JP4415665B2 - Tetrafluoroethylene copolymer - Google Patents
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- JP4415665B2 JP4415665B2 JP2003421190A JP2003421190A JP4415665B2 JP 4415665 B2 JP4415665 B2 JP 4415665B2 JP 2003421190 A JP2003421190 A JP 2003421190A JP 2003421190 A JP2003421190 A JP 2003421190A JP 4415665 B2 JP4415665 B2 JP 4415665B2
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Description
本発明は、テトラフルオロエチレン共重合体に関する。 The present invention relates to a tetrafluoroethylene copolymer.
テトラフルオロエチレンとパーフルオロ（アルキルビニルエーテル）との共重合体（以下、ＰＦＡという。）は、耐熱性、耐薬品性に優れ、化学産業や半導体産業で用いられる配管、チューブ、バルブ、等の部材、ウエハーバスケット、薬液容器、ライニング材料等として広く用いられている。 A copolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether) (hereinafter referred to as PFA) is excellent in heat resistance and chemical resistance, and is used for pipes, tubes, valves, etc. used in the chemical and semiconductor industries. Widely used as wafer baskets, chemical containers, lining materials, etc.
ＰＦＡとしては、テトラフルオロエチレン（以下、ＴＦＥという。）とパーフルオロ（プロピルビニルエーテル）（以下、ＰＰＶＥという。）との共重合体（以下、ＴＦＥ／ＰＰＶＥ共重合体という。）が市販されている。ＴＦＥ／ＰＰＶＥ共重合体を成形した部材は、弾性率及び降伏強度が低く、変形しやすい。そのため、該部材を高応力や圧力下に使用する場合には、耐久性を向上するために、その肉厚を厚くする必要があり、部材設計の制約となる。また、高価なＴＦＥ／ＰＰＶＥ共重合体を多量に使用することは経済的に不利である。ＴＦＥ／ＰＰＶＥ共重合体の部材は高応力下にクラックを発生しやすいことから、耐ストレスクラック性に優れたＰＦＡの開発が要請されている。 As PFA, a copolymer of tetrafluoroethylene (hereinafter referred to as TFE) and perfluoro (propyl vinyl ether) (hereinafter referred to as PPVE) (hereinafter referred to as TFE / PPVE copolymer) is commercially available. . The member formed from the TFE / PPVE copolymer has a low elastic modulus and a low yield strength and is easily deformed. For this reason, when the member is used under high stress or pressure, it is necessary to increase its thickness in order to improve durability, which is a restriction on member design. Moreover, it is economically disadvantageous to use a large amount of expensive TFE / PPVE copolymer. Since TFE / PPVE copolymer members are prone to cracking under high stress, development of PFA excellent in stress cracking resistance is required.
特許文献１には、ＴＦＥとパーフルオロ（エチルビニルエーテル）との共重合体が記載されている。該共重合体は耐屈曲疲労性に優れるが、弾性率、降伏強度の特性についての記載はない。特許文献２には、ＴＦＥと特定のパーフルオロシクロアルキル基を有するパーフルオロ（アルキルビニルエーテル）との共重合体が記載されているが、該共重合体は溶融成形できない。 Patent Document 1 describes a copolymer of TFE and perfluoro (ethyl vinyl ether). The copolymer is excellent in bending fatigue resistance, but there is no description about the elastic modulus and yield strength characteristics. Patent Document 2 describes a copolymer of TFE and perfluoro (alkyl vinyl ether) having a specific perfluorocycloalkyl group, but the copolymer cannot be melt-molded.
本発明者らは、ＴＦＥ、ＰＰＶＥ及び架橋可能な官能基を有するモノマーを共重合させて得たフッ素樹脂を酸素雰囲気下に高温で熱処理することにより、高弾性率のフッ素樹脂を得た（特許文献３を参照。）。しかし、この製造方法は、熱処理時間が長く、生産性が低い。また、架橋可能な官能基が残存する場合にはフッ素樹脂の耐薬品性が充分でない。 The present inventors obtained a fluororesin having a high elastic modulus by heat-treating a fluororesin obtained by copolymerizing TFE, PPVE and a monomer having a crosslinkable functional group at a high temperature in an oxygen atmosphere (patent) See reference 3.) However, this manufacturing method has a long heat treatment time and low productivity. Moreover, when the crosslinkable functional group remains, the chemical resistance of the fluororesin is not sufficient.
本発明の目的は、溶融成形性及び耐薬品性に優れ、弾性率及び降伏強度が高く、耐ストレスクラック性に優れるＴＦＥと特定のパーフルオロビニルエーテルとの共重合体を提供することである。 An object of the present invention is to provide a copolymer of TFE and a specific perfluorovinyl ether which is excellent in melt moldability and chemical resistance, has a high elastic modulus and yield strength, and is excellent in stress crack resistance.
本発明は、テトラフルオロエチレンに基づく重合単位（Ａ）とＣＦ２＝ＣＦＯＲｆ１Ｒｆ２（ここで、Ｒｆ１ はポリフルオロアルキレン基を、Ｒｆ２はエーテル性酸素原子を含んでもよい、４員環または５員環に基づくポリフルオロシクロアルキル基を、表す。）で表されるモノマーに基づく重合単位（Ｂ）を含有し、（Ａ）／（Ｂ）がモル比で９９．７／０．３〜９０／１０であり、容量流速が０．１〜１０００ｍｍ３／秒であることを特徴とするテトラフルオロエチレン共重合体を提供する。 The present invention relates to a polymer unit (A) based on tetrafluoroethylene and CF 2 ═CFOR f1 R f2 (wherein R f1 may contain a polyfluoroalkylene group, and R f2 may contain an etheric oxygen atom) Or a polymer unit (B) based on a monomer represented by the following formula: (A) / (B) in a molar ratio of 99.7 / 0.3. A tetrafluoroethylene copolymer is provided which has a capacity flow rate of 0.1 to 1000 mm 3 / sec.
