JP2991059B2 - Organic fluorine compounds - 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 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]

2. Description of the Related Art Conventionally, organic fluorine compounds have been used in various fields.
For example, an elastomer is obtained by cross-linking a polymer of an organic fluorine compound using a cross-linking agent, and is used as a rubber material and a release agent.

[0003] However, conventional elastomers obtained from organic fluorine compounds may not have sufficient solvent resistance and chemical resistance in some cases, and elastomers having more excellent solvent resistance and chemical resistance are desired.

[0004] Further, it is more desirable that the elastomer used as a sealant, a molded part or the like has further excellent releasability and water repellency.

[0005] The present invention has been made in view of the above circumstances,
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 which gives an elastomer having excellent releasability and water repellency.

[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 secondary amine compound represented by the formula (5) and, if necessary, a compound represented by the following general formula (6) in the presence of an acid acceptor, the compound is represented by the following general formula (1) The present inventors have found that a novel organic fluorine compound can be obtained, and that this organic fluorine compound can be an elastomer having a high fluorine content and a low surface energy, and the present invention has been accomplished.

[0007]

Embedded image Wherein R ¹ and R ² each represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group or a part or all of the hydrogen atoms of these groups substituted with halogen atoms. However, ^one of R ¹ and R ² is an alkenyl group. Q is a group represented by the following general formula (2) or the following general formula (3)

Embedded image (However, in the formula, R ³ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group, an arylene group, or an alkylene 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. A group in which part or all of the hydrogen atoms of the group are substituted with halogen atoms.)

Embedded image (In the formula, R ⁴ and R ^{5 each} represent an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group, or a group in which part or all of the hydrogen atoms of these groups have been substituted with halogen atoms.)
f is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and a is an integer of 0 or more. Accordingly, the present invention provides an organic fluorine compound represented by the above formula (1).

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

[0009]

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Here, as R ¹ and R ² in the above formula (1), a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10, especially 1 to 8 carbon atoms, is suitable, for example, a methyl group , Ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,
Alkyl group such as decyl group, cyclopentyl group, cyclohexyl group, cycloalkyl group such as cycloheptyl group, vinyl group, 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,
Aralkyl groups such as phenylethyl group and phenylpropyl group, or chloromethyl group, bromoethyl group, chloropropyl group, and trifluoro group in which part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, and bromine; Examples include a propyl group, and ^one of R ¹ and R ² is an alkenyl group. In this case, R ¹ is particularly preferably an alkenyl group having 2 to 8 carbon atoms.

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

[0012]

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R ¹ in the above formula (2) is the same as described above, and R ³ is an alkylene group, cycloalkylene group, arylene group having 1 to 20 carbon atoms, particularly 2 to 10 carbon atoms, or hydrogen of these groups. A group in which some or all of the atoms have been substituted with halogen atoms, specifically, a methylene group, an ethylene group,
Alkylene groups such as propylene group, methylethylene group, butylene group and hexamethylene group; cycloalkylene groups such as cyclohexylene group; arylene groups such as phenylene group, tolylene group, xylylene group, naphthylene group and biphenylene group, or these groups A group in which part or all of the hydrogen atoms of the above are 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-, the nitrogen atom is -NR'- (R 'is a hydrogen atom or a group having 1 to 8 carbon atoms,
6 to an alkyl group or an aryl group), and the silicon atom is interposed as a group containing a linear or cyclic organosiloxane or an organosilylene group, for example, as shown below. Can be.

[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) represent an alkylene group or cycloalkylene group having 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms, or a part or all of the hydrogen atoms of these groups is halogen. An alkylene group such as a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, and a hexamethylene group; a cycloalkylene group such as a cyclohexylene group; Examples thereof include groups in which part or all of the hydrogen atoms have been substituted with halogen atoms.

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

[0020]

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In the equation (1), Rf Is bivalent purf
Fluoroalkylene group or divalent perfluoropolyether
And particularly as a divalent perfluoroalkylene group, -C_mF_2m-(Where m = 1 to 10, preferably 1 to 6)
The divalent perfluoropolyate is preferred.
As the alkyl group, those represented by the following formula are preferred.

[0022]

Embedded imageRf Specifically, the following are exemplified.

