JPH0867660A - Organic fluorine compound - Google Patents
Organic fluorine compoundInfo
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- JPH0867660A JPH0867660A JP6295789A JP29578994A JPH0867660A JP H0867660 A JPH0867660 A JP H0867660A JP 6295789 A JP6295789 A JP 6295789A JP 29578994 A JP29578994 A JP 29578994A JP H0867660 A JPH0867660 A JP H0867660A
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- organic fluorine
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐溶剤性、耐薬品性を
有するゴム材料用素材及び離型剤用素材等の原料として
有効に利用することができる新規な有機フッ素化合物に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic fluorine compound which can be effectively used as a raw material for a rubber material and a release agent material having solvent resistance and chemical resistance.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、有機フッ素化合物は、各種分野で使用されており、
例えば有機フッ素化合物のポリマーを架橋剤を用いて架
橋することによりエラストマーを得、これをゴム材料及
び離型剤として利用している。2. Description of the Related Art Conventionally, organic fluorine compounds have been used in various fields,
For example, an elastomer is obtained by crosslinking a polymer of an organic fluorine compound with a crosslinking agent, and this is used as a rubber material and a release agent.
【０００３】しかし、従来の有機フッ素化合物より得ら
れるエラストマーでは、その耐溶剤性、耐薬品性が十分
でない場合があり、より耐溶剤性、耐薬品性に優れるエ
ラストマーが望まれる。However, the elastomer obtained from the conventional organic fluorine compound may not have sufficient solvent resistance and chemical resistance, and an elastomer having more excellent solvent resistance and chemical resistance is desired.
【０００４】また、シーラント、成形部品等として使用
されるエラストマーは、更に離型性、撥水性に優れるも
のがより望ましい。Further, it is more desirable that the elastomer used as a sealant, a molded part or the like has excellent releasability and water repellency.
【０００５】本発明は上記事情に鑑みなされたもので、
耐溶剤性、耐薬品性に優れ、また、離型性、撥水性に優
れたエラストマーを与える新規有機フッ素化合物を提供
することを目的とする。The present invention has been made in view of the above circumstances.
It is an object of the present invention to provide a novel organic fluorine compound which is excellent in solvent resistance and chemical resistance, and also provides an elastomer excellent in mold releasability and water repellency.
【０００６】[0006]
【課題を解決するための手段及び作用】本発明者は上記
目的を達成するため鋭意検討を重ねた結果、例えば下記
一般式（４）で示される両末端に酸フロライド基を有す
る化合物と下記一般式（５）で示される二級アミン化合
物、更に必要に応じて下記一般式（６）で示される化合
物とを受酸剤の存在下で反応させることにより、下記一
般式（１）で示される新規な有機フッ素化合物が得られ
ること、更に、この有機フッ素化合物が、フッ素含有率
が高く、表面エネルギーが低いエラストマーとなり得る
ことを知見し、本発明をなすに至った。Means and Actions for Solving the Problems As a result of intensive studies for achieving the above object, the present inventor has found that, for example, a compound having an acid fluoride group at both terminals and represented by the following general formula (4) and the following general formula By reacting the secondary amine compound represented by the formula (5) and optionally the compound represented by the following general formula (6) in the presence of an acid acceptor, the compound represented by the following general formula (1) is obtained. The present invention has been accomplished by finding that a novel organic fluorine compound can be obtained, and further that this organic fluorine compound can be an elastomer having a high fluorine content and a low surface energy.
【０００７】[0007]
【化４】 従って、本発明は、上記式（１）で示される有機フッ素
化合物を提供する。[Chemical 4] Therefore, the present invention provides an organic fluorine compound represented by the above formula (1).
【０００８】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
ものである。The present invention will be described in more detail below. The organic fluorine compound of the present invention is represented by the following general formula (1).
【０００９】[0009]
【化５】 [Chemical 5]
【００１０】ここで、上記式（１）中のＲ1及びＲ2とし
ては、炭素数１〜１０、特に１〜８の置換又は非置換の
一価炭化水素基が好適であり、例えばメチル基、エチル
基、プロピル基、イソプロピル基、ブチル基、イソブチ
ル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル
基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、
デシル基等のアルキル基、シクロペンチル基、シクロヘ
キシル基、シクロヘプチル基等のシクロアルキル基、ビ
ニル基、アリル基、プロペニル基、イソプロペニル基、
ブテニル基、イソブテニル基、ヘキセニル基、シクロヘ
キセニル基等のアルケニル基、フェニル基、トリル基、
キシリル基、ナフチル基等のアリール基、ベンジル基、
フェニルエチル基、フェニルプロピル基等のアラルキル
基あるいはこれらの基の水素原子の一部又は全部をフッ
素、塩素、臭素等のハロゲン原子等で置換したクロロメ
チル基、ブロモエチル基、クロロプロピル基、トリフル
オロプロピル基などが挙げられる。この場合、Ｒ1は特
に炭素数２〜８のアルケニル基であることが好ましい。Here, as R 1 and R 2 in the above formula (1), a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms is preferable, for example, a methyl group. , Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Alkyl group such as decyl group, cyclopentyl group, cyclohexyl group, cycloalkyl group such as cycloheptyl group, vinyl group, allyl group, propenyl group, isopropenyl group,
Alkenyl groups such as butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group, phenyl group, tolyl group,
Aryl group such as xylyl group and naphthyl group, benzyl group,
Aralkyl groups such as phenylethyl group and phenylpropyl group, or chloromethyl group, bromoethyl group, chloropropyl group, trifluoro group in which some or all of hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine and bromine. Examples thereof include a propyl group. In this case, R 1 is particularly preferably an alkenyl group having 2 to 8 carbon atoms.