本発明のテトラフルオロエチレン共重合体は、弾性率及び降伏強度が高く、耐ストレスクラック性に優れる。また、溶融成形性、耐薬品性、耐熱性に優れる。 The tetrafluoroethylene copolymer of the present invention has high elastic modulus and yield strength, and is excellent in stress crack resistance. Moreover, it is excellent in melt moldability, chemical resistance, and heat resistance.
本発明において、ＣＦ２＝ＣＦＯＲｆ１Ｒｆ２におけるＲｆ１は、ポリフルオロアルキレン基である。好ましくは、炭素原子数が１〜１０で、環構造を有しない、パーフルオロアルキレン基である。Ｒｆ１は、ジフルオロメチレン基、パーフルオロジメチレン基、パーフルオロトリメチレン基が好ましい。Ｒｆ１が存在すると、ＣＦ２＝ＣＦＯＲｆ１Ｒｆ２は、ＴＦＥとの共重合性が良好である。
In the present invention, R f1 in CF 2 ═CFOR f1 R f2 is a polyfluoroalkylene group. Preferably, 1 to 10 carbon atoms, having no ring structure, a perfluoroalkylene group. R f1 is a difluoromethylene group, perfluoro dimethylene group, perfluoro trimethylene group are preferable. When R f1 is present, CF 2 = CFOR f1 R f2 has good copolymerizability with TFE.
Ｒｆ２はエーテル性酸素原子を含んでもよい、４員環または５員環に基づくポリフルオロシクロアルキル基である。好ましくはエーテル性酸素原子を含んでもよい、４員環または５員環に基づくパーフルオロシクロアルキル基である。 R f2 is a polyfluorocycloalkyl group based on a 4-membered ring or a 5-membered ring , which may contain an etheric oxygen atom. Preferably, it is a perfluorocycloalkyl group based on a 4-membered ring or 5-membered ring which may contain an etheric oxygen atom.
前記環としては、エーテル性酸素原子を１又は２個有する環が好ましく、オキソラン環又は１，３ジオキソラン環がより好ましい。環の炭素原子にはポリフルオロアルキル基やポリフルオロアルコキシ基等の置換基が結合していてもよい。該置換基としては、炭素原子数４以下のパーフルオロアルキル基と炭素原子数４以下のパーフルオロアルコキシ基が好ましく、トリフルオロメチル基がより好ましい。Ｒｆ２は、環に酸素原子を有するパーフルオロシクロアルキル基がより好ましい。Ｒｆ２の具体例としては、つぎの構造が挙げられる。 The ring is preferably a ring having 1 or 2 etheric oxygen atoms, more preferably an oxolane ring or a 1,3 dioxolane ring. A substituent such as a polyfluoroalkyl group or a polyfluoroalkoxy group may be bonded to the ring carbon atom. As the substituent, a perfluoroalkyl group having 4 or less carbon atoms and a perfluoroalkoxy group having 4 or less carbon atoms are preferable, and a trifluoromethyl group is more preferable. R f2 is more preferably a perfluorocycloalkyl group having an oxygen atom in the ring. Specific examples of R f2 include the following structures.
ＣＦ２＝ＣＦＯＲｆ１Ｒｆ２で表されるモノマーは、式（１）で表されるモノマー、式（２）で表されるモノマー及び式（３）で表されるモノマーからなる群から選ばれる１種以上であることが好ましい。さらに、式（１）で表されるモノマー：パーフルオロテトラヒドロフルフリルビニルエーテルであることがより好ましい。以下、式（１）で表されるモノマーをＰＴＦＶＥともいう。 The monomer represented by CF 2 = CFOR f1 R f2 is 1 selected from the group consisting of a monomer represented by the formula (1), a monomer represented by the formula (2), and a monomer represented by the formula (3). It is preferable that it is a seed or more. Furthermore, the monomer represented by the formula (1) is more preferably perfluorotetrahydrofurfuryl vinyl ether. Hereinafter, the monomer represented by the formula (1) is also referred to as PTFVE.
式（１）で表されるモノマーは、種々の方法で製造することができるが、例えば、テトラヒドロフルフリルアルコール又は必要に応じてパーフルオロカルボン酸ハライドでエステル化したものをフッ素化し、次いでその生成物又はパーフルオロエステルを液相熱分解した生成物にヘキサフルオロプロペンオキシド（ＨＦＰＯ）を付加し、さらに気相熱分解することにより合成できる。 The monomer represented by the formula (1) can be produced by various methods. For example, fluorination of tetrahydrofurfuryl alcohol or esterification with perfluorocarboxylic acid halide as necessary, followed by formation thereof The product can be synthesized by adding hexafluoropropene oxide (HFPO) to a product obtained by liquid-phase pyrolysis of a product or perfluoroester, and further subjecting it to gas-phase pyrolysis.
