JP2008255179A - Fluorine-containing polyether compound, its manufacturing method, and curable composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing polyether compound capable of being cured without requiring a fluorine-containing organohydrogensiloxane compound having a Si-H bond, excellent in heat-resistance, a low temperature characteristic and moldability and capable of being withstood at use under an acidic condition, to provide its manufacturing method, and to provide a curable composition containing it. <P>SOLUTION: Fluorine-containing carboxylic fluoride XC<SB>6</SB>H<SB>4</SB>ORfO[CF(CF<SB>3</SB>)CF<SB>2</SB>O]<SB>n</SB>CF(CF<SB>3</SB>)COF (Rf: a perfluoroalkylene group, X: I or Br, n: 30-130) is reacted with an aromatic amine YC<SB>6</SB>H<SB>4</SB>NHR<SP>1</SP>(R<SP>1</SP>: H, an alkyl group or a phenyl group, Y: I or Br), to prepare a fluorine-containing polyether compound XC<SB>6</SB>H<SB>4</SB>ORfO[CF(CF<SB>3</SB>)CF<SB>2</SB>O]<SB>n</SB>CF(CF<SB>3</SB>)CONR<SP>1</SP>C<SB>6</SB>H<SB>4</SB>Y. An aromatic boronic ester, an organic palladium compound, and a basic inorganic or organic compound (and organic phosphorous compound) are formulated to the fluorine-containing polyether compound to form a curable fluorine-containing polyether composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fluorine-containing polyether compound, a method for producing the same, and a curable composition containing the same. More specifically, the present invention relates to a fluorine-containing polyether compound that can give a cured product having excellent heat resistance and low-temperature properties and also exhibiting good chemical resistance, a method for producing the same, and a curable composition containing the same.

で表わされる化合物が知られている。
特開平１１−３４３３３６号公報 As the fluorine-containing polyether compound having a functional group at the molecular end, for example, a general formula

The compound represented by is known.
Japanese Patent Laid-Open No. 11-343336

で表わされる化合物が知られている。
特許２９９０６４６号公報 Further, as a more general compound obtained by oligomerizing the main chain structure of the above compound, a general formula

The compound represented by is known.
Japanese Patent No. 2990646

  The compounds represented by these general formulas are cured by a fluorine-containing organohydrogensiloxane compound having a plurality of Si-H groups in the molecule and a platinum compound catalyst, and have excellent properties (chemical resistance, heat resistance, low temperature It is said that an elastomeric molded product having characteristics) can be provided, and in particular, it can be used without loss of flexibility even under a low temperature condition of about -50 ° C. Moreover, the curable composition which has these as a main component has outstanding moldability, and also enables RIM molding. However, since this cured product has a siloxane bond in the intramolecular cross-linked structure, when it is used under acidic conditions such as fluorine hydrogen, it causes undesirable results such as a decrease in its mechanical strength due to chemical degradation. May be given.

On the other hand, as a fluorine-containing elastomer having excellent low temperature characteristics, for example, a vinylidene fluoride / tetrafluoroethylene / perfluoro (methyl vinyl ether) terpolymer is known as a general one, and its glass transition temperature Tg is known. Is about -25 to -35 ° C. In addition, as a fluorine-containing elastomer having a glass transition temperature Tg of −35 ° C. or less, a perfluorovinyl ether compound having a perfluoro (alkoxyalkyl) group side chain as shown below is copolymerized instead of perfluoro (methyl vinyl ether). What was made known is known.
CF ₂ = CFO (CF ₂ ) ₃ OCF ₃
CF ₂ = CFO (CF ₂ ) ₂ O (CF ₂ ) _n CF ₃ (n: 1 to 4)
CF ₂ = CFO (CF ₂ CF ₂ ) _m OCF ₃ (m: 1 to 5)
CF ₂ = CFO (CF ₂ CF ₂ CF ₂ O) _n C _m F _{2m + 1} (n: 1 to 4, m: 1 to 5)
CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] _n CF ₃ (n: 2 to 6)
USP 5,969,216 USP 6,294,627 JP-A 64-52733 JP 2004-348087 A

  Fluorine-containing elastomers copolymerized with these perfluorovinyl ether compounds have excellent chemical resistance such as resistance to acidic conditions such as hydrogen fluoride, and good heat resistance. Equivalent to elastomer.

  The object of the present invention is that it can be cured without the need for a fluorine-containing organohydrogensiloxane compound having a Si-H bond, and is excellent in heat resistance, low-temperature characteristics and molding processability, and also for use under acidic conditions. An object of the present invention is to provide a fluorine-containing polyether compound that gives a cured product that can withstand, a method for producing the same, and a curable composition containing the compound.

