JP2007314586A - Novel fluoropolymer, production method for the polymer, and production method for 1,6-diene ether - Google Patents
Novel fluoropolymer, production method for the polymer, and production method for 1,6-diene ether Download PDFInfo
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Abstract
Description
本発明は、新規な含フッ素重合体、その重合体の製造法およびその中間体である1,6―ジエン型エーテルの製造法に関する。 The present invention relates to a novel fluorine-containing polymer, a method for producing the polymer, and a method for producing 1,6-diene ether as an intermediate thereof.
フッ素系ポリマーの代表例であるポリテトラフルオロエチレン(PTFE)は、高度な耐熱性、耐薬品性を示すが、結晶性であるため不透明である。また、サイトップ(登録商標)やテフロン(登録商標)AFは、非晶質、溶剤可溶の透明ポリマーで、低反射膜などに利用されているが、ガラス転移点が低く、用途に制限をうける。 Polytetrafluoroethylene (PTFE), which is a typical example of a fluoropolymer, exhibits high heat resistance and chemical resistance, but is opaque because it is crystalline. Cytop (registered trademark) and Teflon (registered trademark) AF are amorphous, solvent-soluble transparent polymers that are used in low-reflective coatings, etc., but have a low glass transition point, limiting their use. box office.
一方、オクタフルオロシクロペンテン(OFCP)は工業的に製造されているシクロオレフィンであるが、重合性に乏しいため、モノマーとしての利用例は非常に少ない。 On the other hand, octafluorocyclopentene (OFCP) is an industrially produced cycloolefin, but its use as a monomer is very few because of poor polymerizability.
本発明者らは、フッ素アニオン存在下のOFCPとシリル=エノール=エーテルとの反応では、対応する付加−脱フルオリド生成物であるジビニルエーテルが得られ、この化合物のラジカル重合性は確認できなかったが、カチオン開始によるシクロペンテンペンダントをもつオリゴマー生成が可能であることをすでに報告している。 The present inventors obtained divinyl ether as a corresponding addition-defluoride product in the reaction of OFCP with silyl = enol = ether in the presence of a fluorine anion, and the radical polymerizability of this compound could not be confirmed. Have already reported that oligomer formation with cyclopentene pendants by cation initiation is possible.
本発明は、上記に鑑みなされたもので、新規な含フッ素重合体、その重合体の製造法およびその中間体である下記に示す1,6−ジエン型エーテルの製造法を提供するものである。 The present invention has been made in view of the above, and provides a novel fluoropolymer, a process for producing the polymer, and a process for producing the following 1,6-diene ether, which is an intermediate thereof. .
本発明によれば、下記式(1)で表される構造及び/又は式(2)で表される構造を含有する新規なフッ素系重合体、
1,6−ジエン型エーテルを重合することを特徴とするその重合体の製造法およびオクタフルオロシクロペンテンとホモアリルアルコール又はその誘導体とを反応させることを特徴とする1,6−ジエン型エーテルの製造法が提供される。
According to the present invention, a novel fluoropolymer containing a structure represented by the following formula (1) and / or a structure represented by the formula (2),
Process for producing a polymer characterized by polymerizing 1,6-diene ether and production of 1,6-diene ether characterized by reacting octafluorocyclopentene with homoallyl alcohol or a derivative thereof Law is provided.
本発明によれば、透明性が高く、高いガラス転移点を有し、溶媒可溶で成形性を備えた新規な含フッ素重合体およびその重合体の製造法を得ることができる。 According to the present invention, it is possible to obtain a novel fluoropolymer having high transparency, high glass transition point, solvent-solubility and moldability, and a method for producing the polymer.
上記の式で示される重合体は1.6−ジエン型エーテルを重合することによって得られる。
1.6−ジエン型エーテルは、
オクタフルオロシクロペンテン
キル基またはアリール基を示す)
とを反応させることによって得られる。
The polymer represented by the above formula can be obtained by polymerizing 1.6-diene ether.
