JP3580341B2 - Organic fluorine compounds - Google Patents

Description

【０００８】
【化４】

〔但し、Ｒ^１は同一又は異種の非置換又はハロゲン原子置換一価炭化水素基、Ｒ^２は水素原子又は非置換又はハロゲン原子置換一価炭化水素基、Ｘは下記一般式（２）

（Ｒ^３，Ｒ^４は各々同一又は異種の非置換又はハロゲン原子置換一価炭化水素基、ｐは２〜４の整数である。）
で示される基、Ｒｆは二価パーフルオロアルキレン基又は二価パーフルオロポリエーテル基である。〕
【０００９】
以下、本発明につき更に詳述すると、本発明の有機フッ素化合物は、下記一般式（１）で示される両末端に環状シロキサン基を有する有機フッ素アミド化合物である。
【００１０】
【化５】

〔但し、Ｒ^１は同一又は異種の非置換又はハロゲン原子置換一価炭化水素基、Ｒ^２は水素原子又は非置換又はハロゲン原子置換一価炭化水素基、Ｘは下記一般式（２）

（Ｒ^３，Ｒ^４は各々同一又は異種の非置換又はハロゲン原子置換一価炭化水素基、ｐは２〜４の整数である。）
で示される基、Ｒｆは二価パーフルオロアルキレン基又は二価パーフルオロポリエーテル基である。〕
【００１１】
上記式（１）中、Ｒ^１は同一又は異種の非置換又はハロゲン原子置換一価炭化水素基で、好ましくは炭素数１〜１０、特に１〜８のものであり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、デシル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、ビニル基、アリル基、プロペニル基、ブテニル基、ヘキセニル基、シクロヘキセニル基などのアルケニル基、フェニル基、トリル基、キシリル基、ナフチル基などのアリール基、ベンジル基、フェニルエチル基等のアラルキル基、或いはこれらの基の水素原子が部分的に塩素、臭素、フッ素等のハロゲン原子で置換された基が例示される。
【００１２】
Ｒ^２は水素原子又は一価炭化水素基であり、一価炭化水素基としては、好ましくは炭素数１〜１０、特に１〜８のもので、Ｒ^１と同様の基が例示される。
【００１３】
また、Ｘは上記式（２）で示される基で、置換基Ｒ^３，Ｒ^４は各々同一又は異種の非置換又はハロゲン原子置換一価炭化水素基であり、好ましくは炭素数１〜１０、特に１〜８のもので、Ｒ^１と同様の基が例示される。ｐは２〜４の整数である。
【００１４】
上記二価パーフルオロアルキレン基又は二価パーフルオロポリエーテル基としては、下記のものを例示することができる。なお、下記式でメチル基はＭｅ、フェニル基はＰｈと略記する。
【００１５】
【化６】

【００１６】
本発明の有機フッ素化合物は、例えば下記一般式（１ａ）で示される両末端にビニル基を有する含フッ素化合物と、下記一般式（２ａ）で示される環状ヒドロシロキサンとを白金化合物等の触媒存在下で反応させることにより合成することができる。
【００１７】
【化７】