(ここで、R¹は水素原子、炭素数1〜3のアルキル基またはフェニル基であり、Rfは炭素数2〜4の直鎖状または分岐状のパーフルオロアルキレン基であり、XおよびYはそれぞれ独立にヨウ素原子または臭素原子であり、X、Yのフェニル基上の置換位置は、それぞれ独立にRfO結合置換基およびNR¹結合置換基に対してm-位またはp-位であり、nは30〜130の整数である)で表わされる含フッ素ポリエーテル化合物が提供される。 According to the invention, the general formula

(Where R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, Rf is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms, and X and Y are Each independently an iodine atom or a bromine atom, and the substitution positions on the phenyl groups of X and Y are each independently the m-position or the p-position with respect to the RfO bond substituent and the NR ¹ bond substituent, and n Is an integer of 30 to 130).

(ここで、Rfは炭素数2〜4の直鎖状または分岐状のパーフルオロアルキレン基であり、Xはヨウ素原子または臭素原子であり、Xのフェニル基上の置換位置はRfO結合置換基に対してm-位またはp-位であり、nは30〜130の整数である)で表わされる含フッ素カルボン酸フルオリド化合物を、一般式

(ここで、R¹は水素原子、炭素数1〜3のアルキル基またはフェニル基であり、Yはヨウ素原子または臭素原子であり、Yのフェニル基上の置換位置はNR¹結合置換基に対してm-位またはp-位である)で表わされる芳香族1級または2級アミン化合物と、ピリジンまたはトリエチルアミン等の3級アミン化合物の存在下で反応させることにより製造される。 Such fluorine-containing polyether compounds have the general formula

(Here, Rf is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms, X is an iodine atom or a bromine atom, and the substitution position on the phenyl group of X is the RfO bond substituent. Fluorinated carboxylic acid fluoride compound represented by the general formula: m-position or p-position, n is an integer of 30 to 130)

(Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, Y is an iodine atom or a bromine atom, and the substitution position on the phenyl group of Y is relative to the NR ¹ bond substituent. In the presence of a tertiary amine compound such as pyridine or triethylamine.

The fluorine-containing polyether compound thus obtained is used as a main component of the following curable composition. Specifically, the curable composition concerning this invention is comprised from the following each component.
Component (A) Fluorine-containing polyether compound 100 parts by weight
Component (B) Aromatic boronic ester compound 0.1-10 parts by weight
Component (C) 0 or divalent organopalladium compound 0.0001 to 1 part by weight
Component (D) Basic inorganic compound or basic organic compound 0.1 to 10 parts by weight
Component (E) Organic phosphorus compound 0-5 parts by weight

The fluorine-containing polyether compound according to the present invention can be produced from a readily available raw material by a simple reaction. Moreover, a curable fluorine-containing polyether composition can be formed with a specific hardening | curing agent and a hardening catalyst. This curable fluorine-containing polyether composition has good processability such as an appropriate fluidity at room temperature, and can be applied to various molding methods such as injection molding and RIM. Moreover, by curing it, a cured product having excellent chemical resistance that is excellent in heat resistance and low temperature characteristics and can be used even under acidic conditions such as hydrogen fluoride is obtained. Molded articles obtained by curing such compositions have various characteristics as described above, and therefore various types such as automobile fuel supply system seal materials, oil seal materials, aircraft fuel systems and hydraulic system seal materials, and semiconductor manufacturing equipment seal materials. It is suitably used for applications.

において、nは30〜130の整数であり、好ましくは50〜130の整数である。R¹は、水素原子、炭素数1〜3のアルキル基またはフェニル基であり、特に製造面からは水素原子またはメチル基であることが好ましい。ただし、水素原子の場合には、得られる含フッ素ポリエーテル化合物の粘度が高くなる傾向にある。Rfは、炭素数2〜4の直鎖状または分岐状のパーフルオロアルキレン基であり、特に製造面からは炭素数3のパーフルオロアルキレン基が選ばれ、具体的には-CF₂CF(CF₃)-(ただし、側鎖CF₃基はオキシフェニル基側)または-CF₂CF₂CF₂-が好ましい例として挙げられる。X、Yはそれぞれ独立にヨウ素原子または臭素原子であり、そのフェニル基上の置換位置はそれぞれ独立にRfO結合置換基およびNR¹結合置換基に対してm-位またはp-位である。 Fluorinated polyether compound of the present invention

In the formula, n is an integer of 30 to 130, preferably an integer of 50 to 130. R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and particularly preferably a hydrogen atom or a methyl group from the viewpoint of production. However, in the case of hydrogen atoms, the viscosity of the resulting fluorine-containing polyether compound tends to increase. Rf is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms, and particularly a perfluoroalkylene group having 3 carbon atoms is selected from the viewpoint of production, and specifically, -CF ₂ CF (CF ₃ )-(where the side chain CF ₃ group is on the oxyphenyl group side) or —CF ₂ CF ₂ CF ₂ — is a preferred example. X and Y are each independently an iodine atom or a bromine atom, and the substitution position on the phenyl group is independently the m-position or p-position with respect to the RfO bond substituent and the NR ¹ bond substituent.

