etherifying HOCH 2 CH 2 CH 2 CH 2 OH and the following compound (9) to obtain the following compound (8), which is represented by the formula R f —COF. The following compound (7) is obtained by esterification reaction with the compound, and the following compound (6) is obtained by halogenation reaction of the compound (7), and the following compound is obtained by fluorination reaction of the compound (6). (5) is obtained, the compound (5) is thermally decomposed to obtain the following compound (4), and the compound (4) is thermally decomposed to obtain the following compound (3). 3) can be produced using a method of dehalogenation reaction.
CH 2 = CHCR 1 R 2 X (9)
CH 2 = CHCR 1 R 2 OCH 2 CH 2 CH 2 CH 2 OH (8)
CH 2 = CHCR 1 R 2 OCH 2 CH 2 CH 2 CH 2 OC (O) R f (7)
CH 2 ZCHZCR 1 R 2 OCH 2 CH 2 CH 2 CH 2 OC (O) R f (6)
CF 2 ZCFZCR F 1 R F 2 OCF 2 CF 2 CF 2 CF 2 OC (O) R f (5)
CF 2 ZCFZCR F1 R F2 OCF 2 CF 2 CF 2 COF (4)
CF 2 ZCFZCR F1 R F2 OCF 2 CF = CF 2 (3)
CF 2 = CFCR F1 R F2 OCF 2 CF = CF 2 (2)
However, R 1 and R 2 are groups corresponding to R F1 and R F2 , respectively, R 1 is the same group as R F1 or a group that becomes R F1 by a fluorination reaction, and R 2 is R F2 and The same group or a group that becomes R F2 by a fluorination reaction. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom.
Ｘは、塩素原子、臭素原子またはヨウ素原子が好ましい。
Ｚは、塩素原子または臭素原子である。
Ｒｆは炭素数１〜２０のペフルオロアルキル基または炭素数２〜２０のエーテル性酸素原子を含むペルフルオロアルキル基である。
X is preferably a chlorine atom, a bromine atom or an iodine atom.
Z is a chlorine atom or a bromine atom.
R f is a C 1-20 perfluoroalkyl group or a C 2-20 peroxyalkyl group containing an etheric oxygen atom.
化合物（９）の具体例としては、下記の化合物が挙げられる。
ＣＨ２＝ＣＨＣＨ２Ｃｌ、
ＣＨ２＝ＣＨＣＨ２Ｂｒ、
ＣＨ２＝ＣＨＣＨ２Ｉ、
ＣＨ２＝ＣＨＣＨ（ＣＨ３）Ｃｌ、
ＣＨ２＝ＣＨＣ（ＣＨ３）２Ｃｌ、
ＣＨ２＝ＣＨＣＨ（Ｃ２Ｈ５）Ｃｌ。
Specific examples of the compound (9) include the following compounds.
CH 2 = CHCH 2 Cl,
CH 2 = CHCH 2 Br,
CH 2 = CHCH 2 I,
CH 2 = CHCH (CH 3 ) Cl,
CH 2 = CHC (CH 3 ) 2 Cl,
CH 2 = CHCH (C 2 H 5) Cl.
化合物（２）の具体例としては、下記の化合物が挙げられる。 Specific examples of the compound (2) include the following compounds.
エーテル化反応、エステル化反応、ハロゲン化反応、フッ素化反応、エステル分解反応および脱ハロゲン化反応は、公知の方法にしたがって実施できる。 The etherification reaction, esterification reaction, halogenation reaction, fluorination reaction, ester decomposition reaction and dehalogenation reaction can be carried out according to known methods.
本発明の化合物（１）は、それぞれ分子中に２個の重合性のエポキシ構造を有する化合物である。化合物（１）を重合させることにより下記単位から選ばれる１種以上のモノマー単位を含む重合体（Ａ）を得ることができる。 The compound (1) of the present invention is a compound having two polymerizable epoxy structures in each molecule. By polymerizing the compound (1), a polymer (A) containing one or more monomer units selected from the following units can be obtained.