【００１１】また、上記式（１）においてＱは下記一般
式（２）又は一般式（３）で示される基である。In the above formula (1), Q is a group represented by the following general formula (2) or general formula (3).
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】上記式（２）中のＲ1は前記と同様であ
り、Ｒ3としては、置換又は非置換の二価炭化水素基で
あれば特に限定されないが、炭素数１〜２０、特に２〜
１０の炭化水素基が好適であり、具体的にはメチレン
基、エチレン基、プロピレン基、メチルエチレン基、ブ
チレン基、ヘキサメチレン基等のアルキレン基、シクロ
ヘキシレン基等のシクロアルキレン基、フェニレン基、
トリレン基、キシリレン基、ナフチレン基、ビフェニレ
ン基等のアリーレン基、あるいはこれらの基の水素原子
の一部又は全部をハロゲン原子等で置換した基、あるい
はこれらの置換又は非置換のアルキレン基、アリーレン
基の組み合わせなどが例示される。R 1 in the above formula (2) is the same as described above, and R 3 is not particularly limited as long as it is a substituted or unsubstituted divalent hydrocarbon group, but has 1 to 20 carbon atoms, especially 2 carbon atoms. ~
Hydrocarbon groups of 10 are preferable, specifically, methylene group, ethylene group, propylene group, methylethylene group, butylene group, alkylene group such as hexamethylene group, cycloalkylene group such as cyclohexylene group, phenylene group,
An arylene group such as a tolylene group, a xylylene group, a naphthylene group, and a biphenylene group, or a group in which a part or all of hydrogen atoms of these groups are substituted with a halogen atom, or a substituted or unsubstituted alkylene group or arylene group thereof. And the like are exemplified.
【００１４】また、Ｒ3は結合の途中に酸素原子、窒素
原子、ケイ素原子の１種又は２種以上を介在させても良
い。Further, R 3 may have one or more kinds of oxygen atom, nitrogen atom and silicon atom interposed in the middle of the bond.
【００１５】この場合、酸素原子は−Ｏ−、窒素原子は
−ＮＲ’−（Ｒ’は水素原子又は炭素数１〜８、特に１
〜６のアルキル基又はアリール基である）として介在す
ることができ、またケイ素原子は、例えば下記の基のよ
うに直鎖状又は環状のオルガノシロキサンを含有する基
あるいはオルガノシリレン基として介在することができ
る。In this case, the oxygen atom is -O-, the nitrogen atom is -NR '-(R' is a hydrogen atom or 1 to 8 carbon atoms, and particularly 1
Is an alkyl group or an aryl group of 6), and the silicon atom is present as a group containing a linear or cyclic organosiloxane or an organosilylene group such as the following groups. You can
【００１６】[0016]
【化７】 （但し、Ｒ”は前記Ｒ1，Ｒ2として例示したものと同様
の炭素数１〜８のアルキル基又はアリール基、Ｒ'''は
前記Ｒ3として例示したものと同様の炭素数１〜６のア
ルキレン基又はアリーレン基であり、ｎ＝０〜１０、特
に０〜５の整数である。） このような基としては、下記の基を例示することができ
る。[Chemical 7] (However, R ″ is an alkyl group or aryl group having 1 to 8 carbon atoms similar to those exemplified as R 1 and R 2 , and R ′ ″ is 1 to 8 carbon atoms similar to those exemplified as R 3 . 6 is an alkylene group or an arylene group, and n = 0 to 10, especially an integer of 0 to 5.) As such a group, the following groups can be exemplified.
【００１７】[0017]
【化８】 （Ｍｅはメチル基を示す。）Embedded image (Me represents a methyl group.)
【００１８】更に、上記式（３）中のＲ4及びＲ5として
は、炭素数１〜１０、特に２〜６の置換又は非置換の二
価炭化水素基が好適であり、具体的にはメチレン基、エ
チレン基、プロピレン基、メチルエチレン基、ブチレン
基、ヘキサメチレン基等のアルキレン基、シクロヘキシ
レン基等のシクロアルキレン基、あるいはこれらの基の
水素原子の一部又は全部をハロゲン原子等で置換した基
などが例示される。Further, as R 4 and R 5 in the above formula (3), a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms is preferable, and specifically, Methylene group, ethylene group, propylene group, methylethylene group, butylene group, alkylene group such as hexamethylene group, cycloalkylene group such as cyclohexylene group, or part or all of the hydrogen atoms of these groups are halogen atoms or the like. Examples include substituted groups.