と芳香族1級または2級アミン

とを、ピリジンまたはトリエチルアミン等の3級アミン化合物の存在下で反応させることにより製造することができる。反応は、ハイドロクロロフルオロカーボン、ハイドロフルオロカーボン、ハイドロフルオロエーテル等の含フッ素溶媒、またはこれらの含フッ素溶媒と非プロトン性非フッ素系溶媒との混合溶媒中で-50〜150℃、好ましくは0〜100℃で行われる。含フッ素溶媒の具体例としては、HCFC-225、HFE-449(住友3M製品HFE7100)、HFE-569(住友3M製品HFE-7200)等が挙げられる。非プロトン性非フッ素系溶媒としては、ジエチルエーテル、ジイソプロピルエーテル、シクロペンチルメチルエーテル等が挙げられる。1級アミンまたは2級アミンの溶解性を考慮すると、含フッ素溶媒と非プロトン性非フッ素系溶媒の混合溶媒を用いるのがより好ましい。 The fluorine-containing polyether compound represented by the above general formula is a fluorine-containing carboxylic acid fluoride.

And aromatic primary or secondary amines

Can be reacted in the presence of a tertiary amine compound such as pyridine or triethylamine. The reaction is carried out in a fluorinated solvent such as hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroether, or a mixed solvent of these fluorinated solvent and aprotic non-fluorinated solvent, preferably -50 to 150 ° C, preferably 0 to 100. Done at ℃. Specific examples of the fluorine-containing solvent include HCFC-225, HFE-449 (Sumitomo 3M product HFE7100), HFE-569 (Sumitomo 3M product HFE-7200), and the like. Examples of the aprotic non-fluorinated solvent include diethyl ether, diisopropyl ether, cyclopentyl methyl ether and the like. Considering the solubility of primary amine or secondary amine, it is more preferable to use a mixed solvent of a fluorine-containing solvent and an aprotic non-fluorine solvent.

J. Am. Chem. Soc. 106巻 5544頁 (1984) The fluorine-containing carboxylic acid fluoride compound can be produced, for example, as follows.

J. Am. Chem. Soc. 106 5544 (1984)

などが挙げられる。 Specific examples of the fluorine-containing polyether compound of the present invention include:

Etc.

The curable fluorine-containing polyether composition of the present invention is composed of the following components containing the fluorine-containing polyether compound [component (A)] as a main component.
Component (A) Fluorine-containing polyether compound 100 parts by weight
Component (B) Aromatic boronic ester compound 0.1-10 parts by weight
Component (C) 0 or divalent organopalladium compound 0.0001 to 1 part by weight
Component (D) Basic inorganic compound or basic organic compound 0.1 to 10 parts by weight
Component (E) Organic phosphorus compound 0-5 parts by weight The curing reaction of the curable composition described above is based on a cross-coupling reaction of arylboronic acid or ester thereof with aryl halide (Suzuki-Miyaura reaction) with a palladium catalyst. Is.
Chem. Rev. 95 2457 (1995)

Hereinafter, each component which forms a composition is demonstrated one by one.
In the fluorine-containing polyether compound represented by the above general formula, which is the component (A), n is an integer of 30 to 130. To obtain a cured product having sufficient mechanical strength after curing, n is 50. ~ 130 is preferred. R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, but in order to avoid side reactions in intramolecular or intermolecular hydrogen bonding and curing, an alkyl group or phenyl group having 1 to 3 carbon atoms is preferable. In particular, a methyl group is selected because of easy availability of raw materials. Rf is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms, and particularly a perfluoroalkylene group having 3 carbon atoms is selected from the viewpoint of production, and specifically, -CF ₂ CF (CF ₃ )-(where the side chain CF ₃ group is on the oxyphenyl group side) or —CF ₂ CF ₂ CF ₂ — is a preferred example. X and Y are each independently an iodine atom or a bromine atom, but an iodine atom is preferred from the viewpoint of rapid curing. The substitution positions on the phenyl groups of X and Y are independently m-position or p-position with respect to the RfO bond substituent and the NR ¹ bond substituent. When the substitution position of X and Y is o-position, the curing rate is lowered due to steric factors, which is not preferable.