化合物（１）の重合反応の種類は、特に限定されず、アニオン重合法、カチオン重合法等のイオン重合法、ラジカル重合法等が挙げられる。重合性が良好である観点から、アニオン重合法が好ましい。また重合反応の方法は、特に限定されず、塊状重合法、懸濁重合法、溶液重合法等の方法が採用できる。 The kind of the polymerization reaction of the compound (1) is not particularly limited, and examples thereof include anionic polymerization methods, ionic polymerization methods such as cationic polymerization methods, radical polymerization methods and the like. From the viewpoint of good polymerizability, an anionic polymerization method is preferred. The method for the polymerization reaction is not particularly limited, and methods such as a bulk polymerization method, a suspension polymerization method, and a solution polymerization method can be employed.
アニオン重合法で実施する場合には、アニオン開始剤の存在下に行うのが好ましい。アニオン開始剤としては、ＣｓＦが好ましい。
重合体（Ａ）の重量平均分子量は、５００〜１００００００が好ましく、５００〜５０００００が特に好ましく、５００〜３０００００がとりわけ好ましい。
When it is carried out by an anionic polymerization method, it is preferably carried out in the presence of an anionic initiator. As the anionic initiator, CsF is preferable.
The weight average molecular weight of the polymer (A) is preferably from 500 to 1,000,000, particularly preferably from 500 to 500,000, particularly preferably from 500 to 300,000.
本発明の重合体は、屈折率が低く、透明性、撥水撥油性等に優れることから、光ファイバー材料（光ファイバーのコア材料およびクラッド材料。）、光導波路材料（光導路材料のコア材料およびクラッド材料。）、ペリクル材料、レンズ材料（眼鏡レンズ、光学レンズ、光学セルなど。）等の光学材料；素子（発光素子、太陽電池素子など。）封止材料、層間絶縁膜（半導体素子用、液晶表示体用、多層配線板用など。）、バッファーコート膜、パッシベーション膜、α線遮蔽膜、高密度実装基板用層間絶縁膜、高周波素子（ＲＦ回路素子、ＧａＡｓ素子、ＩｎＰ素子など。）保護膜、ディスプレイ（ＰＤＰ、ＬＣＤ、ＣＲＴ、ＬＣＤなど。）表面保護膜等の電子材料；モーター流体軸受装置における軸受部分等のオイルシール剤；注射器、水素吸蔵合金、バイオセンサー用測定チップ、通気性布帛等の表面改質剤、として有用である。 Since the polymer of the present invention has a low refractive index and is excellent in transparency, water and oil repellency, etc., optical fiber materials (optical fiber core materials and clad materials), optical waveguide materials (core materials and clads of optical path materials) Materials), pellicle materials, optical materials such as lens materials (eyeglass lenses, optical lenses, optical cells, etc.); elements (light emitting elements, solar cell elements, etc.) sealing materials, interlayer insulating films (for semiconductor elements, liquid crystals) For display bodies, multilayer wiring boards, etc.), buffer coat film, passivation film, α-ray shielding film, interlayer insulating film for high-density mounting substrate, high frequency element (RF circuit element, GaAs element, InP element, etc.) protective film , Displays (PDP, LCD, CRT, LCD, etc.) electronic materials such as surface protective films; oil sealants such as bearing parts in motor fluid bearing devices; syringes; Containing absorbing alloy, measuring biosensor chip, is useful as a surface modifier, such as breathable fabric.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらに限定されない。以下においては、Ｍｗを重量平均分子量、ゲルパーミエーションクロマトグラフ法をＧＰＣ法、ＣＣｌ２ＦＣＣｌＦ２をＲ−１１３、ジクロロペンタフルオロプロパンをＲ−２２５、−ＣＦ（ＣＦ３）Ｏ（ＣＦ２）３Ｆ基を−Ｒｆ１基と、記す。また圧力は、特に表記しない限り、絶対圧で示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. In the following, weight average molecular weight M w, gel permeation GPC method chromatographic methods, CCl 2 FCClF 2 to R-113, R-225 the dichloropentafluoropropane, -CF (CF 3) O ( CF 2) The 3 F group is referred to as -R f1 group. Moreover, unless otherwise indicated, the pressure is expressed as an absolute pressure.