本発明において、ＴＦＥに基づく重合単位（Ａ）／ＣＦ２＝ＣＦＯＲｆ１Ｒｆ２で表されるモノマーに基づく重合単位（Ｂ）はモル比で９９．７／０．３〜９０／１０である。（Ｂ）の比率が０．３よりも少ないと、溶融成形ができる程度の分子量では脆い共重合体となり、１０よりも多いと共重合体の弾性率が低い。この範囲にあると弾性率及び降伏強度が高く、耐ストレスクラック性に優れる。好ましくは（Ａ）／（Ｂ）がモル比で９９．５／０．５〜９５．０／５．０であり、より好ましくは９９．０／１．０〜９７．０／３．０である。 In the present invention, the polymer units (B) based on the monomer represented by TFE-based polymer units (A) / CF 2 = CFOR f1 R f2 are 99.7 / 0.3 to 90/10 in molar ratio. When the ratio of (B) is less than 0.3, the copolymer is brittle with a molecular weight that allows melt molding, and when it is more than 10, the elastic modulus of the copolymer is low. Within this range, the elastic modulus and yield strength are high and the stress crack resistance is excellent. Preferably (A) / (B) is 99.5 / 0.5 to 95.0 / 5.0 in molar ratio, more preferably 99.0 / 1.0 to 97.0 / 3.0. is there.
本発明のＴＦＥ共重合体の容量流速（以下、Ｑ値という。）は０．１〜１０００ｍｍ３／秒である。Ｑ値は、含フッ素共重合体の溶融流動性を表す指標であり、分子量の目安となる。Ｑ値が大きいと分子量が低く、小さいと分子量が高いことを示す。本発明におけるＱ値は、島津製作所製フローテスタを用いて、温度３８０℃において、荷重７ｋｇ下に直径２．１ｍｍ、長さ８ｍｍのオリフィス中にＴＦＥ共重合体を押出すときの押出し速度である。Ｑ値が小さすぎると溶融流動性が不充分で、成形品の表面が均一で平滑とはならない。大きすぎるとＴＦＥ共重合体の機械的強度が低い。この範囲にあると溶融成形性に優れる。本発明のＴＦＥ共重合体のＱ値は１〜５００ｍｍ３／秒が好ましく、２〜２００ｍｍ３／秒がより好ましい。 The volume flow rate (hereinafter referred to as Q value) of the TFE copolymer of the present invention is 0.1 to 1000 mm 3 / sec. The Q value is an index representing the melt fluidity of the fluorinated copolymer and is a measure of the molecular weight. A large Q value indicates a low molecular weight, and a small Q value indicates a high molecular weight. The Q value in the present invention is an extrusion speed when a TFE copolymer is extruded into an orifice having a diameter of 2.1 mm and a length of 8 mm under a load of 7 kg at a temperature of 380 ° C. using a flow tester manufactured by Shimadzu Corporation. . If the Q value is too small, the melt fluidity is insufficient, and the surface of the molded product is not uniform and smooth. If it is too large, the mechanical strength of the TFE copolymer is low. Within this range, the melt moldability is excellent. Q values of the TFE copolymer of the present invention is preferably from 1 to 500 mm 3 / sec, 2~200mm 3 / sec is more preferable.
本発明において、ＴＦＥとＣＦ２＝ＣＦＯＲｆ１Ｒｆ２に加えて、ＴＦＥと共重合可能な、その他のモノマーを併用してもよい。その他のモノマーの構造は特に限定されないが、具体例としては、エチレン等の炭化水素系オレフィン；フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、ＣＨ２＝ＣＸ（ＣＦ２）ｎＹ（ここで、Ｘ及びＹは、それぞれ独立に水素又はフッ素原子、ｎは２〜８の整数である。）等の不飽和基に水素原子を有するフルオロオレフィン；ヘキサフルオロプロピレン、クロロトリフルオロエチレン等の不飽和基に水素原子を有しないフルオロオレフィン（ただし、ＴＦＥを除く。）；パーフルオロ（メチルビニルエーテル）、パーフルオロ（エチルビニルエーテル）、ＰＰＶＥ、パーフルオロ（ブチルビニルエーテル）等のパーフルオロ（アルキルビニルエーテル）；
酢酸ビニル等のビニルエステル；アルキルビニルエーテル、グリシジルビニルエーテル、ヒドロキシブチルビニルエーテル、メチルビニロキシブチルカーボネート等のビニルエーテル等が挙げられる。
In the present invention, in addition to TFE and CF 2 ═CFOR f1 R f2 , other monomers copolymerizable with TFE may be used in combination. The structure of the other monomer is not particularly limited. Specific examples include hydrocarbon olefins such as ethylene; vinyl fluoride, vinylidene fluoride, trifluoroethylene, CH 2 ═CX (CF 2 ) n Y (where, X and Y are each independently hydrogen or a fluorine atom, n is an integer of 2 to 8.) A fluoroolefin having a hydrogen atom in an unsaturated group such as; an unsaturated group such as hexafluoropropylene or chlorotrifluoroethylene Fluoroolefin having no hydrogen atom (except TFE); perfluoro (alkyl vinyl ether) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), PPVE, perfluoro (butyl vinyl ether);
Vinyl esters such as vinyl acetate; vinyl ethers such as alkyl vinyl ether, glycidyl vinyl ether, hydroxybutyl vinyl ether, methylvinyloxybutyl carbonate, and the like.