を用いることができる。ここで、R²は炭素数2〜10の直鎖状または分岐状の脂肪族炭化水素基であり、例えば-CH₂C(CH₃)₂CH₂-、-CH₂CH₂CH₂-、-CH(CH₃)₂C(CH₃)₂-、-C(CH₃)₂CH₂C(CH₃)₂-等が挙げられる。具体的な例としては、1,3,5-トリス(4,4,5,5-テトラメチル-1,3,2-ジオキシサボロラン-2-イル)ベンゼン、1,3,5-トリス(5,5-ジメチル-1,3,2-ジオキサボリナン-2-イル)ベンゼン、1,3,5-トリス(4,4,6,6-テトラメチル-1,3,2-ジオキサボリナン-2-イル)ベンゼンが挙げられる。好ましくは、1,3,5-トリス(4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン-2-イル)ベンゼンが製造の容易さから選ばれる。
J. Appl. Poly. Sci. 76巻 1257頁 (2000) Component (B) is an aromatic boronic acid ester compound represented by the following general formula

Can be used. Here, R ² is a linear or branched aliphatic hydrocarbon group having 2 to 10 carbon atoms, such as —CH ₂ C (CH ₃ ) ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, -CH (CH ₃ ) ₂ C (CH ₃ ) _2- , -C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) _2- and the like. Specific examples include 1,3,5-tris (4,4,5,5-tetramethyl-1,3,2-dioxysaborolan-2-yl) benzene, 1,3,5-tris. (5,5-Dimethyl-1,3,2-dioxaborinan-2-yl) benzene, 1,3,5-tris (4,4,6,6-tetramethyl-1,3,2-dioxaborinan-2- Yl) benzene. Preferably, 1,3,5-tris (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene is selected for ease of production.
J. Appl. Poly. Sci. 76 1257 (2000)

  The (B) component aromatic boronic acid ester compound is used in a proportion of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the (A) component fluorinated polyether compound. When the component (B) is less than this, the curing becomes insufficient or the mechanical strength of the obtained cured product is lowered. On the other hand, if it is used at a higher ratio, it is not economical because an effect commensurate with it cannot be expected.

  As the component (C) organic palladium compound used as the curing catalyst, a zero-valent or divalent organic palladium compound is used. The zero-valent organic palladium compound acts as a catalyst for the curing reaction in the zero-valent state as it is. The divalent organopalladium compound exhibits catalytic action after being reduced to zero valence by the component (A), the component (B), or the component (E), which will be described later. The component (C) organic palladium compound is used in a ratio of 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, per 100 parts by weight of the component (A) fluorine-containing polyether compound. If the component (C) is less than this, sufficient curing will not be achieved, while it is not economical to use it in a proportion higher than this.

  As the zero-valent organic palladium compound, tetrakis (triphenylphosphine) palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium and the like are used. Examples of the divalent organic palladium compound include palladium acetate, allyl palladium chloride, bis (triphenylphosphine) palladium chloride, bis (tritert-butylphosphine) palladium chloride, and the like. In particular, palladium acetate is preferably used.

で表わされる(E)成分有機リン化合物を併用することが好ましい。 In addition, when using an organic palladium compound that does not contain a phosphorus compound in the molecule, such as palladium acetate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, and allylpalladium chloride, as a stabilizer, a general formula

It is preferable to use an organic phosphorus compound (E) represented by

Here, R ³ , R ⁴ and R ⁵ are each independently a C1-C10 chain aliphatic hydrocarbon group, a C5-C12 cyclic aliphatic hydrocarbon group or carbon which may have a substituent. It is an aromatic hydrocarbon group of number 6-20. Specific examples of the organic phosphorus compound having an aliphatic hydrocarbon group include tricyclohexylphosphine, tri-tert-butylphosphine, triisopropylphosphine and the like.

で表わされるトリフェニルホスフィン化合物類または一般式

で表わされる、Buchwald配位子と総称される化合物群を用いることもできる。
ＵＳＰ ６，３０７，０８７ ＵＳＰ ６，２９４，６２７ In addition, as an organic phosphorus compound having an aromatic hydrocarbon group, a general formula

Triphenylphosphine compounds represented by the general formula

It is also possible to use a group of compounds generically referred to as Buchwald ligand.
USP 6,307,087 USP 6,294,627

Here, A, B and C are each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms or an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group. R ⁶ is a linear or cyclic aliphatic hydrocarbon group having 1 to ⁶ carbon atoms. Examples of triphenylphosphine compounds include triphenylphosphine, tris (4-methoxyphenyl) phosphine, tris (1,3,5-triisopropylphenyl) phosphine, and the like. Specific examples of the Buchwald ligand include (2-biphenyl) dicyclohexylphosphine, 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl, 2-di-tert-butylphosphino-2', 4 ', 6 Examples thereof include compounds such as' -triisopropylbiphenyl and 2-dicyclohexylphosphino-2'-dimethylaminobiphenyl.