Ｍｗは、特開２０００−７４８９２号公報に記載のＧＰＣ法を用いて測定した。具体的には、Ｒ−２２５（旭硝子社製、商品名：アサヒクリンＡＫ−２２５ＳＥＣグレード１）／ヘキサフルオロイソプロピルアルコール（ＨＦＩＰ）の容量比が９９／１である混合溶媒を移動相として用い、ＰＬｇｅｌ ＭＩＸＥＤ−Ｅカラム（ポリマーラボラトリーズ社製）を２本直列に連結して分析カラムとした。分子量測定用標準試料としてペルフルオロポリエーテルの５種を用いた。移動相流速を１．０ｍＬ／分、カラム温度を３７℃とし、検出器としては蒸発光散乱検出器を用いた。 Mw was measured using the GPC method described in Japanese Patent Application Laid-Open No. 2000-74892. Specifically, a mixed solvent having a volume ratio of R / 225 (manufactured by Asahi Glass Co., Ltd., trade name: Asahiklin AK-225SEC Grade 1) / hexafluoroisopropyl alcohol (HFIP) of 99/1 is used as a mobile phase, and PLgel. Two MIXED-E columns (manufactured by Polymer Laboratories) were connected in series to form an analytical column. Five kinds of perfluoropolyethers were used as standard samples for molecular weight measurement. The mobile phase flow rate was 1.0 mL / min, the column temperature was 37 ° C., and an evaporative light scattering detector was used as the detector.
［例１（合成例）］化合物（２１）の製造例 [Example 1 (Synthesis example)] Production example of compound (21)
（例１−１）化合物（８１）の製造例
水浴下、フラスコにＨＯ（ＣＨ２）４ＯＨ（４８．５ｇ）を投入し、ＫＯＨ（１６．３ｇ）を撹拌しながら投入した。撹拌を続けながら、ＣＨ２＝ＣＨＣＨ２Ｂｒ（３２．０ｇ）をフラスコに１．５時間かけて滴下した。さらに２５℃で２４時間撹拌してから静置して、有機相および水相に分離した２相分離液を得た。つぎに有機相と取り出し、さらに水相を塩酸（１ｍｏｌ／Ｌ）で酸性にしてからトルエン（５０ｍＬ）で３回抽出したトルエン抽出液を得た。有機相とトルエン抽出液をあわせ、つぎに飽和食塩水（２０ｍＬ）で３回洗浄し硫酸マグネシウムで乾燥してから、エバポレータで濃縮して濃縮物を得た。濃縮物をＮＭＲで分析した結果、標記化合物の生成を確認した（収率８５．３％）。
Example 1-1 Production Example of Compound (81) In a water bath, HO (CH 2 ) 4 OH (48.5 g) was charged into a flask, and KOH (16.3 g) was charged with stirring. While continuing stirring, CH 2 = CHCH 2 Br (32.0 g) was added dropwise to the flask over 1.5 hours. The mixture was further stirred at 25 ° C. for 24 hours and then allowed to stand to obtain a two-phase separated liquid separated into an organic phase and an aqueous phase. Next, the organic phase was taken out, and the aqueous phase was acidified with hydrochloric acid (1 mol / L) and then extracted with toluene (50 mL) three times to obtain a toluene extract. The organic phase and the toluene extract were combined, then washed three times with saturated brine (20 mL), dried over magnesium sulfate, and then concentrated with an evaporator to obtain a concentrate. As a result of analyzing the concentrate by NMR, it was confirmed that the title compound was formed (yield 85.3%).
（例１−２）化合物（７１）の製造例
フラスコに、ＮａＦ（１６．８ｇ）、Ｒ−２２５（１００ｇ）および例１−１で得た化合物（８１）（２９．４ｇ）を投入した。つぎに、フラスコの内温を０〜１０℃に保持し、フラスコを撹拌しながら式Ｒｆ１−ＣＯＦで表される化合物（１１０．８ｇ）を４時間かけて滴下した。オートクレーブを２５℃で４時間撹拌してから、フラスコの内温を１５℃以下にして、飽和炭酸水素ナトリウム水溶液（１００ｍＬ）を投入して水溶液を得た。水溶液をＲ−２２５（２００ｍＬ）で３回抽出して得た抽出液を、硫酸マグネシウムで乾燥してからエバポレータで濃縮して濃縮物を得た。濃縮物をＮＭＲで分析した結果、標記化合物の生成を確認した（収率９５．３％）。
Example 1-2 Production Example of Compound (71) NaF (16.8 g), R-225 (100 g) and the compound (81) obtained in Example 1-1 (29.4 g) were charged into a flask. Next, the internal temperature of the flask was maintained at 0 to 10 ° C., and the compound (110.8 g) represented by the formula R f1 —COF was added dropwise over 4 hours while stirring the flask. After the autoclave was stirred at 25 ° C. for 4 hours, the internal temperature of the flask was adjusted to 15 ° C. or lower, and a saturated aqueous sodium hydrogen carbonate solution (100 mL) was added to obtain an aqueous solution. The extract obtained by extracting the aqueous solution three times with R-225 (200 mL) was dried over magnesium sulfate and then concentrated with an evaporator to obtain a concentrate. As a result of analyzing the concentrate by NMR, it was confirmed that the title compound was produced (yield: 95.3%).