その他のモノマーは、特に、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、パーフルオロ（アルキルビニルエーテル）からなる群から選ばれる１種以上が好ましい。得られるＴＦＥ共重合体は、耐熱性、耐薬品性に優れる。その他のモノマーに基づく重合単位（Ｃ）の含有量は、（Ｃ）／（（Ａ）＋（Ｂ）＋（Ｃ））がモル比で０．００１〜０．１が好ましく、０．００２〜０．０８がより好ましい。 The other monomer is particularly preferably at least one selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, and perfluoro (alkyl vinyl ether). The obtained TFE copolymer is excellent in heat resistance and chemical resistance. The content of the polymerized units (C) based on other monomers is preferably (C) / ((A) + (B) + (C)) in a molar ratio of 0.001 to 0.1, preferably 0.002 0.08 is more preferable.
本発明のＴＦＥ共重合体の製造方法は特に限定はなく、一般に用いられているラジカル重合開始剤を用いる重合方法が採用される。重合方法としては、塊状重合、フッ化炭化水素、塩化炭化水素、フッ化塩化炭化水素、アルコール、炭化水素等の有機溶媒を使用する溶液重合、水性媒体及び必要に応じて有機溶媒を使用する懸濁重合、水性媒体及び乳化剤を使用する乳化重合等が挙げられる。 The method for producing the TFE copolymer of the present invention is not particularly limited, and a polymerization method using a generally used radical polymerization initiator is employed. Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols and hydrocarbons, aqueous media, and suspensions using organic solvents as necessary. Examples thereof include suspension polymerization, emulsion polymerization using an aqueous medium and an emulsifier.
ラジカル重合開始剤としては、半減期が１０時間である温度が０〜１００℃である開始剤が好ましく、２０〜９０℃である開始剤がより好ましい。具体例としては、アゾビスイソブチロニトリル等のアゾ化合物、イソブチリルパーオキシド、オクタノイルパーオキシド、ベンゾイルパーオキシド、ラウロイルパーオキシド等の非フッ素系ジアシルパーオキシド、ジイソプロピルパーオキシジカーボネート等のパーオキシジカーボネート、ｔｅｒｔ−ブチルパーオキシピバレート、ｔｅｒｔ−ブチルパーオキシイソブチレート、ｔｅｒｔ−ブチルパーオキシアセテート等のパーオキシエステル、（Ｚ（ＣＦ２）ｐＣＯＯ）２（ここで、Ｚは水素原子、フッ素原子又は塩素原子であり、ｐは１〜１０の整数である。）で表される化合物等の含フッ素ジアシルパーオキシド、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムのような無機過酸化物等が挙げられる。 The radical polymerization initiator is preferably an initiator having a half-life of 10 hours and a temperature of 0 to 100 ° C, more preferably an initiator having a temperature of 20 to 90 ° C. Specific examples include azo compounds such as azobisisobutyronitrile, non-fluorine diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, and diisopropyl peroxydicarbonate. Peroxyesters such as oxydicarbonate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxyacetate, (Z (CF 2 ) p COO) 2 (where Z is hydrogen Inorganic peroxidation such as fluorine-containing diacyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, etc. Thing etc. are mentioned.
ラジカル重合条件も特に限定されず、重合温度は０〜１００℃が好ましく、２０〜９０℃がより好ましい。重合圧力は０．１〜１０ＭＰａが好ましく、０．５〜３ＭＰａがより好ましい。重合時間は１〜３０時間が好ましい。 The radical polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.
本発明において、ＴＦＥ共重合体がフッ素化処理されてなる実質的に不安定末端基を有しないＴＦＥ共重合体であることが好ましい。ここで、実質的に不安定末端基を有しないとは、−ＣＯＦ、−ＣＨ２ＯＨ、−ＣＯ２Ｈ等の不安定末端基を炭素原子百万個あたり１０個以上有しないことを意味する。より好ましくは５個以下である。不安定末端基の数が少ないと、ＴＦＥ共重合体の耐熱性、耐薬品性がさらに向上する。フッ素化処理の方法としては、ＴＦＥ共重合体を２００℃以上の温度下にフッ素ガスと接触させる方法が好ましい。フッ素ガスは窒素ガス等の不活性ガスで希釈して用いることも好ましい。フッ素化処理により、不安定末端基が安定な−ＣＦ３に変換される。 In the present invention, the TFE copolymer is preferably a TFE copolymer that has been subjected to a fluorination treatment and has substantially no unstable terminal group. Here, having substantially no unstable terminal group means having no more than 10 unstable terminal groups such as —COF, —CH 2 OH, and —CO 2 H per million carbon atoms. . More preferably, it is 5 or less. When the number of unstable end groups is small, the heat resistance and chemical resistance of the TFE copolymer are further improved. As a method for the fluorination treatment, a method in which the TFE copolymer is brought into contact with fluorine gas at a temperature of 200 ° C. or higher is preferable. The fluorine gas is also preferably diluted with an inert gas such as nitrogen gas. By the fluorination treatment, the unstable end group is converted to stable —CF 3 .
本発明のＴＦＥ共重合体の用途としては、半導体製造装置や化学プラントの薬液チューブ、継ぎ手、タンク、バルブ、ウエハーバスケット、配管やタンクの内面ライニング、ＯＡ機器のコピーロール、リチウム電池や燃料電池等のパッキン等が挙げられる。 Applications of the TFE copolymer of the present invention include chemical tubes, fittings, tanks, valves, wafer baskets, piping and tank inner linings for semiconductor manufacturing equipment and chemical plants, copy rolls for OA equipment, lithium batteries, fuel cells, etc. The packing etc. are mentioned.
