JP2943644B2 - Fluorine-containing amide compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing amide compound which can be effectively used as a raw material for rubber materials and release agents having heat resistance, solvent resistance and chemical resistance. About.

[0002]

2. Description of the Related Art Conventionally, fluorine-containing organic compounds have been used in various fields. For example, a fluorine-containing elastomer is obtained by crosslinking a polymer of a fluorine-containing organic compound with a crosslinking agent. And a cured resin, which are used as a rubber material, a paint and a release agent.

However, conventional fluorine-containing elastomers and resins may not have sufficient heat resistance, solvent resistance, chemical resistance and the like, and elastomers and resins which are more excellent in heat resistance, solvent resistance, chemical resistance, etc. Is desired.

Further, it is more desirable that the fluoroelastomer or resin used as a paint, a release agent or the like has more excellent releasability and water repellency.

[0005] The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a novel fluorinated amide compound which is excellent in heat resistance, solvent resistance, and chemical resistance and which gives a fluorinated elastomer or resin excellent in mold release properties.

[0006]

The present inventors have made intensive studies to achieve the above object, and as a result, for example, a compound having an acid fluoride group at both terminals represented by the following general formula (4) and a compound represented by the following general formula (4): By reacting a compound of the formula (4) with a compound of the following general formula (6) by reacting a secondary amine compound of the formula (5) or a compound of the formula (5) By reacting the compounds,
The present inventors have found that a novel fluorine-containing amide compound represented by the following general formula (1) can be obtained, and that this fluorine-containing amide compound can be an elastomer having a high fluorine content and a low surface energy. I've reached the point.

[0007]

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Accordingly, the present invention provides a fluorine-containing amide compound represented by the above formula (1).

Hereinafter, the present invention will be described in more detail. The fluorine-containing amide compound of the present invention is represented by the following general formula (1).

[0010]

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Here, R ¹ in the above formula (1) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10, especially 1 to 8, carbon atoms, preferably excluding an aliphatic unsaturated bond. Yes, R ²
Is a hydrogen atom or a monovalent hydrocarbon group similar to R ¹ . R ¹
And R ^{2 as} a monovalent hydrocarbon group include, for example, a methyl group,
Ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, decyl and other alkyl groups, cyclopentyl, cyclohexyl, cycloheptyl and other cycloalkyl groups, vinyl groups , Allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, alkenyl group such as cyclohexenyl group, phenyl group, tolyl group, xylyl group, aryl group such as naphthyl group, benzyl group, phenylethyl group Aralkyl groups such as phenylpropyl group and methylbenzyl group, or chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group and the like in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms. .

In the above formula (1), Q is a group represented by the following general formula (2) or (3).

[0013]

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R ² in the above formula (2) is the same as above, and R ³ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, particularly 2 to 10 carbon atoms. A hydrogen group; specifically, a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, an alkylene group such as a hexamethylene group, a cycloalkylene group such as a cyclohexylene group, a phenylene group, a tolylene group, and a xylylene group. ,
An arylene group such as a naphthylene group and a biphenylene group, a group in which a part of hydrogen atoms of these groups is substituted with a halogen atom, or a combination of these substituted or unsubstituted alkylene groups and arylene groups.

R ³ may have one or more of oxygen, nitrogen and silicon atoms interposed in the bond. In this case, the oxygen atom is -O-, and the nitrogen atom is -NR '.
-(R 'is a hydrogen atom or an alkyl group or an aryl group having 1 to 8, particularly 1 to 6 carbon atoms), and the silicon atom is a straight-chain or cyclic group as shown below. It can be interposed as an organosiloxane-containing group or an organosilylene group.

[0016]

Embedded image (Provided that R ″ is the same alkyl group or aryl group having 1 to 8 carbon atoms as those exemplified as R ¹ and R ² , and R ^{′ ″} is 1 to 2 carbon atoms similar to those exemplified as R ³ . 6 is an alkylene group or an arylene group, and n is an integer of 0 to 10, particularly 0 to 5.) Examples of such a group include the following groups.

[0017]

Embedded image (Me represents a methyl group.)