【００１９】上記式（２）又は式（３）により示される
式（１）中のＱ として具体的には下記の基が例示され
る。なお、以下の化学式において、Ｍｅはメチル基、Ｐ
ｈはフェニル基を示す。It is represented by the above equation (2) or equation (3).
Q in formula (1) The following groups are specifically exemplified as
It In the chemical formulas below, Me is a methyl group, P
h represents a phenyl group.
【００２０】[0020]
【化９】 [Chemical 9]
【００２１】また、式（１）において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
基であり、特に二価パーフルオロアルキレン基としては −ＣmＦ2m− （但し、ｍ＝１〜１０、好ましくは１〜６である。）で
示されるものが好ましく、二価パーフルオロポリエーテ
ル基としては下記式で示されるものが好ましい。In the equation (1), Rf Is a bivalent perf
Luoroalkylene group or divalent perfluoropolyether
Group, and particularly as a divalent perfluoroalkylene group, -CmF2m-(Provided that m = 1 to 10, preferably 1 to 6).
Those shown are preferred, and divalent perfluoropolyethers
As the radical group, those represented by the following formula are preferable.
【００２２】[0022]
【化１０】 Ｒｆ として具体的には、下記のものが例示される。[Chemical 10]Rf Specifically, the following are exemplified.
【００２３】[0023]
【化１１】 [Chemical 11]
【００２４】なお、上記式（１）においてａは０以上の
整数であり、従って、式（１）の有機フッ素化合物は１
分子中に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を１個以上含むものであるが、ａ
は好ましくは０〜１０の整数であり、特に０，１，２，
３，４，５，６が例示される。In the above formula (1), a is an integer of 0 or more, and therefore the organic fluorine compound of the formula (1) is 1
The molecule contains at least one divalent perfluoroalkylene group or divalent perfluoropolyether group.
Is preferably an integer of 0 to 10, and particularly 0, 1, 2,
3, 4, 5 and 6 are exemplified.
【００２５】本発明において、上記有機フッ素化合物
は、粘度（２５℃、以下同様）が数十ｃｓの低粘度ポリ
マーから固形の生ゴム状のポリマーまでを包含するが、
取り扱いやすさの点からは、例えば熱加硫ゴム用として
は生ゴム状のポリマーが、また、液状ゴム用には粘度が
１００〜１０００００ｃｓ程度のポリマーが好適に使用
される。低粘度すぎると得られる硬化物がエラストマー
としての伸びが小さくなり、バランスのとれた物性が得
られない場合が生じる。In the present invention, the above-mentioned organic fluorine compound includes a low viscosity polymer having a viscosity (25 ° C., the same applies hereinafter) of several tens of cs to a solid raw rubber-like polymer.
From the viewpoint of ease of handling, for example, a raw rubber-like polymer is preferably used for a heat-vulcanized rubber, and a polymer having a viscosity of about 100 to 100,000 cs is preferably used for a liquid rubber. If the viscosity is too low, the resulting cured product will have a small elongation as an elastomer, and it may not be possible to obtain balanced physical properties.
【００２６】上記式（１）の有機フッ素化合物は、下記
の方法により得ることができる。即ち、上記式（１）に
おいてａが０である有機フッ素化合物は、例えば下記一
般式（４）で示される両末端に酸フロライド基を有する
化合物と下記一般式（５）で示される二級アミン化合物
とをトリメチルアミン等の受酸剤の存在下で反応させる
ことにより合成することができる。The organic fluorine compound of the above formula (1) can be obtained by the following method. That is, the organic fluorine compound in which a is 0 in the formula (1) is, for example, a compound represented by the following general formula (4) having an acid fluoride group at both ends and a secondary amine represented by the following general formula (5). It can be synthesized by reacting a compound with an acid acceptor such as trimethylamine.
【００２７】[0027]
【化１２】 （Ｒ1、Ｒ2、Ｒｆ は上記と同様の意味を示す。）[Chemical 12](R1, R2, Rf Has the same meaning as above. )
【００２８】更に、上記式（１）においてａが１以上の
整数となる有機フッ素化合物は、例えば上記式（４）に
示される両末端に酸フロライド基を有する化合物と下記
一般式（６） Ｈ−Ｑ −Ｈ …（６） （Ｑ は上記と同様の意味を示す。）で示される両末端に
アミノ基を有する化合物とを受酸剤の存在下で反応さ
せ、更に上記式（５）で示される二級アミン化合物を反
応させることにより合成することができる。Further, in the above formula (1), a is 1 or more.
The organic fluorine compound which is an integer is represented by the above formula (4), for example.
Compounds having an acid fluoride group at both ends shown and the following
General formula (6) H-Q -H ... (6) (Q Has the same meaning as above. ) On both ends
A compound having an amino group is reacted in the presence of an acid acceptor.