で表わされる二座配位子有機リン化合物も用いることができる。ここで、Phは炭素数1〜6の脂肪族炭化水素基または置換基を有し得るフェニル基であり、Zは2価の炭素数1〜10の脂肪族炭化水素基、炭素数6〜20の芳香族炭化水素基またはメタロセン基である。 Other general formulas with two phosphorus atoms in the molecule

A bidentate organophosphorus compound represented by the formula can also be used. Here, Ph is an aliphatic hydrocarbon group having 1 to 6 carbon atoms or a phenyl group which may have a substituent, Z is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, 6 to 20 carbon atoms An aromatic hydrocarbon group or a metallocene group.

  Specific examples include 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphine). Examples include compounds such as fino) ferrocene, 1,1′-bis (ditert-butylphosphino) ferrocene, and 2,2′-bis (diphenylphosphino) -1,1′-binaphthalene.

  The (E) component organic phosphorus compound is used in an amount of 0.5 to 10 molar equivalents, preferably 1 to 4 molar equivalents, relative to the Pd atom of the (C) component organic palladium compound. The component (A) is preferably used at a ratio of 0.1 to 2 parts by weight per 100 parts by weight.

  The basic inorganic compound or basic organic compound of component (D) includes lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and other alkali metal carbonates or hydrogen carbonates. Alkali metal phosphates or hydrogen phosphates such as lithium phosphate, sodium phosphate and potassium phosphate, oxides or hydroxides of alkali metals or alkaline earth metals such as magnesium oxide, calcium hydroxide and sodium hydroxide Products, alkali metal fluorides such as potassium fluoride, sodium fluoride and cesium fluoride, alkali metal acetates such as potassium acetate, sodium methoxide and organic amines. A preferred example is potassium phosphate. The (D) component basic inorganic compound or basic organic compound is used in a proportion of 0.1 to 10 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the (A) component fluorine-containing polyether compound. If component (D) is not added, the curing reaction may be very slow or may not occur at all.

  In the curable fluorine-containing polyether composition, in addition to these components, various fillers, reinforcing agents, pigments and the like having an amount and a purity that do not inhibit the curing reaction are used as appropriate. The composition is prepared by kneading using a three-roll mill, a planetary mixer, etc., and the mixture is cured at room temperature to 200 ° C. by compression molding, injection molding, RIM molding, etc. for about 1 to 60 minutes. If necessary, oven vulcanization (secondary vulcanization) is performed at 50 to 250 ° C. for about 1 to 30 hours.

  Next, the present invention will be described with reference to examples.

Reference Example Synthesis of fluorinated carboxylic acid fluoride compounds

8.5g、フッ化セシウム3.5gおよびテトラグライム39gを混合してからセシウムアルコキシド

のテトラグライム溶液を調製し、次の反応に用いた。 (1) Acid fluoride compounds

Cesium alkoxide after mixing 8.5g, cesium fluoride 3.5g and tetraglyme 39g

A tetraglyme solution was prepared and used for the next reaction.

  (2) A 1 L glass reaction vessel equipped with a stirrer, temperature sensor, gas inlet and dry ice / ethanol cooled condenser was placed in a low-temperature thermostatic chamber, and the alkoxide compound obtained in (3) above was 50 g of a tetraglyme solution containing 23 mmol was charged. After adjusting the internal temperature to −33 to −30 ° C., 20 g of hexafluoropropene was charged from the gas inlet. Next, hexafluoropropene oxide was charged into the reaction vessel at a feed rate of 5 g / hr and hexafluoropropene at a feed rate of 2 g / hr. After 60 hours, the gas supply was stopped and the internal temperature was kept at -33 to -30 ° C for 1 hour. After removing hexafluoropropene from the reaction system under reduced pressure, the temperature was slowly raised to room temperature. The temperature was further raised to 100 ° C., and the hexafluoropropene oligomer was removed from the reaction mixture under reduced pressure. In this way, 345 g of a mixture consisting of cesium fluoride, tetraglyme and fluorine-containing carboxylic acid fluoride was obtained as a pale yellow viscous suspension. This was used in the next step shown in the examples without purification.

s＝F^a(-131ppm)ピーク積分値
t＝F^b(-133ppm)ピーク積分値
u＝F^c(-146ppm)ピーク積分値
注) ケミカルシフトはCFCl₃基準
MF＝1-(s／(2t))＝0.85
ヘキサフルオロプロペンオキシド数平均重合度＝u／t＝72 (3) Further, after a part of the above mixture was converted to an ester form with methanol, the number average polymerization degree of hexafluoropropene oxide and the mole fraction (MF) with the hexafluoropropene oxide oligomer were determined by ¹⁹ F-NMR.

s = F ^a (-131ppm) Peak integrated value
t = F ^b (-133ppm) Peak integral value
u = F ^c (-146ppm) peak integral value
Note) Chemical shift is based on CFCl ₃
MF = 1- (s / (2t)) = 0.85
Hexafluoropropene oxide number average degree of polymerization = u / t = 72