Further, R ⁴ and R ⁵ in the above formula (3) are a substituted or unsubstituted divalent hydrocarbon group having 1 to 10, particularly 2 to 6, carbon atoms, and specifically include a methylene group, An alkylene group such as an ethylene group, a propylene group, a methylethylene group, a butylene group, and a hexamethylene group; a cycloalkylene group such as a cyclohexylene group; or a group in which some of the hydrogen atoms of these groups are substituted with halogen atoms.

Specific examples of Q in the formula (1) represented by the above formula (2) or (3) include the following groups. In the following chemical formula, Me is a methyl group, P
h represents a phenyl group.

[0020]

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[0021]

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In the formula (1), Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and the divalent perfluoroalkylene group is -C _m F _2m- (where m = 1 to 10, preferably 2 to 6.), and the divalent perfluoropolyether group is represented by the following formula.

[0023]

Embedded image The following are specifically exemplified as Rf.

[0024]

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In the above formula (1), a is 0 to 10
Therefore, the fluorine-containing amide compound of the formula (1) contains one or more divalent perfluoroalkylene group or divalent perfluoropolyether group in one molecule, and a is particularly preferably 1 to 6. It is an integer.

In the present invention, the fluorine-containing amide compound of the above formula (1) has a viscosity (25 ° C., the same applies hereinafter) of several tens cs.
From low-viscosity polymers to solid raw rubber-like polymers, but from the viewpoint of ease of handling, for example, raw rubber-like polymers for hot vulcanized rubber, and viscosities of 100 to 100 for liquid rubber. A polymer of about 100,000 cs is preferably used. If the viscosity is too low, the resulting cured product will have a low elongation as an elastomer, and may not have balanced physical properties.

The fluorine-containing amide compound of the above formula (1) is
It can be obtained by the following method. That is, the fluorine-containing amide compound in which a is 0 in the formula (1) is
For example, a compound having an acid fluoride group at both terminals represented by the following general formula (4) and a primary or secondary amine compound represented by the following general formula (5) are reacted in the presence of an acid acceptor such as trimethylamine. Can be synthesized by

[0028]

Embedded image (R ¹ , R ² , and Rf have the same meaning as described above.)

Further, the fluorine-containing amide compound in which a is an integer of 1 or more in the above formula (1) is, for example, a compound having an acid fluoride group at both terminals represented by the above formula (4) and the following general formula (6) HQH (6) (wherein Q has the same meaning as described above) is reacted with a diamine compound in the presence of an acid acceptor, and further reacted with a primary or secondary compound represented by the above formula (5). It can be synthesized by reacting a secondary amine compound.

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 primary or secondary amine compound of the formula (5) is not particularly limited, but is In conversion, the ratio (a) / (a) / the charged amount (a) of the compound of the formula (4) and the charged amount (b) of the compound of the formula (5)
(B) is 0.1 to 1.2 mol / mol, especially 0.2 to
It is preferable that the concentration be 0.5 mol / mol.

The charged amount (a) of the compound of the formula (4) and the charged amount (c) of the compound of the formula (6) are not particularly limited as long as (a) is not smaller than (c) in terms of mole. It is not limited. The repeating unit a in the formula (1) is
By adjusting (a) / (c), an appropriate value according to the purpose can be obtained. By increasing (a) / (c), a polymer having a relatively small molecular weight can be synthesized,
When the value of (a) / (c) approaches 1, a polymer having a large molecular weight can be synthesized.

The conditions for the above reaction are not particularly limited.
20 to 100 ° C for 1 to 8 hours, preferably 20 to 50 ° C
For 2 to 4 hours.

In the fluorinated amide compound of the formula (1), the fluorinated amide compound in which Q has a silicon atom interposed therebetween is, for example, a primary or secondary compound having an aliphatic unsaturated group such as a vinyl group or an allyl group. For example, a compound having a vinyl group at both terminals represented by the following general formula (1 ′) is synthesized by the above reaction using the amine compound of the above formula (5) as a primary amine compound. The compound can be synthesized by reacting an organosiloxane compound having two hydrosilyl groups in the molecule shown in the above) in the presence of an addition reaction catalyst.

[0034]

Embedded image (Wherein, R ¹ , R ² , and Rf have the same meanings as described above). HP—H (7) wherein P is a divalent organic group having a siloxane bond. Specifically, the following groups are exemplified.