The secondary amine compound represented by the above formula (5).
It can be synthesized by adapting it.
【００２９】この場合、式（４）の両末端に酸フロライ
ド基を有する化合物と式（５）の二級アミン化合物との
仕込量の比率は、特に限定されるものではないが、モル
換算で式（４）の化合物の仕込量（ａ）と式（５）の化
合物の仕込量（ｂ）との比率（ａ）／（ｂ）を０．５〜
２ｍｏｌ／ｍｏｌとすると好適である。In this case, the ratio of the charged amounts of the compound having an acid fluoride group at both terminals of the formula (4) and the secondary amine compound of the formula (5) is not particularly limited, but in terms of mol. The ratio (a) / (b) of the charged amount (a) of the compound of formula (4) and the charged amount (b) of the compound of formula (5) is 0.5 to.
It is preferable to set it to 2 mol / mol.
【００３０】また、上記式（４）の化合物の仕込量
（ａ）と式（６）の化合物の仕込量（ｃ）とは、モル換
算で（ａ）を（ｃ）より少なくしない限り、特に限定さ
れるものではない。式（１）中の繰り返し単位ａは、
（ａ）／（ｃ）を調整することにより目的に応じた適宜
な値にすることができ、（ａ）／（ｃ）を大きくすれば
比較的分子量の小さなポリマーを合成することができ、
（ａ）／（ｃ）の値を１に近づければ分子量の大きなポ
リマーを合成することができる。Further, the charged amount (a) of the compound of the formula (4) and the charged amount (c) of the compound of the formula (6) are particularly preferably, unless the amount (a) is less than the molar amount (c). It is not limited. The repeating unit a in formula (1) is
By adjusting (a) / (c), an appropriate value can be obtained according to the purpose, and by increasing (a) / (c), a polymer having a relatively small molecular weight can be synthesized,
When the value of (a) / (c) is close to 1, a polymer having a large molecular weight can be synthesized.
【００３１】上記反応の条件は、特に制限されないが、
２０〜１００℃で１〜８時間、好ましくは２０〜５０℃
で２〜４時間反応させることが好ましい。The conditions of the above reaction are not particularly limited,
20 to 100 ° C for 1 to 8 hours, preferably 20 to 50 ° C
It is preferable to react for 2 to 4 hours.
【００３２】なお、式（１）の有機フッ素化合物におい
て、Ｑ がケイ素原子を介在するものである有機フッ素化
合物は、式（５）の二級アミン化合物として、例えばＲ
1がアリル基等であり、ＨＲ2Ｎ−ＣＨ2ＣＨ＝ＣＨ2等で
示される脂肪族不飽和基を有する二級アミン化合物を使
用して上記反応により例えば下記一般式（７）で示され
る両末端にアリル基を有する化合物を合成し、これと例
えば下記一般式（８）で示される化合物とを付加反応触
媒の存在下で反応させることにより合成することができ
る。The organic fluorine compound of formula (1)
Q Fluorination in which is intercalated with a silicon atom
The compound is, for example, R 2 as a secondary amine compound of the formula (5).
1Is an allyl group, etc., and HR2N-CH2CH = CH2Etc.
The secondary amine compound having an aliphatic unsaturated group shown is used.
For example, the above-mentioned reaction can be used to produce a compound represented by the following general formula (7).
A compound having an allyl group at both ends was synthesized.
For example, a compound represented by the following general formula (8)
It can be synthesized by reacting in the presence of a medium.
It
【００３３】[0033]
【化１３】 （但し、式中Ｒ2，Ｒｆ は前記と同様の意味を示す。）[Chemical 13](However, in the formula R2, Rf Indicates the same meaning as described above. )
【００３４】[0034]
【化１４】 Embedded image
【００３５】この反応で上記式（７）で示される両末端
にアリル基を有する化合物と式（８）の化合物との仕込
量との比率は、モル換算で式（７）の化合物の仕込量
（ｄ）を式（８）の化合物の仕込量（ｅ）より多くしな
くてはならないが、その比率（ｄ）／（ｅ）は最大で２
である。即ち、１＜（ｄ）／（ｅ）≦２である。In this reaction, the ratio of the charged amount of the compound having an allyl group at both ends represented by the above formula (7) to the charged amount of the compound of the formula (8) is the charged amount of the compound of the formula (7) in terms of mol. The amount (d) must be greater than the charged amount (e) of the compound of formula (8), but the ratio (d) / (e) is at most 2
Is. That is, 1 <(d) / (e) ≦ 2.
【００３６】なお、（ｄ）／（ｅ）を大きくすれば比較
的分子量の小さなポリマーを合成することができ、
（ｄ）／（ｅ）の値を１に近づければ分子量の大きなポ
リマーを合成することができる。If (d) / (e) is increased, a polymer having a relatively small molecular weight can be synthesized,
When the value of (d) / (e) is brought close to 1, a polymer having a large molecular weight can be synthesized.