（例１−３）化合物（６１）の製造例
フラスコに、例１−２で得た化合物（７１）（５０．０ｇ）とＣＣｌ４（５０ｍＬ）を投入した。つぎに、フラスコの内温を−１５℃に保持して、フラスコに塩素ガスを２．２７Ｌ／ｈで２時間導入した。フラスコに窒素ガスを２時間導入して塩素ガスを除いてから、フラスコの内溶液を濃縮して濃縮物を得た。濃縮物をＮＭＲで分析した結果、標記化合物の生成を確認した（収率７７％）。
Example 1-3 Production Example of Compound (61) The flask was charged with the compound (71) (50.0 g) obtained in Example 1-2 and CCl 4 (50 mL). Next, the internal temperature of the flask was kept at −15 ° C., and chlorine gas was introduced into the flask at 2.27 L / h for 2 hours. After introducing nitrogen gas into the flask for 2 hours to remove chlorine gas, the solution in the flask was concentrated to obtain a concentrate. As a result of analyzing the concentrate by NMR, it was confirmed that the title compound was formed (yield 77%).
（例１−４）化合物（５１）の製造例
オートクレーブ（内容積５００ｍＬ、ニッケル製）に、Ｒ−１１３（３１２ｇ）を加えて２５℃で撹拌した。オートクレーブガス出口には、２０℃に保持した冷却器、ＮａＦペレット充填層、および−１０℃に保持した冷却器を直列に設置した。−１０℃に保持した冷却器からは、凝縮液をオートクレーブに戻すための液体返送ラインを設置した。オートクレーブに窒素ガスを１時間導入した後、窒素ガスで２０体積％に希釈したフッ素ガス（以下、２０％フッ素ガスという。）を、１０．８Ｌ／ｈで１時間導入した。
(Example 1-4) Production Example of Compound (51) R-113 (312 g) was added to an autoclave (internal volume: 500 mL, made of nickel) and stirred at 25 ° C. At the autoclave gas outlet, a cooler maintained at 20 ° C., a NaF pellet packed bed, and a cooler maintained at −10 ° C. were installed in series. A liquid return line for returning the condensate to the autoclave was installed from the cooler maintained at −10 ° C. After introducing nitrogen gas into the autoclave for 1 hour, fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was introduced at 10.8 L / h for 1 hour.
つぎに、オートクレーブに２０％フッ素ガスを同じ流量で導入しながら、例１−３で得た化合物（６１）（５ｇ）をＲ−１１３（１００ｇ）に溶解した溶液を、４時間かけて注入した。オートクレーブの出口バルブを閉め、２０％フッ素ガスを同じ流量で導入しながら、ベンゼン濃度が０．０１ｇ／ｍＬであるＲ−１１３溶液（９ｍＬ）を２５℃から４０℃にまで加熱しながら注入した。つぎにオートクレーブのベンゼン注入口を閉め、圧力が０．２０ＭＰａになってからオートクレーブのフッ素ガス入り口バルブを閉めて、０．４時間撹拌を続けた。さらに同様の操作を２回繰り返した。ベンゼンの総注入量は０．２１ｇ、Ｒ−１１３の総注入量は２１ｍＬであった。 Next, a solution prepared by dissolving the compound (61) (5 g) obtained in Example 1-3 in R-113 (100 g) was injected over 4 hours while introducing 20% fluorine gas into the autoclave at the same flow rate. . The autoclave outlet valve was closed, and while introducing 20% fluorine gas at the same flow rate, R-113 solution (9 mL) having a benzene concentration of 0.01 g / mL was injected while heating from 25 ° C to 40 ° C. Next, the benzene inlet of the autoclave was closed, and after the pressure reached 0.20 MPa, the fluorine gas inlet valve of the autoclave was closed and stirring was continued for 0.4 hours. Further, the same operation was repeated twice. The total injection amount of benzene was 0.21 g, and the total injection amount of R-113 was 21 mL.