[0035]

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In this reaction, the ratio of the charged amount of the compound having a vinyl group at both terminals represented by the above formula (1 ′) to the compound of the formula (7) is calculated in terms of moles of the compound of the formula (1 ′). The charge (d) must be greater than the charge (e) of the compound of formula (7), but the ratio (d) / (e) is at most 2. That is, 1 <(d) / (e) ≦ 2.

By increasing (d) / (e), a polymer having a relatively small molecular weight can be synthesized.
When the value of (d) / (e) approaches 1, a polymer having a large molecular weight can be synthesized.

[0038] In this case, the catalyst may be selected from the VI of the periodic table.
Group II elements or compounds thereof, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972), complexes of chloroplatinic acid with olefins (U.S. Pat.
No. 159601, No. 3159662, No. 3775
No. 452), platinum black or palladium is alumina,
Silica, carbon-supported carrier, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson's catalyst), etc.
The addition amount can be a catalyst amount. The above complex is preferably used after being dissolved in an alcohol, ketone, ether or hydrocarbon solvent.

The conditions for the above reaction are 50 to 150.
C., preferably at 80 to 120.degree. C. for 2 to 4 hours.

Since the fluorine-containing amide 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 heat-resistant, chemical-resistant and solvent-resistant material for rubber materials and release agent. It can be used for various applications as a raw material for. For example, an elastomer can be obtained by reacting a polymer of a fluorine-containing amide compound having a vinyl group at both terminals of the present invention with a compound having three or more hydrosilyl groups in one molecule in the presence of an addition reaction catalyst. Can be. This elastomer has a high fluorine content, so it has excellent heat resistance, solvent resistance, and chemical resistance.It also has a low surface energy, so it has excellent release properties and water repellency, and sealants, molded parts, extruded parts, and coatings. It can be effectively used as a material, a release agent and the like.

[0041]

The fluorine-containing amide compound of the present invention can be an elastomer or a resin having a high fluorine content and a low surface energy, and is a material for rubber materials having heat resistance, solvent resistance, and chemical resistance. It is effective as a drug material.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the following, Me indicates a methyl group.

Example 1 1000 g of a compound having an acid fluoride group at both terminals represented by the following formula (8) was charged into a 1-liter four-necked flask equipped with a stir bar, a thermometer, a Dim funnel, and a dropping funnel. , A vinylsilylaniline 7 represented by the following formula (9)
A mixture of 2.0 g and 44.8 g of triethylamine was added to 2
It was added dropwise at 0 ° C.

[0044]

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After the addition, the reaction was carried out at 60 ° C. for 2 hours.
The filtrate obtained by filtering the reaction mixture under pressure was subjected to 120 ° C / 3
Stripping under reduced pressure at mmHg yielded 989.5 g of a pale yellow transparent liquid compound. The resulting compound is
Viscosity 9500cs (25 ° C), specific gravity 1.829 (25
° C) and the refractive index was 1.3258 (25 ° C). FIG. 1 shows the results of IR measurement of this compound. 1. From FIG. 1, the following absorption was observed.

[0046]

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When the vinyl group content of this compound was determined, it was 0.035 mol / 100 g. The obtained compound was a polymer of a fluorine-containing amide compound represented by the following structural formula (10). confirmed.

[0048]

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Example 2 500 g of a compound having an acid fluoride group at both terminals represented by the following formula (11) was attached with a stirring bar, a thermometer, a Dim funnel, and a dropping funnel to 500 m.
of a vinylsilylaniline 1 represented by the above formula (9) from a dropping funnel while stirring.
A mixture of 2.4 g and 7.7 g of triethylamine was added to 20
It was added dropwise at ° C.

[0050]

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After the addition, the reaction was carried out at 60 ° C. for 2 hours.
The filtrate obtained by filtering the reaction mixture under pressure was subjected to 120 ° C / 3
After stripping under reduced pressure at mmHg, 469.4 g of a pale yellow transparent liquid compound was obtained. The resulting compound is
Viscosity 21000 cs (25 ° C.), specific gravity 1.884 (25
° C) and the refractive index was 1.3136 (25 ° C). FIG. 2 shows the results of IR measurement of this compound. From FIG. 2, the following absorption was observed.

