JPH08198926A - Fluorine-containing amido compound - Google Patents

Abstract

PURPOSE: To obtain a fluorine-containing amido compound expressed by a specific formula, having high F content, capable of providing an elastomer or a resin having low surface energy and useful as a raw material, etc., for rubber materials having heat resistance, solvent resistance and chemical resistance. CONSTITUTION: This compound is expressed by formula I [R<1> is an (un)saturated monovalent hydrocarbon; R<2> is H or an (un)substituted monovalent hydrocarbon; Q is formula II [R<3> is an (un)substituted divalent hydrocarbon which may be bound through O, N or S] or formula III [R<4> and R<5> are each an (un)substituted divalent hydrocarbon]; Rf is a divalent perfluoroalkylene or perfluoropolyether; (a) is >=0]. Furthermore, the compound is obtained by reacting a compound having acid fluoride groups at both terminals such as FCO-Rf-COF with a primary or secondary amine compound of formula IV in the presence of an acid- receiving agent such as trimethylamine.

Description

Detailed Description of the Invention

[0001]

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, mold release agents, etc. having heat resistance, solvent resistance and chemical resistance. Regarding

[0002]

BACKGROUND OF THE INVENTION 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. A resin cured product is obtained and 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, etc., and elastomers and resins having more excellent heat resistance, solvent resistance, chemical resistance, etc. Is desired.

Further, it is more desirable that the fluorine-containing elastomer or resin used as a coating material, a release agent or the like has excellent releasability and water repellency.

The present invention has been made in view of the above circumstances.
It is an object of the present invention to provide a novel fluorine-containing amide compound which is excellent in heat resistance, solvent resistance, chemical resistance, and also has excellent releasability.

[0006]

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 with a secondary amine compound represented by the formula (5) or first by reacting a compound represented by the formula (4) with a compound represented by the following general formula (6), the compound represented by the formula (5) By reacting the compound,
It was found that a novel fluorine-containing amide compound represented by the following general formula (1) can be obtained, and further, that this fluorine-containing amide compound can be an elastomer having a high fluorine content and a low surface energy, and the present invention is achieved. It came to eggplant.

[0007]

[Chemical 4]

Therefore, the present invention provides a fluorinated amide compound represented by the above formula (1).

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

[0010]

Embedded image

Here, R ¹ in the above formula (1) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 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 the monovalent hydrocarbon group of R ² is, for example, a methyl group,
Alkyl group such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group, decyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group and cycloheptyl group, vinyl group , Alkenyl groups such as allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group Examples include aralkyl groups such as phenylpropyl group and methylbenzyl group, or chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group in which some or all of hydrogen atoms of these groups are substituted with halogen atoms. To be

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

[0013]

[Chemical 6]

R ² 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 it has 1 to 20 carbon atoms, especially 2 carbon atoms. ~
10 divalent hydrocarbon groups are preferred, and 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, tolylene group, xylylene group, naphthylene group, arylene group such as biphenylene group, or part of hydrogen atoms of these groups Examples thereof include groups substituted with a halogen atom or the like, or combinations of these substituted or unsubstituted alkylene groups and arylene groups.

Further, R ³ may have one or more kinds of oxygen atom, nitrogen atom and silicon atom interposed in the middle of 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 carbon atoms, particularly 1 to 6 carbon atoms), and the silicon atom is a linear or cyclic group such as the following groups. Can be present as an organosiloxane-containing group or an organosilylene group.

[0016]

[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]

Embedded image (Me represents a methyl group.)

Further, R ⁴ and R ⁵ in the above formula (3) are substituted or unsubstituted divalent hydrocarbon groups having 1 to 10 carbon atoms, especially 2 to 6 carbon atoms, specifically, 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, or a group obtained by substituting a part of hydrogen atoms of these groups with a halogen atom or the like. It is illustrated.

The following groups are specifically exemplified as Q in the formula (1) represented by the formula (2) or the formula (3). In the chemical formulas below, Me is a methyl group, P
h represents a phenyl group.

[0020]

[Chemical 9]

[0021]

[Chemical 10]

Further, in the formula (1), Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and particularly as the divalent perfluoroalkylene group, —C _m F _2m — (where m = 1 10 and preferably 2 to 6) are preferable, and as the divalent perfluoropolyether group, those represented by the following formula are preferable.

[0023]

[Chemical 11] Specific examples of Rf include the following.

[0024]

[Chemical 12]

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

In the present invention, the fluorine-containing amide compound of the above formula (1) has a viscosity (25 ° C., the same below) of several tens cs.
From low viscosity polymers to solid raw rubber-like polymers, from the viewpoint of ease of handling, for example, a raw rubber-like polymer for a heat-vulcanized rubber and a viscosity of 100 to 100 for a liquid rubber are included. A polymer of about 100,000 cs is preferably used. 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.