[0023]

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In the above formula (1), a is an integer of 0 or more. Therefore, the organic fluorine compound of the formula (1) is 1
A molecule containing one or more divalent perfluoroalkylene group or divalent perfluoropolyether group in the molecule,
Is preferably an integer of 0 to 10, especially 0, 1, 2,
3, 4, 5, and 6 are exemplified.

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 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 hot vulcanized rubber, and a polymer having a viscosity of about 100 to 100,000 cs is preferably used for liquid rubber. 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 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 above formula (1) is, for example, a compound having an acid fluoride group at both terminals represented by the following general formula (4) and a secondary amine represented by the following general formula (5) The compound can be synthesized by reacting the compound with an acid acceptor such as trimethylamine.

[0027]

Embedded image(R¹, R^Two, Rf Has the same meaning as described above. )

Further, in the above formula (1), a is 1 or more.
The organic fluorine compound which is an integer is, for example, the above formula (4)
A compound having an acid fluoride group at both ends shown and the following
General formula (6) HQ −H (6) (Q Has the same meaning as described above. ) At both ends
Reacts with a compound having an amino group in the presence of an acid acceptor.
And further reacting the secondary amine compound represented by the above formula (5)
Can be synthesized.

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 is calculated in terms of mol. The ratio (a) / (b) of the charged amount (a) of the compound of the formula (4) to the charged amount (b) of the compound of the formula (5) is from 0.5 to
It is preferable to set it to 2 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.

The organic fluorine compound of the formula (1)
And Q Fluorination in which is mediated by a silicon atom
The compound is a secondary amine compound of the formula (5), for example, R
¹Is an allyl group or the like, and HR^TwoN-CH_TwoCH = CH_TwoEtc.
Using a secondary amine compound having an aliphatic unsaturated group
By the above reaction, for example, the compound represented by the following general formula (7) is used.
Of compounds having allyl groups at both ends
For example, a compound represented by the following general formula (8)
It can be synthesized by reacting in the presence of a medium.
You.

[0033]

Embedded image(Where R^Two, Rf Has the same meaning as described above. )

[0034]

Embedded image

In this reaction, the ratio of the amount of the compound of the formula (8) to the amount of the compound of the formula (8) and the amount of the compound of the formula (7) in terms of moles is expressed by the following formula. (D) must be greater than the charge (e) of the compound of formula (8), but the ratio (d) / (e) is at most 2
It is. 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.

[0037] In this case, the catalyst may be the VI in 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 organofluorine 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 a rubber material and a release agent material having chemical resistance and solvent resistance. It can be used for applications. For example, an elastomer can be obtained by reacting a polymer of an organic fluorine compound having both ends blocked with an alkenyl group and a compound having three or more hydrosilyl groups in one molecule in the presence of an addition reaction catalyst. . This elastomer has a high fluorine content, so it has excellent solvent resistance and chemical resistance.It also has a low surface energy, so it has excellent mold releasability and water repellency. It can be used effectively as a mold agent and the like.

[0040]

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 material for solvent-resistant and chemical-resistant rubber materials and a material for mold release agents. It is.

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 189.2 g (viscosity: 430 cs; 25 ° C.) of a compound having an acid fluoride group at both terminals represented by the following formula (9) was equipped with a stirring bar, a thermometer, a Dim funnel, and a 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 with stirring.

[0043]

Embedded image

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 189.5 g of a pale yellow, transparent liquid compound. The resulting compound is
Viscosity 841cs (25 ° C), specific gravity 1.832 (25
° C) and the refractive index was 1.3138 (25 ° C). FIG. 1 shows the results of IR measurement of this compound. 1. From FIG. 1, the following absorption was observed.

[0045]

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The amount of allyl groups in this compound was determined to be 0.031 mol / 100 g. 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]

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Example 2 The same apparatus as in Example 1 was charged with 189.2 g of a compound having an acid fluoride group at both terminals represented by the above formula (9) (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 performed in the same manner as in Example 1.
190.1 g of a pale yellow transparent liquid compound was obtained.

The compound obtained had a viscosity of 1192 cs (2
5 ° C.), specific gravity 1.841 (25 ° C.), refractive index 1.320
8 (25 ° C.). FIG. 2 shows the results of IR measurement of this compound. From FIG. 2, the following absorption was observed.