参考例で得られた含フッ素カルボン酸フルオリド、フッ化セシウムおよびテトラグライムからなる混合物60g(約4.7ミリモル)を、含フッ素系溶媒(住友3M製品HFE-7100)50mlに溶解し、そこにトリエチルアミン1.0g(1.0ミリモル)およびジエチルエーテル20mlを加えた。これに、p-ヨード-N-メチルアニリン1.6g(7.0ミリモル)を加え、室温で1時間反応を行った。得られた反応混合物を飽和食塩水に加え、分離した有機層を無水硫酸マグネシウムで乾燥、ロ過した。減圧下でロ液から含フッ素系溶媒およびジエチルエーテルを留去した後、得られた粘稠な液体をジエチルエーテルで数回洗浄し、次いで減圧下でジエチルエーテルを完全に留去した。このようにして、含フッ素ポリエーテル化合物〔PFPE-I〕

を僅かに黄色味を帯びた透明な液体として49g得た。E型粘時計(東機産業製TEV-22)により粘度を測定したところ、13Pa・s(25℃)であった。
¹⁹F-NMR(ケミカルシフトはCFCl₃基準)： -123ppm(F^b)
-145ppm(F^c)
¹H-NMR(ケミカルシフトはTMS基準)： 7.5ppm(H^a、H^e)
6.6ppm(H^b、H^d)
3.1ppm(H^c)
IR(neat)： 1703cm^-1(C=O)
1490cm^-1(Ar) Example 1
Synthesis of fluorinated polyether compound [PFPE-I]

60 g (about 4.7 mmol) of a mixture composed of fluorine-containing carboxylic acid fluoride, cesium fluoride and tetraglyme obtained in Reference Example was dissolved in 50 ml of a fluorine-containing solvent (Sumitomo 3M product HFE-7100), and triethylamine 1.0 was added thereto. g (1.0 mmol) and 20 ml of diethyl ether were added. To this, 1.6 g (7.0 mmol) of p-iodo-N-methylaniline was added and reacted at room temperature for 1 hour. The obtained reaction mixture was added to saturated brine, and the separated organic layer was dried over anhydrous magnesium sulfate and filtered. After distilling off the fluorine-containing solvent and diethyl ether from the filtrate under reduced pressure, the resulting viscous liquid was washed several times with diethyl ether, and then diethyl ether was completely distilled off under reduced pressure. In this way, fluorine-containing polyether compound [PFPE-I]

Was obtained as a slightly yellowish transparent liquid. The viscosity was 13 Pa · s (25 ° C.) as measured with an E-type viscometer (TEV-22 manufactured by Toki Sangyo).
¹⁹ F-NMR (chemical shift based on CFCl ₃ ): -123 ppm (F ^b )
-145ppm (F ^c )
¹ H-NMR (chemical shift from ^{TMS): 7.5ppm (H a, H} e)
6.6ppm (H ^b, H ^d)
3.1ppm (H ^c)
IR (neat): 1703cm ^-1 (C = O)
1490cm ^-1 (Ar)

参考例で得られた含フッ素カルボン酸フルオリド、フッ化セシウムおよびテトラグライムからなる混合物50g(約4.0ミリモル)を、含フッ素系溶媒(HFE-7100)50mlに溶解し、そこにトリエチルアミン0.8g(0.8ミリモル)およびジエチルエーテル20mlを加えた。これに、p-ブロモ-N-メチルアニリン1.1g(6.0ミリモル)を加え、室温で1時間反応を行った。得られた反応混合物を飽和食塩水に加え、分離した有機層を無水硫酸マグネシウムで乾燥、ロ過した。減圧下でロ液から含フッ素系溶媒およびジエチルエーテルを留去した後、得られた粘稠な液体をジエチルエーテルで数回洗浄し、次いで減圧下でジエチルエーテルを完全に留去した。このようにして、含フッ素ポリエーテル化合物〔PFPE-IBr〕

を僅かに黄色味を帯びた透明な液体として41g得た。E型粘時計(TEV-22)により粘度を測定したところ、10Pa・s(25℃)であった。
¹⁹F-NMR(ケミカルシフトはCFCl₃基準)： -123ppm(F^b)
-145ppm(F^c)
¹H-NMR(ケミカルシフトはTMS基準)： 7.4ppm(H^a、H^e)
6.6ppm(H^b、H^d)
3.1ppm(H^c)
IR(neat)： 1700cm^-1(C=O)
1490cm^-1(Ar) Example 2
Synthesis of fluorinated polyether compound [PFPE-IBr]