以下、実施例及び比較例を挙げて本発明を詳細に説明するが、本発明はこれらに限定されない。なお、ＴＦＥ共重合体の組成、引張強度、引張伸度、引張弾性率、引張降伏強度、ＭＩＴ折り曲げ寿命は、以下に記載の方法で測定した。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these. The composition, tensile strength, tensile elongation, tensile modulus, tensile yield strength, and MIT bending life of the TFE copolymer were measured by the methods described below.
［ＴＦＥ共重合体の組成］旭硝子研究報告１９９０、４０（１）、７５の記載に準じて、ＴＦＥ共重合体を熱溶融状態で１９Ｆ−ＮＭＲ測定する方法によって求めた。 [Composition of TFE Copolymer] According to the description of Asahi Glass Research Report 1990, 40 (1), 75, the TFE copolymer was determined by 19 F-NMR measurement in a hot melt state.
［引張強度、引張伸度、引張弾性率、引張降伏強度」ＡＳＴＭ Ｄ３１５９に準じて、試験片を用いて引張速度５０ｍｍ／秒にて測定した。 [Tensile Strength, Tensile Elongation, Tensile Elastic Modulus, Tensile Yield Strength] Measured according to ASTM D3159 using a test piece at a tensile speed of 50 mm / sec.
［ＭＩＴ折り曲げ寿命］ＡＳＴＭ Ｄ２１７６に準じて、荷重１．２５ｋｇ、折り曲げ角度±１３５度、室温の条件下に、折り曲げ試験機（東洋精機社製、ＭＩＴ−Ｄ）を用いて試料の折り曲げ試験を行った。試料が破断するまでの折り曲げ回数がＭＩＴ折り曲げ寿命である。ＭＩＴ折り曲げ寿命は、ＴＦＥ共重合体の耐ストレスクラック性の指標となり、ＭＩＴ折り曲げ寿命が永いほど耐ストレスクラック性に優れる。試料は、ＴＦＥ共重合体を３４０℃で圧縮成形して得た厚さ０．２２０〜０．２３６ｍｍのフィルムを、幅１２．５ｍｍの短冊状に打ち抜いて作成した。 [MIT bending life] In accordance with ASTM D2176, a sample bending test was performed using a bending tester (MITO-D, manufactured by Toyo Seiki Co., Ltd.) under conditions of a load of 1.25 kg, a bending angle of ± 135 degrees, and room temperature. It was. The number of bendings until the sample breaks is the MIT bending life. The MIT bending life is an index of the stress crack resistance of the TFE copolymer, and the longer the MIT bending life, the better the stress crack resistance. The sample was prepared by punching a film having a thickness of 0.220 to 0.236 mm obtained by compression-molding a TFE copolymer at 340 ° C. into a strip shape having a width of 12.5 mm.
（参考例１）
（エステル化反応）
２−テトラヒドロフルフリルアルコールを２０ｇとトリエチルアミンを２１．８ｇとをフラスコに入れ、氷浴下撹拌し、ＦＣＯＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３の７１．５ｇを内温を１０℃以下に保ちながら１時間かけて滴下した。滴下終了後、室温で２時間撹拌し、水５０ｍＬを内温１５℃以下で加え、得られた粗液を分液し、水で洗浄し、硫酸マグネシウムで乾燥し、ろ過し、減圧蒸留を行い、式（ＩＩ）のエステル化合物６６．３ｇを得た。
(Reference Example 1)
(Esterification reaction)
20 g of 2-tetrahydrofurfuryl alcohol and 21.8 g of triethylamine are placed in a flask and stirred in an ice bath, and 71.5 g of FCOCF (CF 3 ) OCF 2 CF 2 CF 3 is kept at an internal temperature of 10 ° C. or lower. The solution was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, 50 mL of water was added at an internal temperature of 15 ° C. or lower, the obtained crude liquid was separated, washed with water, dried over magnesium sulfate, filtered, and distilled under reduced pressure. To obtain 66.3 g of an ester compound of the formula (II).
（フッ素反応）
５００ｍＬのニッケル製オートクレーブに、トリクロロトリフルオロエタン（Ｒ−１１３）を３１３ｇ加えて撹拌し、２５℃に保った。窒素ガスを１時間吹き込んだ後、窒素ガスで２０％に希釈したフッ素ガスを、流速８．０８Ｌ／ｈで１時間吹き込んだ。次に、フッ素ガスを同じ流速で吹き込みながら、エステル化で得た化合物（ＩＩ）５．０１ｇをＲ−１１３の１００ｇに溶解した溶液を４．７時間かけて注入した。さらに、フッ素ガスを同じ流速で吹き込みながら、ベンゼン濃度が０．０１ｇ／ｍＬのＲ−１１３溶液を２５℃から４０℃にまで昇温しながら９ｍＬ注入し、０．４時間撹拌を続けた。次に、圧力を常圧にし、反応器内温度を４０℃に保ちながら、上記のベンゼン溶液を６ｍＬ注入し、０．４時間撹拌を続け、さらに、同様の操作を３回繰り返した。ベンゼンの注入総量は０．３３ｇ、Ｒ−１１３の注入総量は３３ｍＬであった。
(Fluorine reaction)
To a 500 mL nickel autoclave, 313 g of trichlorotrifluoroethane (R-113) was added and stirred, and kept at 25 ° C. After blowing nitrogen gas for 1 hour, fluorine gas diluted to 20% with nitrogen gas was blown for 1 hour at a flow rate of 8.08 L / h. Next, while blowing fluorine gas at the same flow rate, a solution prepared by dissolving 5.01 g of the compound (II) obtained by esterification in 100 g of R-113 was injected over 4.7 hours. Further, 9 mL of an R-113 solution having a benzene concentration of 0.01 g / mL was injected while raising the temperature from 25 ° C. to 40 ° C. while blowing fluorine gas at the same flow rate, and stirring was continued for 0.4 hours. Next, 6 mL of the above benzene solution was injected while maintaining the pressure in the reactor at 40 ° C., stirring was continued for 0.4 hours, and the same operation was repeated three times. The total amount of benzene injected was 0.33 g, and the total amount of R-113 injected was 33 mL.