つぎに、オートクレーブに窒素ガスを１時間導入してフッ素ガスを除いてから、オートクレーブの内溶液をデカンテーションして反応粗液を得た。反応粗液を濃縮して得た濃縮物をＮＭＲで分析した結果、標記化合物の生成を確認した（収率９５％）。 Next, nitrogen gas was introduced into the autoclave for 1 hour to remove the fluorine gas, and then the inner solution of the autoclave was decanted to obtain a reaction crude liquid. As a result of NMR analysis of the concentrate obtained by concentrating the reaction crude liquid, the production of the title compound was confirmed (yield 95%).
（例１−５）化合物（４１）の製造例
蒸留塔を備えたフラスコに、例１−４と同様の方法で得た濃縮物（１４４．１ｇ）とＫＦ粉末（２．１ｇ）を投入した。フラスコを、１００℃に加熱して４時間撹拌してから減圧すると、６５℃／１３．３３ｋＰａ（絶対圧）の留分が得られた。留分をＮＭＲで分析した結果、標記化合物の生成を確認した（収率６３％）。
Example 1-5 Production Example of Compound (41) A flask equipped with a distillation tower was charged with a concentrate (144.1 g) obtained in the same manner as in Example 1-4 and KF powder (2.1 g). . When the flask was heated to 100 ° C. and stirred for 4 hours and then depressurized, a fraction of 65 ° C./13.33 kPa (absolute pressure) was obtained. As a result of analyzing the fraction by NMR, it was confirmed that the title compound was formed (yield 63%).
（例１−６）化合物（３１）の製造例
フラスコに、例１−５で得た化合物（４１）（２３．９ｇ）を投入し、さらに１質量％のフェノールフタレイン数滴を加えて撹拌すると、フラスコ内溶液が青色に呈色した。つぎに、フラスコを撹拌しながら、１０質量％のＮａＯＨを含むエタノール溶液をフラスコの内容液が赤色になるまで滴下した。
(Example 1-6) Production Example of Compound (31) The flask was charged with the compound (41) (23.9 g) obtained in Example 1-5, and a few drops of 1% by mass phenolphthalein were added and stirred. Then, the solution in the flask was colored blue. Next, while stirring the flask, an ethanol solution containing 10% by mass of NaOH was added dropwise until the content of the flask became red.
該内溶液を、エバポレーターで濃縮し、真空乾燥器（８０℃）を用いて２４時間乾燥した結果、ＣＦ２ＣｌＣＦＣｌＣＦ２Ｏ（ＣＦ２）３ＣＯＯＮａ（２４．８ｇ）を得た。つぎに、メタノール−ドライアイストラップ、液体窒素トラップを順に塔頂部に設置した蒸留塔を備えたフラスコに、ＣＦ２ＣｌＣＦＣｌＣＦ２Ｏ（ＣＦ２）３ＣＯＯＮａ（２４．８ｇ）を投入した。フラスコ内を減圧にし、２５０℃で６時間加熱すると、メタノール−ドライアイストラップと液体窒素トラップに留出液が溜まった。留出液をＮＭＲで分析した結果、標記化合物の生成を確認した（収率８７％）。 The inner solution was concentrated with an evaporator and dried for 24 hours using a vacuum dryer (80 ° C.). As a result, CF 2 ClCFClCF 2 O (CF 2 ) 3 COONa (24.8 g) was obtained. Next, CF 2 ClCFClCF 2 O (CF 2 ) 3 COONa (24.8 g) was charged into a flask equipped with a distillation tower in which a methanol-dry ice trap and a liquid nitrogen trap were installed in this order. When the inside of the flask was evacuated and heated at 250 ° C. for 6 hours, the distillate accumulated in the methanol-dry ice strap and the liquid nitrogen trap. As a result of analyzing the distillate by NMR, it was confirmed that the title compound was produced (yield 87%).