The fluorine-containing amide compound of the above formula (1) is
It can be obtained by the following method. That is, the fluorinated amide compound in which a is 0 in the above formula (1) is
For example, a compound represented by the following general formula (4) having an acid fluoride group at both ends 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]

[Chemical 13] (R ¹ , R ² and Rf have the same meanings as 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 represented by the above formula (4) having an acid fluoride group at both ends and the following general formula (6). H-Q-H (6) (Q has the same meaning as described above) is reacted with a diamine compound represented by the formula (5) in the presence of an acid acceptor, and the primary or secondary structure represented by the formula (5) is used. It can be synthesized by reacting a primary amine compound.

In this case, the ratio of the amount of the compound having an acid fluoride group at both ends of the formula (4) and the primary or secondary amine compound of the formula (5) to be charged is not particularly limited, but the molar ratio is not limited. The ratio (a) of the charged amount (a) of the compound of formula (4) and the charged amount (b) of the compound of formula (5) in terms of conversion
0.1 to 1.2 mol / mol (b), especially 0.2 to
0.5 mol / mol is suitable.

In addition, the charged amount (a) of the compound of the formula (4) and the charged amount (c) of the compound of the formula (6) are, in particular, unless the amount (a) is less than the converted amount (c) on a molar basis. 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.

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.

In the fluorine-containing amide compound of the formula (1), the fluorine-containing amide compound in which Q has a silicon atom interposed is a primary or secondary fluorine-containing amide compound having an aliphatic unsaturated group such as a vinyl group or an allyl group. By using the amine compound of the above formula (5) as the primary amine compound, a compound having vinyl groups at both ends represented by the following general formula (1 ′) is synthesized by the above reaction. ) And an organosiloxane compound having two hydrosilyl groups in the molecule can be synthesized in the presence of an addition reaction catalyst.

[0034]

Embedded image (However, in the formula, R ¹ , R ² , and Rf have the same meanings as described above.) H-P-H (7) where P is a divalent organic group having a siloxane bond, and Specifically, the following groups are exemplified.

[0035]

[Chemical 15]

In this reaction, the ratio of the charged amount of the compound having a vinyl group at both ends represented by the above formula (1 ') and the compound of the formula (7) is calculated in terms of mol of the compound of the formula (1'). The charged amount (d) must be greater than the charged amount (e) of the compound of formula (7), but the ratio (d) / (e) is 2 at maximum. That is, 1 <(d) / (e) ≦ 2.

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.

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.

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.

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 is a heat-resistant, chemical-resistant, solvent-resistant material for rubber materials, material for release agents, etc. It can be used as a raw material for various purposes. For example, an elastomer can be obtained by reacting a polymer of a fluorine-containing amide compound having vinyl groups at both ends of the present invention with a compound having three or more hydrosilyl groups in one molecule in the presence of an addition reaction catalyst. You can This elastomer has a high fluorine content, so it has excellent heat resistance, solvent resistance, and chemical resistance. Also, because it has low surface energy, it has excellent releasability and water repellency, and it is a sealant, molded part, extruded part, and coating. It can be effectively used as a material, a release agent and the like.

[0041]

Industrial Applicability The fluorine-containing amide compound of the present invention can be an elastomer or 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, and a mold release. It is effective as a material for drugs.

[0042]

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

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

[0044]

Embedded image

After the dropping, the reaction is carried out at 60 ° C. for 2 hours,
The filtrate obtained by filtering the reaction mixture under pressure is 120 ° C./3.
After vacuum stripping with mmHg, 989.5 g of a pale yellow transparent liquid compound was obtained. The obtained compound is
Viscosity 9500 cs (25 ° C), specific gravity 1.829 (25
C.) and the refractive index was 1.3258 (25.degree. C.). The result of IR measurement of this compound is shown in FIG. From FIG. 1, the following absorption was recognized.

[0046]

[Chemical 17]

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

[0048]

Embedded image

Example 2 500 g of a compound represented by the following formula (11) having an acid fluoride group at both ends and equipped with a stirring bar, a thermometer, a Dimroth, and a dropping funnel.
A vinylsilylaniline 1 represented by the above formula (9) was charged from a dropping funnel while being charged in a 4-necked flask having a volume of 1 l.
20 g of a mixture of 2.4 g and 7.7 g of triethylamine
It was added dropwise at ° C.

[0050]

[Chemical 19]

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.
After vacuum stripping with mmHg, 469.4 g of a pale yellow transparent liquid compound was obtained. The obtained compound is
Viscosity 21000cs (25 ℃), specific gravity 1.884 (25
C.) and the refractive index was 1.3136 (25.degree. C.). The result of IR measurement of this compound is shown in FIG. From FIG. 2, the following absorption was recognized.