50 g (about 4.0 mmol) of a mixture comprising the fluorinated carboxylic acid fluoride, cesium fluoride and tetraglyme obtained in Reference Example was dissolved in 50 ml of a fluorinated solvent (HFE-7100), and 0.8 g (0.8 g) of triethylamine was dissolved therein. Mmol) and 20 ml of diethyl ether were added. To this, 1.1 g (6.0 mmol) of p-bromo-N-methylaniline was added and reacted at room temperature for 1 hour. The obtained reaction mixture was added to saturated brine, and the separated organic layer was dried over anhydrous magnesium sulfate and filtered. After distilling off the fluorine-containing solvent and diethyl ether from the filtrate under reduced pressure, the resulting viscous liquid was washed several times with diethyl ether, and then diethyl ether was completely distilled off under reduced pressure. In this way, fluorine-containing polyether compound [PFPE-IBr]

Was obtained as a slightly yellowish transparent liquid. The viscosity was measured with an E-type viscometer (TEV-22) and found to be 10 Pa · s (25 ° C.).
¹⁹ F-NMR (chemical shift based on CFCl ₃ ): -123 ppm (F ^b )
-145ppm (F ^c )
¹ H-NMR (chemical shift from ^{TMS): 7.4ppm (H a, H} e)
6.6ppm (H ^b, H ^d)
3.1ppm (H ^c)
IR (neat): 1700cm ^-1 (C = O)
1490cm ^-1 (Ar)

Example 3
100 parts by weight of the fluorine-containing polyether compound of Example 1
1,3,5-tris (4,4,5,5-tetramethyl-1,3,2-3 parts by weight
Dioxaborolan-2-yl) benzene palladium acetate 0.15 parts by weight
2- (biphenyl) dicyclohexylphosphine 0.5 parts by weight Potassium phosphate 5 parts by weight or more of each component is added to a mixed solvent consisting of 120 parts by weight of ethanol, 25 parts by weight of water and 300 parts by weight of benzotrifluoride, and at room temperature under a nitrogen atmosphere. The volatiles were removed at 40 ° C. under reduced pressure. To the obtained mixture, 10 parts by weight of acetylene black was mixed to prepare a curable composition.

  This curable composition was compression-molded at 130 ° C. for 10 minutes, and then subjected to oven vulcanization (secondary vulcanization) at 80 ° C., 5 hours, and 200 ° C. for 10 hours in a nitrogen atmosphere in order to obtain a test piece. It was.

About the obtained curable composition and vulcanizate, the following each item was measured.
Curing test: using a Monsanto disk rheometer, 130 ° C. at t _10, t _90, ML, measured normal state physical properties values of MH: JIS K6250, K6253 compliant compression set: ASTM D395 Method B compliant
For P-24 O-ring, measured at 200 ° C for 70 hours Low temperature characteristics: Measured for TR ₁₀ and TR ₂₀ in accordance with ASTM D1329 Methanol immersion test: After immersion in methanol at 25 ° C for 70 hours Measure volume change rate Hydrofluoric acid immersion test: Measure volume change rate after immersion in 10% by weight hydrofluoric acid aqueous solution at 25 ° C for 70 hours

Example 4
Instead of 2- (biphenyl) dicyclohexylphosphine used in Example 3, 0.4 parts by weight of triphenylphosphine was compression molded at 130 ° C. for 10 minutes and then subjected to oven heating at 80 ° C. for 5 hours and 200 ° C. for 10 hours. Sulfur (secondary vulcanization) was sequentially performed in a nitrogen atmosphere to obtain a test piece.

Comparative example
CF ₂ = CH ₂ / CF ₂ = CF ₂ / CF ₂ = CFOCF ₃ / CF ₂ = CFO (CF ₂ C (CF ₃ ) O) ₅ CF ₃ / CF ₂ = CFOCF ₂ CF ₂ Br (copolymerization molar ratio 70 / 10/10/9/1) copolymer (ηsp / c = 1.2; measured for 1 wt% C ₆ F ₆ solution, polymer Mooney viscosity (121 ° C.) 70) 100 parts by weight,
MT carbon black (Cancab product THERMAX N900) 30 parts by weight triallyl isocyanurate (Nippon Kasei product TAIC M60) 6 部
Organic peroxide (NIPPON OIL & PRODUCTS PERHEXA 25B-40) 1.4 〃
ZnO 4 〃
Is added and mixed with two rolls. This mixture is compression-molded at 180 ° C for 10 minutes to vulcanize a 2mm thick sheet and P-24 O-ring, which are further oven-treated at 230 ° C for 24 hours. Sulfur (secondary vulcanization) was performed, and the same measurements as in Examples 3 to 4 were performed.