（例１−７）化合物（２１）の製造例
還流液を捕集する容器を備えた還流コンデンサー、および滴下漏斗を備えたフラスコに、亜鉛（４．５ｇ）およびジメチルホルムアミド（３ｍＬ）を入れた。つぎにフラスコ内を３３．３ｋＰａ（絶対圧）に減圧して、フラスコの内温を７０〜７５℃に保持した。つづいて例１−６で得た化合物（２１）（５．７ｇ）をジメチルホルムアミド（２７ｇ）に溶解した溶液を、滴下漏斗からフラスコへゆっくりと滴下すると該容器に液体が留出した。留出が停止するまで捕集した液体（３．４ｇ）をＮＭＲで分析した結果、収率７３％で標記化合物を得た。標記化合物の純度は７４％であった。さらに液体を精留した結果、純度９９％の標記化合物を得た。
Example 1-7 Production Example of Compound (21) Zinc (4.5 g) and dimethylformamide (3 mL) were placed in a reflux condenser equipped with a container for collecting the reflux liquid and a flask equipped with a dropping funnel. . Next, the inside of the flask was reduced to 33.3 kPa (absolute pressure), and the internal temperature of the flask was maintained at 70 to 75 ° C. Subsequently, when a solution obtained by dissolving the compound (21) (5.7 g) obtained in Example 1-6 in dimethylformamide (27 g) was slowly dropped into the flask from the dropping funnel, the liquid was distilled into the container. The liquid collected until the distillation stopped (3.4 g) was analyzed by NMR. As a result, the title compound was obtained in a yield of 73%. The purity of the title compound was 74%. Further, the liquid was rectified to obtain the title compound having a purity of 99%.
化合物（２１）の１９Ｆ−ＮＭＲ（２８２．７ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）δ（ｐｐｍ）：−７２．１（４Ｆ）、−９１．７（２Ｆ）、−１０４．９（２Ｆ）、−１９０．０（２Ｆ）。 19 F-NMR of compound (21) (282.7 MHz, solvent: CDCl 3 , standard: CFCl 3 ) δ (ppm): −72.1 (4F), −91.7 (2F), −104.9 ( 2F), -190.0 (2F).
［例２（参考例）］化合物（ｅｐｏ）の製造例 [Example 2 (Reference Example)] Production Example of Compound (epo)
還流コンデンサーを備えたフラスコに、１２質量％の次亜塩素酸ナトリウムを含む水溶液（１５０ｍＬ）とアセトニトリル（２５ｍＬ）を加えた。つづいて内温を０℃に保持しながら化合物（ｅｐｏ１）（１６．３ｇ）を加え、５時間撹拌した。つぎに塩化トリオクチルメチルアンモニウム１０滴を加え、さらに０℃で１７時間撹拌した。つぎに０℃のまま静置した。静置後、上相を抜き出し、下相を飽和重曹水で洗浄した。洗浄後、上相の飽和重曹水を抜き出した。続いて、減圧留去することにより化合物（ｅｐｏ）（１．０３ｇ）を得た。生成物をＮＭＲで分析した結果、標記化合物の生成を確認した（収率３．３％）。
化合物（ｅｐｏ）の１９Ｆ−ＮＭＲ（２８２．７ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）δ（ｐｐｍ）：−８１．３（２Ｆ）、−９５．０（２Ｆ）、−１８２．４（２Ｆ）。
An aqueous solution (150 mL) containing 12% by mass of sodium hypochlorite and acetonitrile (25 mL) were added to a flask equipped with a reflux condenser. Subsequently, the compound (epo1) (16.3 g) was added while maintaining the internal temperature at 0 ° C., and the mixture was stirred for 5 hours. Next, 10 drops of trioctylmethylammonium chloride was added, and the mixture was further stirred at 0 ° C. for 17 hours. Next, it left still with 0 degreeC. After standing, the upper phase was extracted, and the lower phase was washed with saturated aqueous sodium hydrogen carbonate. After washing, the saturated aqueous sodium bicarbonate solution was extracted. Then, the compound (epo) (1.03g) was obtained by depressurizingly distilling. As a result of NMR analysis of the product, it was confirmed that the title compound was formed (yield 3.3%).
19 F-NMR (282.7 MHz, solvent: CDCl 3 , standard: CFCl 3 ) δ (ppm) of compound (epo): −81.3 (2F), −95.0 (2F), −182.4 ( 2F).