（但し、Ｒ^１〜Ｒ^４，Ｒｆ，ｐはそれぞれ上記と同様の意味を示す。）
【００１８】
上記反応において、上記式（１ａ）の含フッ素化合物と上記式（２ａ）の環状ヒドロシロキサンとの混合割合は、モル比で１：２〜１：３、特に１：２〜１：２．５の範囲が好ましい。触媒としては、周期表第ＶＩＩＩ族元素又はその化合物が好ましく、例えば塩化白金酸、アルコール変性塩化白金酸（米国特許第３２２０９７２号参照）、塩化白金酸とオレフィンとのコンプレックス（米国特許第３１５９６０１号、同第３１５９６６２号、同第３７７５４５２号参照）、白金黒又はパラジウムなどをアルミナ、シリカ、カーボンなどの担体に担持させたもの、ロジウム−オレフィンコンプレックス、クロロトリス（トリフェニルホスフィン）ロジウム（ウィルキンソン触媒）などが挙げられる。なお、これらのコンプレックスはアルコール系、ケトン系、エーテル系、炭化水素系の溶剤に溶解して用いることが望ましい。なお、触媒の添加量は、触媒量である。
【００１９】
反応条件は適宜調整できるが、５０〜１５０℃、特に８０〜１２０℃で１〜６時間、特に２〜４時間行うことが好適である。
【００２０】
反応終了後は、活性炭で濾過処理し、揮発成分を減圧留去するなどして、目的の式（１）の有機フッ素化合物を得ることができる。
【００２１】
本発明の有機フッ素化合物（含フッ素アミド化合物）は、種々の用途に利用することができる。即ち、本発明の上記式（１）で示される両末端に環状シロキサン基を有するポリマーは、テトラブチルホスホニウムヒドロキサイドのようなシロキサン結合をクラッキングする触媒の存在下にて反応させることによりエラストマーを得ることができる。このエラストマーはフッ素含有率が高いため耐溶剤性、耐薬品性に優れ、また、低表面エネルギーを有するため離型性、撥水性に優れており、シーラント、成形部品、押出部品、被覆材料、離型剤などに有用である。
【００２２】
【発明の効果】
本発明の有機フッ素化合物は、フッ素含有率が高く、耐溶剤性、耐薬品性、離型剤、撥水性に優れたエラストマーを与えるもので、シーラント、成形部品、押出部品、被覆材料、離型剤用素材の原料として幅広く利用することができる。
【００２３】
【実施例】
以下、実施例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００２４】
〔実施例１〕
撹拌棒、温度計、ジムロート、滴下ロートを付した３００ｍｌ四つ口セパラフラスコに下記式（ａ）で示される両末端にシリルビニル基を有する化合物１００．０ｇ、メタキシレンヘキサフロライド１０．０ｇと塩化白金酸をＣＨ_２＝ＣＨＳｉＭｅ_２ＯＳｉＭｅ_２ＣＨ＝ＣＨ_２で変性した触媒０．１ｇを仕込み、撹拌しながら、滴下ロートより下記式（ｂ）の環状ヒドロシロキサン３．１０ｇを１００℃で滴下した。滴下後、１００℃で２時間反応させ、活性炭で処理し、濾過した後、揮発成分を減圧留去することにより、透明な液体９８．９ｇが得られた。この液体は粘度８２５０ｃｓ（２５℃）、比重１．８４４８（２５℃）、屈折率１．３１６２（２５℃）であった。このもののＩＲ（図１参照）、^１Ｈ−ＮＭＲを測定したところ、以下の吸収が認められ、下記構造式の化合物（ｃ）が得られたことを確認した。
【００２５】
【化８】

【００２６】
【化９】

【００２７】
〔実施例２〕
撹拌棒、温度計、ジムロート、滴下ロートを付した３００ｍｌ四つ口セパラフラスコに上記式（ａ）で示される両末端にシリルビニル基を有する化合物１００．０ｇ、メタキシレンヘキサフロライド１０．０ｇと塩化白金酸をＣＨ_２＝ＣＨＳｉＭｅ_２ＯＳｉＭｅ_２ＣＨ＝ＣＨ_２で変性した触媒０．１ｇを仕込み、撹拌しながら、滴下ロートより下記式（ｂ’）の環状ヒドロシロキサン４．２０ｇを１００℃で滴下した。滴下後、１００℃で２時間反応させ、活性炭で処理し、濾過した後、揮発成分を減圧留去することにより、透明な液体９８．９ｇが得られた。この液体は粘度１０５００ｃｓ（２５℃）、比重１．８２１７（２５℃）、屈折率１．３１８６（２５℃）であった。このもののＩＲ（図２参照）、^１Ｈ−ＮＭＲを測定したところ、以下の吸収が認められ、下記構造式の化合物（ｄ）が得られたことを確認した。
【化１１】