（パーフルオロエステル熱分解反応）
フッ素化で得た化合物（ＩＩＩ）２．１ｇを０．０２ｇのＮａＦ粉末と共にフラスコに仕込み、撹拌を行いながら１４０℃で加熱した。フラスコ上部には−１０℃に温度調節した還流器を設置した。冷却後２．０ｇの液状サンプルを回収し、これを精密蒸留して化合物（ＩＶ）０．８ｇを得た。
(Perfluoroester thermal decomposition reaction)
2.1 g of compound (III) obtained by fluorination was charged into a flask together with 0.02 g of NaF powder and heated at 140 ° C. while stirring. A reflux condenser whose temperature was adjusted to −10 ° C. was installed at the top of the flask. After cooling, 2.0 g of a liquid sample was collected, and this was precision distilled to obtain 0.8 g of compound (IV).
（パーフルオロテトラヒドロフルフリルビニルエーテル合成反応）
オートクレーブ中に脱水乾燥したＣｓＦ１６．５ｇを仕込んだ後に、反応器内を脱気し、化合物（ＩＶ）６６２ｇ（２．７ｍｏｌ）とテトラグライム１３９ｇを仕込んだ後に、反応器を−２０℃に冷却し、ヘキサフルオロプロピレンオキシド（ＨＦＰＯ）を反応器内圧が微減圧を保つように連続的に４５０ｇ（２．７ｍｏｌ）供給し、反応を行った。反応終了後に分液ロートにより１０１０ｇを回収し、テトラグライムで洗浄した後、ＫＯＨ３３０ｇを溶解した水溶液に滴下し、中和後水を留去した。得られた白色個体を減圧乾燥し、減圧状態を保ったまま液体窒素温度に冷却した金属製トラップを接続し、乾燥機内の温度を２７０℃まで昇温した。分解反応によって発生するガスを金属トラップ内に回収しながら、ガス発生が終了するまで反応を継続し、化合物（Ｉ）（ＰＴＦＶＥ：式（１）で表されるモノマー）７００ｇを得た。
(Perfluorotetrahydrofurfuryl vinyl ether synthesis reaction)
After charging 16.5 g of dehydrated and dried CsF in an autoclave, the inside of the reactor was degassed, and after adding 662 g (2.7 mol) of compound (IV) and 139 g of tetraglyme, the reactor was cooled to −20 ° C. Then, 450 g (2.7 mol) of hexafluoropropylene oxide (HFPO) was continuously supplied so that the internal pressure of the reactor was kept at a slightly reduced pressure, to carry out the reaction. After completion of the reaction, 1010 g was recovered with a separatory funnel, washed with tetraglyme, then dropped into an aqueous solution in which 330 g of KOH was dissolved, and water was distilled off after neutralization. The obtained white solid was dried under reduced pressure, a metal trap cooled to liquid nitrogen temperature was connected while maintaining the reduced pressure state, and the temperature in the dryer was raised to 270 ° C. While collecting the gas generated by the decomposition reaction in the metal trap, the reaction was continued until the gas generation was completed to obtain 700 g of Compound (I) (PTFVE: monomer represented by the formula (1)).
（参考例２）
２−テトラヒドロフルフリルアルコールに替えて、２，２−ジメチル−４−メチロール−１，３−ジオキソランを用いること以外、参考例１の反応手順と同様にして、式（２）で表されるモノマーを得た。
(Reference Example 2)
A monomer represented by the formula (2) in the same manner as in the reaction procedure of Reference Example 1, except that 2,2-dimethyl-4-methylol-1,3-dioxolane is used instead of 2-tetrahydrofurfuryl alcohol. Got.
（参考例３）
２−テトラヒドロフルフリルアルコールに替えて、２，４−ジメチル−２−メチロール−１，３−ジオキソランを用いること以外、参考例１の反応手順と同様にして、式（３）で表されるモノマーを得た。
(Reference Example 3)
A monomer represented by the formula (3) in the same manner as in the reaction procedure of Reference Example 1, except that 2,4-dimethyl-2-methylol-1,3-dioxolane is used instead of 2-tetrahydrofurfuryl alcohol. Got.