［例３（実施例）］化合物（１１）の製造例
フラスコに、化合物（２１）（７０．０ｇ）と（ＣＦ３）３Ｎ（３１６．６ｇ）を加えた。フラスコの内温を０℃保持しながら、１２質量％の次亜塩素酸ソーダを含む水溶液（４００ｇ）と塩化トリオクチルメチルアンモニウム（０．５０ｇ）を加え２相系溶液を得た。
Example 3 (Example) Production Example of Compound (11) Compound (21) (70.0 g) and (CF 3 ) 3 N (316.6 g) were added to a flask. While maintaining the internal temperature of the flask at 0 ° C., an aqueous solution (400 g) containing 12 mass% sodium hypochlorite and trioctylmethylammonium chloride (0.50 g) were added to obtain a two-phase solution.
つぎにフラスコ内を４時間撹拌してから、フラスコを静置しフラスコ内溶液の上相を抜き出した。つづいてフラスコに１２質量の％次亜塩素酸ソーダを含む水溶液（１２０ｇ）と塩化トリオクチルメチルアンモニウム（０．１０ｇ）を加え、フラスコ内を１時間撹拌する操作を行った。さらに該操作を９回行った。 Next, after stirring the inside of the flask for 4 hours, the flask was allowed to stand and the upper phase of the solution in the flask was extracted. Subsequently, an aqueous solution (120 g) containing 12 mass% sodium hypochlorite and trioctylmethylammonium chloride (0.10 g) were added to the flask, and the inside of the flask was stirred for 1 hour. Furthermore, this operation was performed 9 times.
つづいてフラスコを静置し、フラスコ内溶液の下相の液を抜き出して飽和チオ硫酸ナトリウム水溶液（１００ｍＬ）で洗浄した。さらに減圧留去して粗生成物（５１．５ｇ）を得た。粗生成物を１９Ｆ−ＮＭＲで分析した結果、下記化合物（１１）の生成を確認した（収率６０％）。粗生成物をさらに精留して高純度な化合物（１１）を得た。 Subsequently, the flask was allowed to stand, and the lower phase liquid in the flask was extracted and washed with a saturated aqueous sodium thiosulfate solution (100 mL). Further, the residue was distilled under reduced pressure to obtain a crude product (51.5 g). As a result of analyzing the crude product by 19 F-NMR, it was confirmed that the following compound (11) was produced (yield 60%). The crude product was further rectified to obtain a highly pure compound (11).
化合物（１１）の１９Ｆ−ＮＭＲ（２８２．７ＭＨｚ、溶媒：ＣＤＣｌ３、基準：ＣＦＣｌ３）δ（ｐｐｍ）：−６８．９（４Ｆ）、−１１７．９（２Ｆ）、−１２８．５（２Ｆ）、−１５３．５（２Ｆ）。 19 F-NMR (282.7 MHz, solvent: CDCl 3 , standard: CFCl 3 ) δ (ppm) of compound (11): −68.9 (4F), −117.9 (2F), −128.5 ( 2F), -153.5 (2F).
［例４（実施例）］重合体（Ａ）の製造例
耐圧反応器（ガラス製、内容積２０ｍＬ）に、化合物（１１）（５．６ｇ）、ＣＨ３Ｏ（ＣＨ２ＣＨ２Ｏ）４ＣＨ３（２ｇ）、テトラヒドロフラン（４ｇ）およびＣｓＦ（０．００７ｇ）を仕込んでから、反応器内を凍結脱気した。つぎに反応器の内温を−３０℃に保持しながら２４時間重合を行い、さらに内温を−１０℃に保持しながら２０時間重合を行った。反応器内容物を回収しその結果、グリース状の重合体（３．４ｇ、以下、重合体（Ａ）という。）を得た。
[Example 4 (Example)] Polymer Preparation pressure resistant reactor (A) (made of glass, internal capacity 20mL), a compound (11) (5.6g), CH 3 O (CH 2 CH 2 O) 4 After charging CH 3 (2 g), tetrahydrofuran (4 g) and CsF (0.007 g), the inside of the reactor was freeze-degassed. Next, polymerization was carried out for 24 hours while maintaining the internal temperature of the reactor at -30 ° C, and polymerization was further carried out for 20 hours while maintaining the internal temperature at -10 ° C. The reactor contents were recovered, and as a result, a grease-like polymer (3.4 g, hereinafter referred to as polymer (A)) was obtained.