[0052]

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The amount of the vinyl group in this compound was determined to be 0.013 mol / 100 g. The obtained compound was a polymer of a fluorine-containing amide compound represented by the following structural formula (12). confirmed.

[0054]

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Example 3 A compound (76.9 g) having an acid fluoride group at both terminals represented by the above formula (8) was provided with a stirring bar, a thermometer, a Dim funnel, and a dropping funnel to 200 m.
Then, a mixture of 1.14 g of 2,5-dimethylpiperazine and 2.9 g of triethylamine was added dropwise at 20 ° C. from a dropping funnel while stirring.
After the dropwise addition, the reaction was carried out at 60 ° C. for 2 hours. Thereafter, 0.36 g of vinylsilylaniline represented by the formula (9) was added, and the reaction was further carried out at 60 ° C. for 2 hours.
As a result, 72.9 g of a pale yellow transparent liquid compound was obtained.

The compound obtained had a viscosity of 43200 cs
(25 ° C.). FIG. 3 shows the results of IR measurement of this compound. From FIG. 3, the following absorption was observed.

[0057]

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When the vinyl group content of this compound was determined, it was 0.005 mol / 100 g, and the obtained compound was a polymer of a fluorine-containing amide compound represented by the following structural formula (13). confirmed.

[0059]

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Example 4 100.0 g of a compound having a vinyl group at both ends represented by the above formula (10) (viscosity: 9500 c) obtained in Example 1 in the same apparatus as in Example 3
s; 25 ° C) and meta-xylene hexafluoride 50.0
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. Thereafter, 4.25 g of cyclotetrasiloxane represented by the following formula (14) was added dropwise from a dropping funnel, and a reaction was performed.

[0061]

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After the dropwise addition, the disappearance of cyclotetrasiloxane was confirmed by gas chromatography while aging, then cooled to room temperature, activated carbon (1.5 g) was added, and the mixture was stirred for 2 hours. This was subjected to the same post-treatment as in Example 1 to obtain 99.2 g of a transparent liquid compound.

The compound obtained had a viscosity of 87500 cs
(25 ° C.). FIG. 4 shows the results of IR measurement of this compound. From FIG. 4, the following absorption was observed.

[0064]

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When the vinyl group content of this compound was determined, it was 0.009 mol / 100 g. The obtained compound was a polymer of a fluorine-containing amide compound represented by the following structural formula (15). confirmed.

[0066]

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Example 5 A compound represented by the following formula (16) having an acid fluoride group at both terminals at 81.6 g was equipped with a stirring bar, a thermometer, a Dim funnel, and a dropping funnel to 200 m.
Then, a mixture of 2.8 g of vinylsilylaniline represented by the following formula (17) and 1.0 g of triethylamine was added dropwise at 20 ° C. from a dropping funnel with stirring to a four-necked four-necked separa flask.

[0068]

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After the addition, the reaction was carried out at 60 ° C. for 2 hours.
The filtrate obtained by filtering the reaction mixture under pressure was subjected to 120 ° C / 3
After stripping under reduced pressure at mmHg, 76.8 g of a pale yellow transparent liquid compound was obtained. The obtained compound had a viscosity of 9800 cs (25 ° C.) and a specific gravity of 1.873 (25
° C) and the refractive index was 1.3126 (25 ° C). FIG. 5 shows the result of IR measurement of this compound. From FIG. 5, the following absorption was observed.

[0070]

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When the vinyl group content of this compound was determined, it was 0.013 mol / 100 g. The obtained compound was a polymer of a fluorine-containing amide compound represented by the following structural formula (18). confirmed.

[0072]

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[Application Example 1] The polymer obtained in Example 1 and represented by the above formula (10) (viscosity 9500 cs, average molecular weight 5720, vinyl group content 0.035 mol / 100
g) 10 parts by weight of a fumed silica having a specific surface area of 200 m ² / g treated with a trimethylsiloxy group was added to 100 parts by weight, mixed, heat-treated, and then mixed on a three-roll mill. 45.0 parts by weight of fluorinated cyclic siloxane represented by), chloroplatinic acid CH ₂ = CH
0.2 parts by weight of a toluene solution (platinum concentration: 1.0% by weight) of a catalyst modified with SiMe ₂ OSiMe ₂ CH ＝ CH ₂ was added and mixed.