【００３７】この場合、上記触媒としては周期表第ＶＩ
ＩＩ族元素又はその化合物、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錯体（米国特許第３
１５９６０１号、同第３１５９６６２号、同第３７７５
４５２号参照）、白金黒又はパラジウム等をアルミナ、
シリカ、カーボン等の担体に担持させたもの、ロジウム
−オレフィン錯体、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）等を使用し得、
その添加量は触媒量とすることができる。上記の錯体は
アルコール系、ケトン系、エーテル系、炭化水素系の溶
剤に溶解して使用することが好ましい。In this case, as the above-mentioned catalyst,
Group II elements or compounds thereof, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,209,972), chloroplatinic acid and olefin complexes (US Pat.
159601, 3159662, 3775
452), platinum black or palladium, etc., on alumina,
Those supported on a carrier such as silica or carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), etc. may be used.
The added amount can be a catalytic amount. The above complex is preferably used by dissolving it in an alcohol-based, ketone-based, ether-based or hydrocarbon-based solvent.
【００３８】また、上記反応の条件は、５０〜１５０
℃、好ましくは８０〜１２０℃で２〜４時間反応させる
ことが好ましい。The reaction conditions are 50 to 150.
It is preferable to carry out the reaction at ℃, preferably 80 to 120 ℃ for 2 to 4 hours.
【００３９】本発明の有機フッ素化合物は、フッ素含有
率が高く、表面エネルギーが低いエラストマーとなり得
るために、耐薬品性、耐溶剤性のゴム材料用素材及び離
型剤用素材等の原料として種々の用途に利用することが
できる。例えば、両末端がアルケニル基で封鎖された有
機フッ素化合物のポリマーと一分子中に３つ以上のヒド
ロシリル基を有する化合物とを付加反応触媒の存在下に
て反応させれば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、離型剤等として有効に使用することが
できる。Since the organic fluorine compound of the present invention can be an elastomer having a high fluorine content and a low surface energy, it can be used as a raw material for chemical-resistant and solvent-resistant materials for rubber materials and release agents. Can be used for. For example, an elastomer can be obtained by reacting a polymer of an organic fluorine compound having both ends blocked with alkenyl groups with a compound having three or more hydrosilyl groups in one molecule in the presence of an addition reaction catalyst. . Since this elastomer has a high fluorine content, it has excellent solvent resistance and chemical resistance, and because it has low surface energy, it has excellent releasability and water repellency, and it has excellent sealant, molded parts, extruded parts, coating materials, and release materials. It can be effectively used as a mold agent and the like.
【００４０】[0040]
【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、表面エネルギーが低いエラストマーとなり
得るもので、耐溶剤性、耐薬品性のゴム材料用素材、離
型剤用素材などとして有効である。EFFECTS OF THE INVENTION The organic fluorine compound of the present invention can be an elastomer having a high fluorine content and a low surface energy, and is effective as a solvent-resistant and chemical-resistant material for rubber materials, a material for release agents, etc. Is.
【００４１】[0041]
【実施例】以下、実施例を示して本発明を具体的に説明
するが、本発明は下記実施例に制限されるものではな
い。EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples.
【００４２】［実施例１］下記式（９）で示される両末
端に酸フロライド基を有する化合物１８９．２ｇ（粘
度：４３０ｃｓ；２５℃）を撹拌棒、温度計、ジムロー
ト、滴下ロートを付した３００ｍｌ四つ口フラスコ内に
仕込み、撹拌しながら滴下ロートよりイソプロピルアリ
ルアミン７．１ｇとトリエチルアミン６．１ｇとの混合
物を２０℃にて滴下した。Example 1 189.2 g of a compound represented by the following formula (9) having an acid fluoride group at both ends (viscosity: 430 cs; 25 ° C.) was attached to a stir bar, thermometer, Dimroth, and dropping funnel. A 300 ml four-necked flask was charged, and a mixture of 7.1 g of isopropylallylamine and 6.1 g of triethylamine was added dropwise at 20 ° C. from a dropping funnel while stirring.
【００４３】[0043]
【化１５】 [Chemical 15]
【００４４】滴下後に、６０℃にて反応を２時間行い、
反応混合物を加圧濾過して得られた濾液を１２０℃／３
ｍｍＨｇで減圧ストリップしたところ、淡黄色透明な液
状化合物１８９．５ｇが得られた。得られた化合物は、
粘度８４１ｃｓ（２５℃）、比重１．８３２（２５
℃）、屈折率１．３１３８（２５℃）であった。この化
合物をＩＲ測定した結果を図１に示す。図１より、以下
に示す吸収が認められた。After dropping, the reaction was carried out at 60 ° C. for 2 hours,
The filtrate obtained by filtering the reaction mixture under pressure is 120 ° C./3.
When vacuum stripping was performed at mmHg, 189.5 g of a pale yellow transparent liquid compound was obtained. The obtained compound is
Viscosity 841cs (25 ° C), specific gravity 1.832 (25
C.) and the refractive index was 1.3138 (25.degree. C.). The result of IR measurement of this compound is shown in FIG. From FIG. 1, the following absorption was recognized.