The measurement results of the above Examples 3 to 4 and Comparative Example are shown in the following table.
table
Measurement item Example 3 Example 4 Comparative example
[Curing test]
Test temperature (℃) 130 130 180
t ₁₀ (min) 0.5 0.5 0.5
t ₉₀ (min) 1.2 1.1 2.6
ML (dN ・ m) 0.2 0.2 2.0
MH (dN ・ m) 2.7 2.6 10.7
[Normal properties]
Hardness 51 50 59
100% modulus (MPa) 1.2 1.1 4.5
Strength at break (MPa) 2.7 2.5 11.3
Elongation at break (%) 240 240 180
(Compression set)
200 ℃, 70 hours (%) 60 62 24
(Low temperature characteristics)
TR ₁₀ (℃) -47 -47 -39
TR ₂₀ (℃) -34 -34 -29
[Methanol immersion test]
Volume change rate (%) +3 +3 +4
[Hydrofluoric acid immersion test]
Volume change rate (%) +1 +1 +3

Claims (15)

General formula

(Where R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, Rf is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms, and X and Y are Each independently an iodine atom or a bromine atom, and the substitution positions on the phenyl groups of X and Y are each independently the m-position or the p-position with respect to the RfO bond substituent and the NR ¹ bond substituent, and n Is an integer of 30 to 130). In the above general formula, Rf is -CF ₂ CF ₂ CF ₂ - fluoropolyether compound of a is claim 1, wherein. 2. The fluorine-containing polyether compound according to claim 1, wherein Rf is —CF ₂ CF (CF ₃ ) — (wherein the side chain CF ₃ group is on the oxyphenyl group side).   The fluorine-containing polyether compound according to claim 1, wherein X and Y in the general formula are iodine atoms. The fluorine-containing polyether compound according to claim ¹ , wherein R ¹ in the general formula is a methyl group.   The fluorine-containing polyether compound according to claim 1, wherein n is an integer of 50 to 130 in the general formula. General formula

(Here, Rf is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms, X is an iodine atom or a bromine atom, and the substitution position on the phenyl group of X is the RfO bond substituent. Fluorinated carboxylic acid fluoride compound represented by the general formula: m-position or p-position, n is an integer of 30 to 130)

(Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, Y is an iodine atom or a bromine atom, and the substitution position on the phenyl group of Y is relative to the NR ¹ bond substituent. 2. The method for producing a fluorinated polyether compound according to claim 1, wherein the reaction is carried out with an aromatic primary or secondary amine compound represented by the formula (M-position or p-position).   The method for producing a fluorinated polyether compound according to claim 7, wherein the reaction is carried out in the presence of pyridine or a tertiary amine compound. (A) 100 parts by weight of the fluorine-containing polyether compound according to claim 1
(B) General formula

(Where R ² is a straight chain of 2 to 10 carbon atoms or
(This is a branched divalent aliphatic hydrocarbon group.)
Aromatic boronic acid ester compound represented by 0.1 to 10 parts by weight
(C) Zero or divalent organopalladium compound 0.0001 to 1 part by weight
(D) Basic inorganic compound or basic organic compound 0.1 to 10 parts by weight
(E) General formula

(Wherein R ³ , R ⁴ , and R ⁵ are each independently a C 1-10 chain aliphatic hydrocarbon group that can have a substituent, or a C 5-12 cycloaliphatic group. (A hydrocarbon group or an aromatic hydrocarbon group having 6 to 20 carbon atoms)
Or general formula

(Where Ph is an aliphatic hydrocarbon group having 1 to 6 carbon atoms or a phenyl group that may have a substituent,
Z is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms,
(It is an aromatic hydrocarbon group or metallocene group having 6 to 20 carbon atoms)
A curable fluorine-containing polyether composition comprising 0 to 5 parts by weight of an organic phosphorus compound represented by the formula:   The curable fluorinated polyether composition according to claim 9, wherein X and Y are iodine atoms, and the fluorinated polyether compound according to claim 1 is used as component (A). (B) Component aromatic boronic acid ester compound is 1,3,5-tris (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene

The curable fluorine-containing polyether composition according to claim 9.   The curable fluorine-containing polyether composition according to claim 9, wherein the divalent organic palladium compound (C) is palladium acetate.   The curable fluorinated polyether composition according to claim 9, wherein the component (D) basic inorganic compound is potassium phosphate. Component (E) is an organic phosphorus compound represented by the following general formula:

(Here, A, B, and C are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group or dialkylamino group having an alkyl group having 1 to 3 carbon atoms.)
The curable fluorine-containing polyether composition of Claim 9 represented by these. Component (E) is an organic phosphorus compound represented by the following general formula:

(Here, A, B, and C are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group or dialkylamino group having an alkyl group having 1 to 3 carbon atoms, (R ⁶ is a linear or cyclic aliphatic hydrocarbon group having 1 to ⁶ carbon atoms)
The curable fluorine-containing polyether composition of Claim 9 represented by these.