［実施例１］
１．２リットルの撹拌機付き圧力容器に、イオン交換水の５９０ｇ、ＣＨＦＣｌＣＦ２ＣＦ２Ｃｌの３５３ｇ、ＰＴＦＶＥの５４．８ｇ、メタノールの１６．４ｇを仕込み、５０℃の内温で、ＴＦＥを圧力が１．２１ＭＰａになるまで仕込んだ。ついで（ＣＦ３ＣＦ２ＣＦ２ＣＯＯ）２の０．１％溶液（溶媒：ＣＨＦＣｌＣＦ２ＣＦ２Ｃｌ）（以下、開始剤溶液という。）の３ｍＬを仕込み、５０℃で重合を開始させた。重合中に開始剤溶液は断続的に仕込み、合計２０．２ｍＬを仕込んだ。重合の進行にともない、圧力が低下するので、圧力が一定になるようにＴＦＥを連続的に後仕込みした。後仕込みのＴＦＥ量が１４５ｇになったところで内温を室温まで冷却し、未反応ＴＦＥを空放し、圧力容器を開放した。圧力容器の内容物をガラスフィルターで濾過してスラリー状のＴＦＥ共重合体を得た。得られたスラリーを１２０℃で８時間乾燥して白色のＴＦＥ共重合体の１５５ｇを得た。得られたＴＦＥ共重合体は、ＴＦＥに基づく重合単位／ＰＴＦＶＥに基づく重合単位のモル比が９８．３／１．７であり、Ｑ値は１．７ｍｍ３／秒であった。引張強度は３２．６ＭＰａ、引張伸度は３１０％、降伏強度は１４．０ＭＰａ、引張弾性率は１５４ＭＰａ、ＭＩＴ折り曲げ寿命は１２３万回であった。
[Example 1]
Charge 590 g of ion-exchange water, 353 g of CHFCClCF 2 CF 2 Cl, 54.8 g of PTFVE, and 16.4 g of methanol into a 1.2 liter pressure vessel equipped with a stirrer, and pressurize TFE at an internal temperature of 50 ° C. Was charged to 1.21 MPa. Subsequently, 3 mL of a 0.1% solution of (CF 3 CF 2 CF 2 COO) 2 (solvent: CHFCClCF 2 CF 2 Cl) (hereinafter referred to as initiator solution) was charged, and polymerization was started at 50 ° C. During the polymerization, the initiator solution was charged intermittently, and a total of 20.2 mL was charged. As the polymerization progressed, the pressure decreased, so TFE was continuously charged to keep the pressure constant. When the amount of TFE added later became 145 g, the internal temperature was cooled to room temperature, unreacted TFE was discharged, and the pressure vessel was opened. The contents of the pressure vessel were filtered through a glass filter to obtain a slurry-like TFE copolymer. The obtained slurry was dried at 120 ° C. for 8 hours to obtain 155 g of a white TFE copolymer. The obtained TFE copolymer had a molar ratio of polymerized units based on TFE / polymerized units based on PTFVE of 98.3 / 1.7 and a Q value of 1.7 mm 3 / sec. The tensile strength was 32.6 MPa, the tensile elongation was 310%, the yield strength was 14.0 MPa, the tensile modulus was 154 MPa, and the MIT bending life was 1,230,000 times.
［実施例２］
実施例１の圧力容器に、イオン交換水の５９０ｇ、ＣＨＦＣｌＣＦ２ＣＦ２Ｃｌの３５３ｇ、ＰＴＦＶＥの１１．０ｇ、ＰＰＶＥの３３．９ｇ、メタノールの１７．６ｇを仕込み、５０℃の内温で、ＴＦＥを圧力が１．２１ＭＰａになるまで仕込んだ。ついで、実施例１で用いたと同じ開始剤溶液の３ｍＬを仕込み、５０℃で重合を開始させた。重合中に開始剤溶液は断続的に仕込み、合計１６．７ｍＬを仕込んだ。重合の進行にともない、圧力が低下するので、圧力が一定になるようにＴＦＥを連続的に後仕込みした。後仕込みのＴＦＥ量が１４５ｇになったところで内温を室温まで冷却し、未反応ＴＦＥを空放し、圧力容器を開放した。圧力容器の内容物をガラスフィルターで濾過してスラリー状のＴＦＥ共重合体を得た。得られたスラリーを１２０℃で８時間乾燥して白色のＴＦＥ共重合体の１５３ｇを得た。得られたＴＦＥ共重合体の組成は、ＴＦＥに基づく重合単位／ＰＴＦＶＥに基づく重合単位／ＰＰＶＥに基づく重合単位はモル比で９８．４／０．４／１．２であり、Ｑ値は２．２ｍｍ３／秒であった。引張強度は３６．９ＭＰａ、引張伸度は３６０％、降伏強度は１３．６ＭＰａ、引張弾性率は１４６ＭＰａ、ＭＩＴ折り曲げ寿命は８８万回であった。
[Example 2]
The pressure vessel of Example 1 was charged with 590 g of ion-exchanged water, 353 g of CHFCClCF 2 CF 2 Cl, 11.0 g of PTFVE, 33.9 g of PPVE, and 17.6 g of methanol, and at an internal temperature of 50 ° C., TFE Was charged until the pressure reached 1.21 MPa. Next, 3 mL of the same initiator solution used in Example 1 was charged, and polymerization was started at 50 ° C. During the polymerization, the initiator solution was charged intermittently for a total of 16.7 mL. As the polymerization progressed, the pressure decreased, so TFE was continuously charged to keep the pressure constant. When the amount of TFE added later became 145 g, the internal temperature was cooled to room temperature, unreacted TFE was discharged, and the pressure vessel was opened. The contents of the pressure vessel were filtered through a glass filter to obtain a slurry-like TFE copolymer. The obtained slurry was dried at 120 ° C. for 8 hours to obtain 153 g of a white TFE copolymer. The composition of the obtained TFE copolymer was such that the polymer unit based on TFE / polymer unit based on PTFVE / polymer unit based on PPVE had a molar ratio of 98.4 / 0.4 / 1.2, and the Q value was 2 It was 2 mm 3 / sec. The tensile strength was 36.9 MPa, the tensile elongation was 360%, the yield strength was 13.6 MPa, the tensile modulus was 146 MPa, and the MIT bending life was 880,000 times.