【００４５】[0045]
【化１６】 Embedded image
【００４６】また、この化合物のアリル基量を定量した
ところ、０．０３１モル／１００ｇであり、得られた化
合物は、下記構造式（１０）で示される有機フッ素化合
物のポリマーであることが確認された。The amount of allyl group in this compound was determined to be 0.031 mol / 100 g, and it was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (10). Was done.
【００４７】[0047]
【化１７】 [Chemical 17]
【００４８】［実施例２］実施例１と同様の装置に上記
式（９）で示される両末端に酸フロライド基を有する化
合物１８９．２ｇ（粘度：４３０ｃｓ；２５℃）を仕込
み、撹拌しながら滴下ロートよりアリルアニリン９．６
ｇとトリエチルアミン６．１ｇの混合物を２０℃にて滴
下し、実施例１と同様に反応、後処理を行ったところ、
淡黄色透明な液状化合物１９０．１ｇが得られた。Example 2 A device similar to that of Example 1 was charged with 189.2 g of a compound represented by the above formula (9) having an acid fluoride group at both ends (viscosity: 430 cs; 25 ° C.) and stirred. Allylaniline 9.6 from dropping funnel
g and triethylamine (6.1 g) were added dropwise at 20 ° C., and the reaction and post-treatment were carried out in the same manner as in Example 1,
190.1 g of a pale yellow transparent liquid compound was obtained.
【００４９】得られた化合物は、粘度１１９２ｃｓ（２
５℃）、比重１．８４１（２５℃）、屈折率１．３２０
８（２５℃）であった。この化合物をＩＲ測定した結果
を図２に示す。図２より、以下に示す吸収が認められ
た。The obtained compound has a viscosity of 1192 cs (2
5 ° C), specific gravity 1.841 (25 ° C), refractive index 1.320
It was 8 (25 degreeC). The result of IR measurement of this compound is shown in FIG. From FIG. 2, the following absorption was recognized.
【００５０】[0050]
【化１８】 [Chemical 18]
【００５１】また、この化合物のアリル基量を定量した
ところ、０．０３１モル／１００ｇであり、得られた化
合物は、下記構造式（１１）で示される有機フッ素化合
物のポリマーであることが確認された。The amount of allyl group in this compound was determined to be 0.031 mol / 100 g, and it was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (11). Was done.
【００５２】[0052]
【化１９】 [Chemical 19]
【００５３】［実施例３］上記式（９）で示される両末
端に酸フロライド基を有する化合物７６．９ｇ（粘度：
４３０ｃｓ；２５℃）を撹拌棒、温度計、ジムロート、
滴下ロートを付した２００ｍｌ四つ口フラスコ内に仕込
み、撹拌しながら滴下ロートより２，５−ジメチルピペ
ラジン１．１４ｇとトリエチルアミン２．９ｇとの混合
物を２０℃にて滴下した。滴下後に、６０℃にて反応を
２時間行い、その後、メチルアリルアミン０．３６ｇを
添加し、更に、実施例１と同様に反応、後処理を行った
ところ、淡黄色透明な液状化合物７２．９ｇが得られ
た。Example 3 76.9 g of a compound represented by the above formula (9) having an acid fluoride group at both ends (viscosity:
430 cs; 25 ° C.), stirring rod, thermometer, Dimroth,
A 200 ml four-necked flask equipped with a dropping funnel was charged, and a mixture of 1.14 g of 2,5-dimethylpiperazine and 2.9 g of triethylamine was added dropwise at 20 ° C. from the dropping funnel while stirring. After the dropwise addition, the reaction was carried out at 60 ° C. for 2 hours, then 0.36 g of methylallylamine was added, and the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain 72.9 g of a pale yellow transparent liquid compound. was gotten.
【００５４】得られた化合物は、粘度２５２００ｃｓ
（２５℃）であった。この化合物をＩＲ測定した結果を
図３に示す。図３より、以下に示す吸収が認められた。The compound obtained has a viscosity of 25,200 cs.
(25 ° C). The result of IR measurement of this compound is shown in FIG. From FIG. 3, the following absorption was recognized.
【００５５】[0055]
【化２０】 Embedded image
【００５６】また、この化合物のアリル基量を定量した
ところ、０．００５モル／１００ｇであり、得られた化
合物は、下記構造式（１２）で示される有機フッ素化合
物のポリマーであることが確認された。The amount of allyl group in this compound was determined to be 0.005 mol / 100 g, and it was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (12). Was done.