[0052]

Embedded image

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

[0054]

[Chemical 21]

Example 3 76.9 g of the compound represented by the above formula (8) having an acid fluoride group at both ends was equipped with a stirring bar, a thermometer, a Dimroth, and a dropping funnel to 200 m.
A mixture of 2,4-dimethylpiperazine (1.14 g) and triethylamine (2.9 g) was added dropwise at 20 ° C. with stirring into a 4-necked 4-neck flask and stirring.
After the dropping, the reaction was carried out at 60 ° C. for 2 hours, then 0.36 g of vinylsilylaniline represented by the above formula (9) was added, and the reaction was further carried out at 60 ° C. for 2 hours.
When post-treatment was carried out in the same manner as in, 72.9 g of a pale yellow transparent liquid compound was obtained.

The compound obtained has a viscosity of 43,200 cs.
(25 ° C). The result of IR measurement of this compound is shown in FIG. From FIG. 3, the following absorption was recognized.

[0057]

[Chemical formula 22]

The vinyl group content of this compound was determined to be 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]

[Chemical formula 23]

Example 4 100.0 g of a compound obtained in Example 1 having a vinyl group at both ends, which was obtained in Example 1 in the same apparatus as in Example 3 (viscosity: 9500c)
s; 25 ° C) and meta-xylene hexafluoride 50.0
g and were heated with stirring to 90 ° C., and 0.1 g of a 2% solution of chloroplatinic acid in isopropyl alcohol was added. Then, 4.25 g of cyclotetrasiloxane represented by the following formula (14) was added dropwise with a dropping funnel to carry out a reaction.

[0061]

[Chemical formula 24]

After the dropwise addition, while confirming the disappearance of cyclotetrasiloxane by gas chromatography while aging, the mixture was cooled to room temperature, charged with 1.5 g of activated carbon and 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.

The compound obtained has a viscosity of 87500 cs.
(25 ° C). The result of IR measurement of this compound is shown in FIG. From FIG. 4, the following absorption was recognized.

[0064]

[Chemical 25]

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

[0066]

[Chemical formula 26]

Example 5 81.6 g of a compound represented by the following formula (16) having an acid fluoride group at both ends was provided with a stirring rod, a thermometer, a Dimroth, and a dropping funnel at 200 m.
The mixture was placed in a 4-necked separ flask of 1, and 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. with stirring with a dropping funnel.

[0068]

[Chemical 27]

After the 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.
After vacuum stripping with 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.degree. C.). The result of IR measurement of this compound is shown in FIG. From FIG. 5, the following absorption was observed.

[0070]

[Chemical 28]

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

[0072]

[Chemical 29]

[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 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 and heat-treated, and then mixed on a three-roll mill. ) Fluorine-containing cyclic hydrogen siloxane 45.0 parts by weight, chloroplatinic acid (CH ₂ ═CH)
0.2 parts by weight of a toluene solution of a catalyst modified with SiMe ₂ OSiMe ₂ CH = CH ₂ (platinum concentration 1.0% by weight) was added and mixed.

[0074]

Embedded image

This was degassed under reduced pressure, placed in a rectangular frame having a thickness of 2 mm, and evacuated again to 120 kg / cm ² ,
It was press-cured at 150 ° C. for 10 minutes. The test piece was cut out from the cured sample, and the physical properties were measured according to JIS K6301, and the results shown below 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, using the above test pieces, heat resistance, chemical resistance, solvent swelling property, low temperature characteristics and moisture permeability were measured. 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 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 the fluorinated amide compound of Example 2.

FIG. 3 is a chart showing an IR spectrum of a fluorinated amide compound of Example 3.

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

5 is a chart showing an IR spectrum of a fluorinated amide compound of Example 5. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 83/07 LRP 83/08 LRN (72) Inventor Takatoshi Matsuda Daijin, Matsuida-cho, Usui-gun, Gunma Prefecture No. 1 No. 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Yasushi Yamamoto Matsuda-cho, Usui-gun Gunma Prefecture Hitomi No. 1 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. A fluorine-containing amide compound represented by the following general formula (1). Embedded image [Wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group,
R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group,
Q is a group represented by the following general formula (2) or the following general formula (3): (However, R ³ in the formula represents a substituted or unsubstituted divalent hydrocarbon group which may have one or more oxygen atoms, nitrogen atoms and silicon atoms interposed in the middle of the bond.) (However, in the formula, R ⁴ and R ⁵ represent a substituted or unsubstituted divalent hydrocarbon group.), Rf is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and a is 0. It is an integer above the above. ]