【００２８】
【化１０】

【図面の簡単な説明】
【図１】実施例１で得られた式（ｃ）の有機フッ素化合物のＩＲスペクトルを示すグラフである。
【図２】実施例２で得られた式（ｄ）の有機フッ素化合物のＩＲスペクトルを示すグラフである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel organic fluorine compound that is useful as a raw material for a material for a heat-resistant, solvent-resistant, and chemical-resistant rubber material and a material for a release agent.
[0002]
Problems to be solved by the prior art and the invention
Conventionally, an organic fluorine compound has been used in various fields, for example, an elastomer is obtained by crosslinking a polymer of an organic fluorine compound using a crosslinking agent, and this is used as a rubber material and a release agent.
[0003]
However, elastomers obtained from conventional organic fluorine compounds may not have sufficient solvent resistance and chemical resistance in some cases, and elastomers having more excellent solvent resistance and chemical resistance are desired.
[0004]
Further, it is more desirable that the elastomer used as a sealant, a molded part or the like has further excellent releasability and water repellency.
[0005]
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel organic fluorine compound which provides an elastomer having excellent solvent resistance and chemical resistance, and excellent mold release properties and water repellency.
[0006]
Means for Solving the Problems and Embodiments of the Invention
The present inventors have conducted intensive studies on organic fluorine compounds in order to achieve the above object, and as a result, a fluorine-containing compound having a vinyl group at both terminals represented by the following general formula (1a) and the following general formula (2a) Is reacted in the presence of a catalyst to obtain a novel organic fluorine compound (fluorine-containing amide compound) represented by the following general formula (1). By reacting in the presence of a cracking catalyst, an elastomer with a high fluorine content and excellent solvent resistance, chemical resistance, release properties, and water repellency is provided, and sealants, molded parts, extruded parts, coating materials, The present inventors have found that they are useful as raw materials of a material for a release agent, and have accomplished the present invention.
[0007]
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[0008]
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Wherein R ¹ is the same or different unsubstituted or halogen-substituted monovalent hydrocarbon group, R ² is a hydrogen atom or unsubstituted or halogen-substituted monovalent hydrocarbon group, and X is the following general formula (2)

(R ³ and R ⁴ are the same or different unsubstituted or halogen atom-substituted monovalent hydrocarbon groups, and p is an integer of 2 to 4.)
And Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group. ]
[0009]
Hereinafter, the present invention will be described in more detail. The organic fluorine compound of the present invention is an organic fluorine amide compound having a cyclic siloxane group at both terminals represented by the following general formula (1).
[0010]
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Wherein R ¹ is the same or different unsubstituted or halogen-substituted monovalent hydrocarbon group, R ² is a hydrogen atom or unsubstituted or halogen-substituted monovalent hydrocarbon group, and X is the following general formula (2)