【００５７】[0057]
【化２１】 [Chemical 21]
【００５８】［実施例４］実施例３と同様の装置に下記
式（１３）で示される両末端にアリル基を有する化合物
１００．０ｇ（粘度：１１９２ｃｓ；２５℃）とメタキ
シレンヘキサフロライド５０．０ｇとを仕込み、撹拌し
ながら９０℃に加熱して、塩化白金酸のイソプロピルア
ルコール２％溶液０．１ｇを添加した。その後、滴下ロ
ートにて下記式（１４）で示されるシクロテトラシロキ
サン３．６６ｇを滴下し、反応を行った。Example 4 100.0 g of a compound represented by the following formula (13) having an allyl group at both ends (viscosity: 1192 cs; 25 ° C.) and metaxylene hexafluoride 50 were placed in the same apparatus as in Example 3. 0.0 g was added, and the mixture was heated to 90 ° C. with stirring, and 0.1 g of a 2% solution of chloroplatinic acid in isopropyl alcohol was added. Then, 3.66 g of cyclotetrasiloxane represented by the following formula (14) was added dropwise with a dropping funnel to carry out a reaction.
【００５９】[0059]
【化２２】 [Chemical formula 22]
【００６０】滴下後、熟成させながらガスクロマトグラ
フでシクロテトラシロキサンの消失を確認した後、室温
まで冷却し、活性炭１．５ｇを投入して２時間撹拌し
た。これに実施例１と同様の後処理を行ったところ、透
明な液状化合物９９．２ｇが得られた。After dropping, after confirming the disappearance of cyclotetrasiloxane by gas chromatography while aging, the mixture was cooled to room temperature, 1.5 g of activated carbon was added, and the mixture was stirred for 2 hours. When this was subjected to the same post-treatment as in Example 1, 99.2 g of a transparent liquid compound was obtained.
【００６１】得られた化合物は、粘度３０７００ｃｓ
（２５℃）であった。この化合物をＩＲ測定した結果を
図４に示す。図４より、以下に示す吸収が認められた。The obtained compound has a viscosity of 30700 cs.
(25 ° C). The result of IR measurement of this compound is shown in FIG. From FIG. 4, the following absorption was recognized.
【００６２】[0062]
【化２３】 [Chemical formula 23]
【００６３】また、この化合物のアリル基量を定量した
ところ、０．００７モル／１００ｇであり、得られた化
合物は、下記構造式（１５）で示される有機フッ素化合
物のポリマーであることが確認された。The amount of allyl group of this compound was determined to be 0.007 mol / 100 g, and it was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (15). Was done.
【００６４】[0064]
【化２４】 [Chemical formula 24]
【００６５】［実施例５］実施例１と同様の装置に下記
式（１６）で示される両末端に酸フロライド基を有する
化合物２００．０ｇ（粘度：２１００ｃｓ；２５℃）を
仕込み、撹拌しながら滴下ロートよりアリルアニリン
３．６ｇとトリエチルアミン２．８ｇの混合物を２０℃
にて滴下し、実施例１と同様に反応、後処理を行ったと
ころ、淡黄色透明な液状化合物１９５．１ｇが得られ
た。Example 5 A device similar to that of Example 1 was charged with 200.0 g (viscosity: 2100 cs; 25 ° C.) of a compound represented by the following formula (16) having an acid fluoride group at both ends, and stirred. From the dropping funnel, a mixture of 3.6 g of allylaniline and 2.8 g of triethylamine was added at 20 ° C.
Then, the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain 195.1 g of a pale yellow transparent liquid compound.
【００６６】[0066]
【化２５】 [Chemical 25]
【００６７】得られた化合物は、粘度３３００ｃｓ（２
５℃）、比重１．８８３（２５℃）、屈折率１．３０９
（２５℃）であった。この化合物をＩＲ測定した結果を
図５に示す。図５より、以下に示す吸収が認められた。The obtained compound had a viscosity of 3300 cs (2
5 ° C), specific gravity 1.883 (25 ° C), refractive index 1.309
(25 ° C). The result of IR measurement of this compound is shown in FIG. From FIG. 5, the following absorption was observed.
【００６８】[0068]
【化２６】 [Chemical formula 26]
【００６９】また、この化合物のアリル基量を定量した
ところ、０．０１１モル／１００ｇであり、得られた化
合物は、下記構造式（１７）で示される有機フッ素化合
物のポリマーであることが確認された。The amount of allyl group in this compound was determined to be 0.011 mol / 100 g, and it was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (17). Was done.
【００７０】[0070]
【化２７】 [Chemical 27]
【図１】実施例１の有機フッ素化合物のＩＲスペクトル
を示すチャートである。FIG. 1 is a chart showing an IR spectrum of an organic fluorine compound of Example 1.
【図２】実施例２の有機フッ素化合物のＩＲスペクトル
を示すチャートである。2 is a chart showing an IR spectrum of the organic fluorine compound of Example 2. FIG.
【図３】実施例３の有機フッ素化合物のＩＲスペクトル
を示すチャートである。FIG. 3 is a chart showing an IR spectrum of the organic fluorine compound of Example 3.
【図４】実施例４の有機フッ素化合物のＩＲスペクトル
を示すチャートである。4 is a chart showing an IR spectrum of an organic fluorine compound of Example 4. FIG.