重合体（Ａ）を１９Ｆ−ＮＭＲを用いて解析した結果、化合物（１１）のエポキシ構造に起因するフッ素原子のピークは完全に消失しており、重合体（Ａ１）は下記単位（Ａ１１）、下記単位（Ａ２１）および下記単位（Ａ３１）を含む重合体であることを確認した。重合体（Ａ）のＭｗは１０００であった。また、膜厚０．８５μｍの重合体（Ａ）の１９３ｎｍの波長光に対する透過率は、約９０％であった。 As a result of analyzing the polymer (A) using 19 F-NMR, the peak of the fluorine atom due to the epoxy structure of the compound (11) has completely disappeared, and the polymer (A1) has the following unit (A11): It was confirmed that the polymer contained the following unit (A21) and the following unit (A31). Mw of the polymer (A) was 1000. Further, the transmittance of the polymer (A) having a film thickness of 0.85 μm with respect to light having a wavelength of 193 nm was about 90%.
［例５（実施例）］化合物（１１）と化合物（ｅｐｏ）の共重合反応による共重合体（Ａ）の製造例
耐圧反応器（ガラス製、内容積２０ｍＬ）に、化合物（１１）（１．１ｇ）、化合物（ｅｐｏ）（０．７ｇ）、ＣＨ３Ｏ（ＣＨ２ＣＨ２Ｏ）４ＣＨ３（０．３ｇ）、テトラヒドロフラン（０．６ｇ）、ＣｓＦ（４．４ｍｇ）を仕込んでから反応器内を凍結脱気した。つぎに内温を−３０℃に保持しながら２４時間重合を行い、さらに内温を−１０℃に保持しながら２０時間重合を行った。反応器内容物を回収しその結果、グリース状の重合体（１．０ｇ、以下、共重合体（Ａ）という。）を得た。
Example 5 (Example) Production Example of Copolymer (A) by Copolymerization Reaction of Compound (11) and Compound (epo) In a pressure resistant reactor (made of glass, internal volume 20 mL), compound (11) (1 0.1 g), compound (epo) (0.7 g), CH 3 O (CH 2 CH 2 O) 4 CH 3 (0.3 g), tetrahydrofuran (0.6 g), CsF (4.4 mg) The inside of the reactor was frozen and degassed. Next, polymerization was carried out for 24 hours while maintaining the internal temperature at −30 ° C., and further polymerization was carried out for 20 hours while maintaining the internal temperature at −10 ° C. The reactor contents were recovered, and as a result, a grease-like polymer (1.0 g, hereinafter referred to as copolymer (A)) was obtained.
共重合体（Ａ）を１９Ｆ−ＮＭＲを用いて解析した結果、化合物（１１）および化合物（ｅｐｏ）のエポキシ構造に起因するフッ素原子のピークは完全に消失しており、共重合体（Ａ）は単位（Ａ１１）、単位（Ａ２１）、単位（Ａ３１）および下記単位（Ｅｐｏ）を含む重合体であることを確認した。重合体（Ａ）のＭｗは１０００であった。 As a result of analyzing the copolymer (A) using 19 F-NMR, the peak of the fluorine atom due to the epoxy structure of the compound (11) and the compound (epo) has completely disappeared, and the copolymer (A ) Was confirmed to be a polymer containing unit (A11), unit (A21), unit (A31) and the following unit (Epo). Mw of the polymer (A) was 1000.
本発明の化合物は、重合性の化合物として有用である。本発明の化合物を重合させた重合体は、特に短波長光に対する透明性に優れることから、ペリクル材料等の光学材料として有用である。
The compound of the present invention is useful as a polymerizable compound. A polymer obtained by polymerizing the compound of the present invention is particularly useful as an optical material such as a pellicle material because of its excellent transparency to short wavelength light.
Claims (4)
ＣＦ２＝ＣＦＣＲＦ１ＲＦ２ＯＣＦ２ＣＦ＝ＣＦ２ （２）
CF 2 = CFCR F1 R F2 OCF 2 CF = CF 2 (2)
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