[0074]

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This was defoamed under reduced pressure, placed in a rectangular frame having a thickness of 2 mm, evacuated again, and dried at 120 kg / cm ² .
Press hardening was performed at 150 ° C. for 10 minutes. The test piece was cut out from the cured sample, and the physical properties were measured in accordance with JIS K6301, and the following results were obtained.

Hardness (JIS-A) 46 Elongation (%) 240 Tensile strength (kgf / cm ² ) 59 (JIS-A: Measured using an A-type spring hardness tester specified in JIS K6301)

Next, heat resistance, chemical resistance, solvent swellability, low-temperature characteristics and moisture permeability were measured using the test pieces. The results are shown in Table 1, Table 2, Table 3, Table 4, and Table 5.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

[Table 4]

[0082]

[Table 5]

[Brief description of the drawings]

FIG. 1 is a chart showing an IR spectrum of a fluorine-containing amide compound of Example 1.

FIG. 2 is a chart showing an IR spectrum of a fluorine-containing amide compound of Example 2.

FIG. 3 is a chart showing an IR spectrum of a fluorine-containing amide compound of Example 3.

FIG. 4 is a chart showing an IR spectrum of the fluorine-containing amide compound of Example 4.

FIG. 5 is a chart showing an IR spectrum of a fluorine-containing amide compound of Example 5.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Koji Matsuda, Inventor, Silicone Electronics Materials Research Laboratory, Shinjuku Chemical Industry Co., Ltd. 1-10, Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture (72) Yasushi Yamamoto, Usui-gun, Gunma Prefecture No. 1 Hitomi, Matsuida-machi, Japan Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) References JP-A-8-199070 (JP, A) JP-A-8-100482 (JP, A) JP 6-256500 (JP, A) JP-A-6-234923 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 65/00-65/32 C08G 69/40-69 / 42 CA (STN)

Claims (2)

(57) [Claims] 1. A fluorine-containing amide compound represented by the following general formula (1). Embedded image [However, in the formula, R ¹ is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, and a group in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms. Selected monovalent hydrocarbon group, R ²
Is a hydrogen atom or a monovalent hydrocarbon group similar to R ^1, and Q is a group represented by the following general formula (2) or (3): (However, in the formula, R ³ represents an alkylene group, a cycloalkylene group, an arylene group having 1 to 20 carbon atoms which may have one or more of an oxygen atom, a nitrogen atom and a silicon atom interposed therebetween. And a divalent hydrocarbon group selected from a group obtained by substituting a part of the hydrogen atoms of the group with a halogen atom, and a group obtained by combining the above-mentioned alkylene group and arylene group.) (Wherein, R ⁴ and R ⁵ represent a divalent hydrocarbon group having 1 to 10 carbon atoms and selected from an alkylene group, a cycloalkylene group and a group in which a part of hydrogen atoms of these groups is substituted with a halogen atom) Rf is a divalent perfluoroalkylene group represented by —C _m F _2m — (m = 1 to 10) or a compound represented by the following formula: A is a divalent perfluoropolyether group selected from the groups represented by ] ^2. The aryl group of R ¹ and R ² is a phenyl group,
A tolyl group or a xylyl group, an aralkyl group is a benzyl group, a phenylethyl group, a phenylpropyl group or a methylbenzyl group, and the arylene group of R ³ is a phenylene group, a tolylene group, a xylylene group, a naphthylene group or a biphenylene group. , R ^3, the oxygen atom intervening in the bond is —O—, the nitrogen atom is —NR′— (R ′ is a hydrogen atom or an alkyl group or an aryl group having 1 to 8 carbon atoms), and the silicon atom is ] (However, R ″ is an alkyl group or aryl group having 1 to 8 carbon atoms, R ″ ′ is an alkylene group or arylene group having 1 to 6 carbon atoms, and n is an integer of 0 to 10.) The fluorinated amide compound according to claim 1, wherein