【図５】実施例５の有機フッ素化合物のＩＲスペクトル
を示すチャートである。5 is a chart showing an IR spectrum of the organic fluorine compound of Example 5. FIG.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松田 高至 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子材料 技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Takatoshi Matsuda 1 Hitomi, Otomi, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory
Claims (1)
化合物。 【化１】 ［但し、式中Ｒ1及びＲ2はそれぞれ置換又は非置換の一
価炭化水素基、Ｑは下記一般式（２）又は下記一般式
（３）で示される基 【化２】 （但し、式中Ｒ3は結合途中に酸素原子、窒素原子及び
ケイ素原子の１種又は２種以上を介在させてもよい置換
又は非置換の二価炭化水素基を示す。） 【化３】 （但し、式中Ｒ4及びＲ5は置換又は非置換の二価炭化水
素基を示す。）、Ｒｆ は二価のパーフルオロアルキレン
基又は二価のパーフルオロポリエーテル基であり、ａは
０以上の整数である。］1. An organic fluorine represented by the following general formula (1):
Compound. [Chemical 1][However, in the formula R1And R2Is a substituted or unsubstituted
Valent hydrocarbon group, Q is the following general formula (2) or the following general formula
A group represented by (3)(However, in the formula R3Is an oxygen atom, a nitrogen atom and
Substitution that may have one or more silicon atoms interposed
Alternatively, it represents an unsubstituted divalent hydrocarbon group. ) [Chemical 3](However, in the formula RFourAnd RFiveIs a substituted or unsubstituted divalent hydrocarbon
Indicates a basic group. ), Rf Is a divalent perfluoroalkylene
Group or a divalent perfluoropolyether group, a is
It is an integer of 0 or more. ]
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6295789A JP2991059B2 (en) | 1994-06-23 | 1994-11-04 | Organic fluorine compounds |
| DE69529097T DE69529097T2 (en) | 1994-06-23 | 1995-06-22 | Crosslinkable compositions containing organic fluorine compounds |
| EP95304369A EP0688762B1 (en) | 1994-06-23 | 1995-06-22 | Organic fluorine compounds and curable compositions containing them |
| EP98104740A EP0851003B1 (en) | 1994-06-23 | 1995-06-22 | Curable compositions containing organic fluorine compounds |
| US08/494,566 US5705586A (en) | 1994-06-23 | 1995-06-22 | Organic fluorine compounds and curable compositions |
| DE69523822T DE69523822T2 (en) | 1994-06-23 | 1995-06-22 | Organic fluorine compounds and crosslinkable compositions containing them |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-164635 | 1994-06-23 | ||
| JP16463594 | 1994-06-23 | ||
| JP6295789A JP2991059B2 (en) | 1994-06-23 | 1994-11-04 | Organic fluorine compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0867660A true JPH0867660A (en) | 1996-03-12 |
| JP2991059B2 JP2991059B2 (en) | 1999-12-20 |
Family
ID=26489661
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|---|---|---|---|
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| Country | Link |
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| JP (1) | JP2991059B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006335955A (en) * | 2005-06-03 | 2006-12-14 | Shin Etsu Chem Co Ltd | Fluorine-containing amide compound and its manufacturing method |
| JP2008019398A (en) * | 2006-07-14 | 2008-01-31 | Shin Etsu Chem Co Ltd | Curable fluorine-containing composition |
| US7538170B2 (en) | 2002-03-14 | 2009-05-26 | Daikin Industries, Ltd. | Fluorocopolymer, process for producing fluorocopolymer, fluorocopolymer curable composition, and cured object |
| JP2011201941A (en) * | 2010-03-24 | 2011-10-13 | Shin-Etsu Chemical Co Ltd | Fluorine-modified amino group-containing organopolysiloxane, and method for producing the same |
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1994
- 1994-11-04 JP JP6295789A patent/JP2991059B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
| US7538170B2 (en) | 2002-03-14 | 2009-05-26 | Daikin Industries, Ltd. | Fluorocopolymer, process for producing fluorocopolymer, fluorocopolymer curable composition, and cured object |
| EP2085408A1 (en) | 2002-03-14 | 2009-08-05 | Daikin Industries, Ltd. | Fluorocopolymer curable composition, and cured object |
| US7915361B2 (en) | 2002-03-14 | 2011-03-29 | Daikin Industries, Ltd. | Fluorocopolymer, process for producing fluorocopolymer, fluorocopolymer curable composition, and cured object |
| JP2006335955A (en) * | 2005-06-03 | 2006-12-14 | Shin Etsu Chem Co Ltd | Fluorine-containing amide compound and its manufacturing method |
| JP4498218B2 (en) * | 2005-06-03 | 2010-07-07 | 信越化学工業株式会社 | Fluorine-containing amide compound and process for producing the same |
| JP2008019398A (en) * | 2006-07-14 | 2008-01-31 | Shin Etsu Chem Co Ltd | Curable fluorine-containing composition |
| JP2011201941A (en) * | 2010-03-24 | 2011-10-13 | Shin-Etsu Chemical Co Ltd | Fluorine-modified amino group-containing organopolysiloxane, and method for producing the same |
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| JP2991059B2 (en) | 1999-12-20 |
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