［比較例１］
ＰＴＦＶＥの替わりにＰＰＶＥの４２．４ｇ、メタノールの１８．９ｇ、開始剤溶液の合計１２．９ｍｌ仕込んだ以外は実施例１と同様にして、ＴＦＥ共重合体の１５０ｇを得た。得られたＴＦＥ共重合体の組成は、ＴＦＥに基づく重合単位／ＰＰＶＥに基づく重合単位がモル比で９８．５／１．５であり、Ｑ値は２．３であった。引張強度は３３．１ＭＰａ、引張伸度は３４０％、降伏強度は１３．３ＭＰａ、引張弾性率は１４１ＭＰａ、ＭＩＴ折り曲げ寿命は７８万回であった。
[Comparative Example 1]
150 g of TFE copolymer was obtained in the same manner as in Example 1 except that 42.4 g of PPVE, 18.9 g of methanol, and a total of 12.9 ml of the initiator solution were charged instead of PTFVE. As for the composition of the obtained TFE copolymer, the polymer unit based on TFE / polymer unit based on PPVE was 98.5 / 1.5 in a molar ratio, and the Q value was 2.3. The tensile strength was 33.1 MPa, the tensile elongation was 340%, the yield strength was 13.3 MPa, the tensile modulus was 141 MPa, and the MIT bending life was 780,000 times.
［実施例３］
ＰＴＦＶＥの替わりに式（２）で表されるモノマーの７０．７ｇ仕込む以外は実施例１と同様にして、ＴＦＥ共重合体の１５７ｇを得る。得られるＴＦＥ共重合体の組成は、ＴＦＥに基づく重合単位／式（２）で表されるモノマーに基づく重合単位がモル比で９８．３／１．７であり、Ｑ値は２．０ｍｍ３／秒である。引張強度は３３．０ＭＰａ、引張伸度は３２０％、降伏強度は１３．９ＭＰａ、引張弾性率は１５５ＭＰａ、ＭＩＴ折り曲げ寿命は１１５万回である。
[Example 3]
157 g of a TFE copolymer is obtained in the same manner as in Example 1 except that 70.7 g of the monomer represented by the formula (2) is charged instead of PTFVE. The composition of the obtained TFE copolymer is such that the polymer unit based on the TFE-based polymer unit / the monomer represented by the formula (2) has a molar ratio of 98.3 / 1.7, and the Q value is 2.0 mm 3. / Sec. The tensile strength is 33.0 MPa, the tensile elongation is 320%, the yield strength is 13.9 MPa, the tensile elastic modulus is 155 MPa, and the MIT bending life is 1.15 million times.
［実施例４］
ＰＴＦＶＥの替わりに式（３）で表されるモノマーの７０．７ｇ仕込む以外は実施例１と同様にして、ＴＦＥ共重合体の１５６ｇを得る。得られるＴＦＥ共重合体の組成は、ＴＦＥに基づく重合単位／式（３）で表されるモノマーに基づく重合単位がモル比で９８．４／１．６であり、Ｑ値は２．３ｍｍ３／秒である。引張強度は３３．５ＭＰａ、引張伸度は３００％、降伏強度は１４．０ＭＰａ、引張弾性率は１５２ＭＰａ、ＭＩＴ折り曲げ寿命は１０８万回である。
[Example 4]
156 g of TFE copolymer is obtained in the same manner as in Example 1 except that 70.7 g of the monomer represented by the formula (3) is charged instead of PTFVE. The composition of the obtained TFE copolymer is such that the polymer unit based on TFE / the polymer unit based on the monomer represented by formula (3) is 98.4 / 1.6 in terms of molar ratio, and the Q value is 2.3 mm 3. / Sec. The tensile strength is 33.5 MPa, the tensile elongation is 300%, the yield strength is 14.0 MPa, the tensile elastic modulus is 152 MPa, and the MIT bending life is 1.08 million times.
本発明のテトラフルオロエチレン共重合体は、化学産業や半導体産業における種々の部材用の成形材料として有用である。
The tetrafluoroethylene copolymer of the present invention is useful as a molding material for various members in the chemical industry and the semiconductor industry.
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| WO2004056887A1 (en) * | 2002-12-19 | 2004-07-08 | Asahi Glass Company, Limited | Tetrafluoroethylene copolymer |
| JP4834966B2 (en) * | 2004-07-02 | 2011-12-14 | 旭硝子株式会社 | Tetrafluoroethylene copolymer |
| EP2128150A1 (en) * | 2006-12-20 | 2009-12-02 | Asahi Glass Company, Limited | Fluorine-containing compound and fluorine-containing polymer |
| TW200912963A (en) * | 2007-08-08 | 2009-03-16 | Daikin Ind Ltd | Covered electric wire and coaxial cable |
| JP5445699B2 (en) * | 2012-02-01 | 2014-03-19 | ダイキン工業株式会社 | Sealing material |
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2003
- 2003-12-18 JP JP2003421190A patent/JP4415665B2/en not_active Expired - Fee Related
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