The 1.6-diene ether is
Octafluorocyclopentene
It is obtained by reacting.
1,6−ジエン型エーテルの製造反応は、ホモアリルアルコール又はその誘導体1モルに対してオクタフルオロシクロペンテンを1〜10モル、好ましくは2〜4モルとして行うことが好ましい。通常大気圧下で行なわれ、KOHの存在下に非溶媒で行なうことが好ましい。反応時間は通常1ないし24時間とされる。この反応は下記の式で示される。 The production reaction of 1,6-diene ether is preferably carried out with 1 to 10 moles, preferably 2 to 4 moles of octafluorocyclopentene per mole of homoallyl alcohol or a derivative thereof. Usually, it is carried out under atmospheric pressure, and it is preferably carried out with a non-solvent in the presence of KOH. The reaction time is usually 1 to 24 hours. This reaction is represented by the following formula.
重合体は、1,6−ジエン型エーテルの重合によって得られるが、塊状重合で行なうことが好ましい。重合温度は、60℃〜120℃の範囲で行なうことが好ましい。重合時間は通常4〜48時間、好ましくは6〜12時間とされる。 The polymer is obtained by polymerization of 1,6-diene type ether, but it is preferably carried out by bulk polymerization. The polymerization temperature is preferably in the range of 60 ° C to 120 ° C. The polymerization time is usually 4 to 48 hours, preferably 6 to 12 hours.
開始剤として一般的なラジカル開始剤を使用でき、過酸化ベンゾイル、アゾビスイソブチロニトリル等が用いられる。 A general radical initiator can be used as the initiator, and benzoyl peroxide, azobisisobutyronitrile and the like are used.
上記の式(1)および式(2)におけるnの値は100以下の整数とされるが、通常は60以下とされる。 The value of n in the above formulas (1) and (2) is an integer of 100 or less, but is usually 60 or less.
本発明になる重合体のガラス転移点の範囲は175〜195℃とされる。
(実施例1)
The range of the glass transition point of the polymer according to the present invention is 175 to 195 ° C.
Example 1
1―(3−ブテニルオキシ)―2,3,3,4,4,5,5―ヘプタフルオロシクロペンテンの合成
アルゴン雰囲気下、OFCP2.09g(9.86mmol)に水酸化カリウム0.44g(7.84mmol)を加え、0℃に冷却し、3−ブテン−1−オール0.26ml(3mmol)をゆっくり滴下した。0℃で1時間撹拌後、室温に昇流し、2時間撹拌した。水で洗浄し、有機層を無水硫酸ナトリウムにより乾燥後、得られた油状残渣を常圧蒸留した。収量0.70g(2.7mmol)。収率88%。この生成物の各種スペクトルを図1、図2、図3に示す。
(実施例2〜6)
Synthesis of 1- (3-butenyloxy) -2,3,3,4,4,5,5-heptafluorocyclopentene In an argon atmosphere, 2.09 g (9.86 mmol) of OFCP and 0.44 g (7.84 mmol) of potassium hydroxide The solution was cooled to 0 ° C., and 0.26 ml (3 mmol) of 3-buten-1-ol was slowly added dropwise. After stirring at 0 ° C. for 1 hour, the mixture was warmed to room temperature and stirred for 2 hours. After washing with water and drying the organic layer with anhydrous sodium sulfate, the resulting oily residue was distilled at atmospheric pressure. Yield 0.70 g (2.7 mmol). Yield 88%. Various spectra of this product are shown in FIG. 1, FIG. 2, and FIG.