(R ³ and R ⁴ are the same or different unsubstituted or halogen atom-substituted monovalent hydrocarbon groups, and p is an integer of 2 to 4.)
And Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group. ]
[0011]
In the above formula (1), R ¹ is the same or different unsubstituted or halogen-substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, especially 1 to 8 carbon atoms, such as methyl group, ethyl group Alkyl groups such as propyl, butyl, pentyl, hexyl and decyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl, allyl, propenyl, butenyl, hexenyl and cyclohexenyl groups , An aryl group such as phenyl group, tolyl group, xylyl group, and naphthyl group, an aralkyl group such as benzyl group and phenylethyl group, or a hydrogen atom of these groups is partially replaced by a halogen atom such as chlorine, bromine or fluorine The following groups are exemplified.
[0012]
R ² is a hydrogen atom or a monovalent hydrocarbon group, and the monovalent hydrocarbon group preferably has 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and examples thereof are the same as those of R ¹ .
[0013]
X is a group represented by the above formula (2), and the substituents R ³ and R ⁴ are the same or different unsubstituted or halogen-substituted monovalent hydrocarbon groups, preferably having 1 to 10 carbon atoms; in particular those of 1 to 8, the same groups as ^{R 1} are exemplified. p is an integer of 2 to 4.
[0014]
Examples of the divalent perfluoroalkylene group or the divalent perfluoropolyether group include the following. In the following formula, a methyl group is abbreviated as Me, and a phenyl group is abbreviated as Ph.
[0015]
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[0016]
The organic fluorine compound of the present invention comprises, for example, a fluorine-containing compound having a vinyl group at both terminals represented by the following general formula (1a) and a cyclic hydrosiloxane represented by the following general formula (2a) in the presence of a catalyst such as a platinum compound. It can be synthesized by reacting under the following conditions.
[0017]
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(However, R ^{1 to} R ⁴ , Rf, and p each have the same meaning as described above.)
[0018]
In the above reaction, the mixing ratio of the fluorine-containing compound of the above formula (1a) and the cyclic hydrosiloxane of the above formula (2a) is 1: 2-1: 3, particularly 1: 2-1: 2.5, in molar ratio. Is preferable. The catalyst is preferably a Group VIII element of the periodic table or a compound thereof, for example, chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,209,722), a complex of chloroplatinic acid and an olefin (US Pat. No. 3,159,601, Nos. 3159662 and 3775452), platinum black or palladium supported on a carrier such as alumina, silica or carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), and the like. No. It is desirable that these complexes be used by dissolving them in an alcohol, ketone, ether, or hydrocarbon solvent. The amount of catalyst added is the amount of catalyst.
[0019]
The reaction conditions can be appropriately adjusted, but it is preferable to carry out the reaction at 50 to 150 ° C, particularly 80 to 120 ° C, for 1 to 6 hours, particularly 2 to 4 hours.
[0020]
After the completion of the reaction, the desired organic fluorine compound of the formula (1) can be obtained by filtration with activated carbon and distilling off volatile components under reduced pressure.
[0021]
The organic fluorine compound (fluorine-containing amide compound) of the present invention can be used for various uses. That is, the polymer of the present invention having a cyclic siloxane group at both terminals represented by the above formula (1) is reacted in the presence of a catalyst for cracking a siloxane bond such as tetrabutylphosphonium hydroxide to obtain an elastomer. be able to. This elastomer has a high fluorine content and therefore has excellent solvent resistance and chemical resistance, and has a low surface energy, so it has excellent release properties and water repellency. Useful for molds and the like.
[0022]
【The invention's effect】
The organic fluorine compound of the present invention has a high fluorine content and gives an elastomer having excellent solvent resistance, chemical resistance, release agent, and water repellency. Sealant, molded part, extruded part, coating material, mold release It can be widely used as a raw material for drug materials.
[0023]
【Example】
EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.
[0024]
[Example 1]
A 300 ml four-necked separa flask equipped with a stirring rod, a thermometer, a Dim funnel, and a dropping funnel was charged with 100.0 g of a compound having a silylvinyl group at both ends represented by the following formula (a), 10.0 g of metaxylene hexafluoride, and chloride 0.1 g of a catalyst obtained by modifying platinic acid with CH ₂ ＣＨCHSiMe ₂ OSiMe ₂ CH ＝ CH ₂ was charged, and 3.10 g of a cyclic hydrosiloxane of the following formula (b) was added dropwise at 100 ° C. from a dropping funnel with stirring. After the dropwise addition, the mixture was reacted at 100 ° C. for 2 hours, treated with activated carbon, filtered, and the volatile components were distilled off under reduced pressure to obtain 98.9 g of a transparent liquid. This liquid had a viscosity of 8250 cs (25 ° C.), a specific gravity of 1.8448 (25 ° C.), and a refractive index of 1.3162 (25 ° C.). The IR (see FIG. 1) and ¹ H-NMR of this product were measured. As a result, the following absorption was recognized, and it was confirmed that the compound (c) having the following structural formula was obtained.
[0025]
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[0026]
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[0027]
[Example 2]
In a 300 ml four-necked separa flask equipped with a stirring rod, a thermometer, a Dim funnel, and a dropping funnel, 100.0 g of a compound having a silylvinyl group at both ends represented by the above formula (a), 10.0 g of meta-xylene hexafluoride and chloride were added. 0.1 g of a catalyst obtained by modifying platinic acid with CH ₂ ＣＨCHSiMe ₂ OSiMe ₂ CH ＝ CH ₂ was charged, and while stirring, 4.20 g of a cyclic hydrosiloxane of the following formula (b ′) was dropped at 100 ° C. from a dropping funnel. . After the dropwise addition, the mixture was reacted at 100 ° C. for 2 hours, treated with activated carbon, filtered, and the volatile components were distilled off under reduced pressure to obtain 98.9 g of a transparent liquid. This liquid had a viscosity of 10500 cs (25 ° C.), a specific gravity of 1.8217 (25 ° C.), and a refractive index of 1.3186 (25 ° C.). When IR (see FIG. 2) and ¹ H-NMR of this product were measured, the following absorptions were recognized, and it was confirmed that the compound (d) having the following structural formula was obtained.
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[0028]
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[Brief description of the drawings]
FIG. 1 is a graph showing an IR spectrum of the organic fluorine compound of the formula (c) obtained in Example 1.
FIG. 2 is a graph showing an IR spectrum of the organofluorine compound of the formula (d) obtained in Example 2.

Claims (1)

An organic fluorine compound represented by the following general formula (1).

Wherein R ¹ is the same or different unsubstituted or halogen-substituted monovalent hydrocarbon group, R ² is a hydrogen atom or unsubstituted or halogen-substituted monovalent hydrocarbon group, and X is the following general formula (2)

(R ³ and R ⁴ are the same or different unsubstituted or halogen atom-substituted monovalent hydrocarbon groups, and p is an integer of 2 to 4.)
And Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group. ]

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