(Examples 2 to 6)
1―(3―ブテニロキシ)―2,3,3,4,4,5,5―ヘプタフルオロシクロペンテンの単独塊状重合
ガラス製重合管に1―(ブテニルオキシ)―2,3,3,4,4,5,5―ヘプタフルオロシクロペンテン1.32g(5mmol)と過酸化ベンゾイル0.0061g(0.5mol%)を入れ、(1)−78℃冷却下脱気および(2)室温融解を3回繰り返し、封管した。80℃で24時間重合後、得られたポリマーを少量のテトラヒドロフランに溶かし、メタノール中に滴下し、再沈殿、デカンテーションの後、含有溶媒を減圧留去した。ポリマー収率85%。
Homofluoropolymerization of 1- (3-butenyloxy) -2,3,3,4,4,5,5-heptafluorocyclopentene 1- (butenyloxy) -2,3,3,4,4,4 in a glass polymerization tube Putting 1.32 g (5 mmol) of 5,5-heptafluorocyclopentene and 0.0061 g (0.5 mol%) of benzoyl peroxide, repeating (1) degassing under cooling at −78 ° C. and (2) melting at room temperature three times. Sealed. After polymerization at 80 ° C. for 24 hours, the obtained polymer was dissolved in a small amount of tetrahydrofuran and dropped into methanol. After reprecipitation and decantation, the solvent contained was distilled off under reduced pressure. Polymer yield 85%.
開始剤の仕込み比率を変化させ重合を行なった結果を表1に示す。 Table 1 shows the results of polymerization by changing the charge ratio of the initiator.
いずれの開始剤でも、重量平均分子量約8,000〜15,000程度のポリマーが得られた。一般的なビニル化合物のラジカル重合と同様に、開始剤の増量により分子量が減少する傾向も認められた。示差走査熱量計(DSC)によるガラス転移点が約190℃でサイトップ(登録商標)の108℃よりも高かった。熱重量分析における10%減量温度は290〜345℃であった。図7に示すUV−visスペクトルからBPOを用いた場合には280nm以上、AIBNを用いた場合には245nm以上の紫外及び可視領域で完全に透明であることが示される。 In any initiator, a polymer having a weight average molecular weight of about 8,000 to 15,000 was obtained. Similar to the radical polymerization of general vinyl compounds, a tendency for the molecular weight to decrease with an increase in the initiator was also observed. The glass transition point by a differential scanning calorimeter (DSC) was about 190 ° C., which was higher than 108 ° C. of Cytop (registered trademark). The 10% weight loss temperature in thermogravimetric analysis was 290 to 345 ° C. From the UV-vis spectrum shown in FIG. 7, it is shown that the film is completely transparent in the ultraviolet and visible regions of 280 nm or more when BPO is used and AIBN is 245 nm or more.
また、一定濃度0.5mol%の開始剤(BPO)を用い、80℃(熱分解半減期約4.5時間)で重合時間を変化させて重合を行った結果、重合時間にかかわらず分子量がほぼ一定であったことから、BPO分解速度より重合反応速度の方が極端に速いことが示唆された(表2)。 Moreover, as a result of carrying out the polymerization by changing the polymerization time at 80 ° C. (thermal decomposition half-life: about 4.5 hours) using an initiator (BPO) having a constant concentration of 0.5 mol%, the molecular weight was reduced regardless of the polymerization time. Since it was almost constant, it was suggested that the polymerization reaction rate was extremely faster than the BPO decomposition rate (Table 2).
生成したポリマーの1H−NMR(図4)では、ビニルプロトンシグナル、19F−NMR(図5)ではシクロペンテニル基のC(sp2)−Fシグナルの完全な消失が確認された。また、IRスペクトル(図6)から炭素−炭素二重結合の吸収も完全に消失した。 1 H-NMR (FIG. 4) of the produced polymer confirmed the complete disappearance of the vinyl proton signal and 19 F-NMR (FIG. 5) of the C (sp 2 ) -F signal of the cyclopentenyl group. Further, the absorption of the carbon-carbon double bond completely disappeared from the IR spectrum (FIG. 6).
この結果から、ホモアリル部分のみがビニル重合し、シクロペンテニルをペンダントとする構造3aは含まれず、ホモアリルおよびシクロペンテニルの両方の二重結合が重合に関与した、縮環型3b及びスピロ型3cのいずれか又は双方の環化構造を含有するポリマーであると推測できる(nは100以下の整数である)。 From this result, only the homoallyl moiety is vinyl polymerized, and the structure 3a having cyclopentenyl as a pendant is not included. Or a polymer containing both cyclized structures (n is an integer of 100 or less).
本発明の重合体には、テトラヒドロフラン、ジクロロメタン等の有機溶媒であることから、1,6−ジエン型エーテルに含まれる二種類の炭素−炭素二重結合がランダムに重合に関与した三次元網目構造は生成していないことが確認できる。 Since the polymer of the present invention is an organic solvent such as tetrahydrofuran and dichloromethane, a three-dimensional network structure in which two types of carbon-carbon double bonds contained in 1,6-diene ether are randomly involved in polymerization. Can be confirmed.
本発明になる新規な含フッ素重合体は、高ガラス転移点(Tg)、透明性、溶剤可溶性を示す高機能ポリマーであり、多くの用途が見込まれ、低反射コート、半導体絶縁材、半導体リソグラフィーにおけるペリクルなど先端技術分野の用途に有効である。 The novel fluorine-containing polymer according to the present invention is a high-functional polymer exhibiting a high glass transition point (Tg), transparency, and solvent solubility, and is expected to have many uses, such as a low-reflection coating, a semiconductor insulating material, and semiconductor lithography. It is effective for applications in advanced technology fields such as pellicles.
Claims (3)
A process for producing 1,6-diene ethers, characterized by reacting octafluorocyclopentene with homoallyl alcohol or a derivative thereof.
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WO2010134509A1 (en) * | 2009-05-19 | 2010-11-25 | 国立大学法人茨城大学 | Fluorine-containing 1,6-diene ether compound and fluorine-containing polymer |
WO2011021598A1 (en) | 2009-08-19 | 2011-02-24 | 国立大学法人茨城大学 | Transparent fluorine-containing polymer |
JP2012051863A (en) * | 2010-09-03 | 2012-03-15 | Ibaraki Univ | New fluorine-containing compound, method for producing polymer of the fluorine-containing compound, and optical element, functional thin film and resist membrane comprising the polymer of the fluorine-containing compound |
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Cited By (10)
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WO2010134509A1 (en) * | 2009-05-19 | 2010-11-25 | 国立大学法人茨城大学 | Fluorine-containing 1,6-diene ether compound and fluorine-containing polymer |
US20120065320A1 (en) * | 2009-05-19 | 2012-03-15 | Nissan Chemical Industries, Ltd. | Fluorine-containing 1,6-diene ether compound and fluorine-containing polymer |
JP5652919B2 (en) * | 2009-05-19 | 2015-01-14 | 国立大学法人茨城大学 | Fluorine-containing 1,6-diene ether compound and fluorine-containing polymer |
WO2011021598A1 (en) | 2009-08-19 | 2011-02-24 | 国立大学法人茨城大学 | Transparent fluorine-containing polymer |
EP2468779A1 (en) * | 2009-08-19 | 2012-06-27 | Ibaraki University | Transparent fluorine-containing polymer |
CN102666612A (en) * | 2009-08-19 | 2012-09-12 | 国立大学法人茨城大学 | Transparent fluorine-containing polymer |
EP2468779A4 (en) * | 2009-08-19 | 2013-01-02 | Univ Ibaraki | Transparent fluorine-containing polymer |
US8871332B2 (en) | 2009-08-19 | 2014-10-28 | Ibaraki University | Transparent fluorine-containing polymer |
JP5737656B2 (en) * | 2009-08-19 | 2015-06-17 | 国立大学法人茨城大学 | Transparent fluoropolymer |
JP2012051863A (en) * | 2010-09-03 | 2012-03-15 | Ibaraki Univ | New fluorine-containing compound, method for producing polymer of the fluorine-containing compound, and optical element, functional thin film and resist membrane comprising the polymer of the fluorine-containing compound |
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