[0050]

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When the amount of allyl groups in this compound was determined, it was 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]

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Example 3 76.9 g of a compound having an acid fluoride group at both terminals represented by the above formula (9) (viscosity:
430 cs; 25 ° C.) with a 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 dropped at 20 ° C. from the dropping funnel with stirring. After the dropwise addition, the reaction was carried out at 60 ° C. for 2 hours. Thereafter, 0.36 g of methylallylamine was added, and the reaction and post-treatment were carried out in the same manner as in Example 1. As a result, 72.9 g of a pale yellow transparent liquid compound was obtained. was gotten.

The compound obtained had a viscosity of 25200 cs
(25 ° C.). FIG. 3 shows the results of IR measurement of this compound. From FIG. 3, the following absorption was observed.

[0055]

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The amount of allyl groups in this compound was determined to be 0.005 mol / 100 g. 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]

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Example 4 In the same apparatus as in Example 3, 100.0 g of a compound having an allyl group at both terminals represented by the following formula (13) (viscosity: 1192 cs; 25 ° C.) and m-xylene hexafluoride 50 were used. Then, the mixture was heated to 90 ° C. while stirring, and 0.1 g of a 2% solution of chloroplatinic acid in isopropyl alcohol was added. Thereafter, 3.66 g of cyclotetrasiloxane represented by the following formula (14) was added dropwise from a dropping funnel to carry out a reaction.

[0059]

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After the dropwise addition, the disappearance of cyclotetrasiloxane was confirmed by gas chromatography while aging, and 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 30700 cs
(25 ° C.). FIG. 4 shows the results of IR measurement of this compound. From FIG. 4, the following absorption was observed.

[0062]

Embedded image

When the amount of allyl groups in this compound was determined, it was 0.007 mol / 100 g. 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]

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Example 5 The same apparatus as in Example 1 was charged with 200.0 g of a compound represented by the following formula (16) having an acid fluoride group at both terminals (viscosity: 2100 cs; 25 ° C.) and stirred. A mixture of 3.6 g of allylaniline and 2.8 g of triethylamine was added from the dropping funnel to 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]

Embedded image

The obtained compound had a viscosity of 3300 cs (2
5 ° C.), specific gravity 1.883 (25 ° C.), refractive index 1.309
(25 ° C.). FIG. 5 shows the result of IR measurement of this compound. From FIG. 5, the following absorption was observed.

[0068]

Embedded image

When the amount of allyl groups in this compound was determined, it was 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]

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[Brief description of the drawings]

FIG. 1 is a chart showing an IR spectrum of an organic fluorine compound of Example 1.

FIG. 2 is a chart showing an IR spectrum of the organic fluorine compound of Example 2.

FIG. 3 is a chart showing an IR spectrum of the organic fluorine compound of Example 3.

FIG. 4 is a chart showing an IR spectrum of the organic fluorine compound of Example 4.

FIG. 5 is a chart showing an IR spectrum of the organic fluorine compound of Example 5.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Koji Matsuda, Inventor, 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside Silicone Electronic Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (56) References JP-A-6-1850 (JP, A) JP-A-5-331292 (JP, A) JP-A-6-271765 (JP, A) JP-A-61-166834 (JP, A) JP-A-63-22550 (JP, A) JP-A-2-99519 (JP, A) JP-A-57-99551 (JP, A) JP-T-Hei 6-504804 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) CA ( STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. An organic fluorine compound represented by the following general formula (1). Embedded image Wherein R ¹ and R ² each represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group or a part or all of the hydrogen atoms of these groups substituted with halogen atoms. However, ^one of R ¹ and R ² is an alkenyl group. Q is a group represented by the following general formula (2) or the following general formula (3): (However, in the formula, R ³ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group, an arylene group, or an alkylene 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. A group in which part or all of the hydrogen atoms of a group are substituted with halogen atoms.) (In the formula, R ⁴ and R ^{5 each} represent an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group, or a group in which part or all of the hydrogen atoms of these groups have been substituted with halogen atoms.) A is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and a is an integer of 0 or more. ] 2. In the formula (2), R ³ is -O-, -N
R ′-(R ′ is a hydrogen atom or an alkyl group or an aryl group having 1 to 8 carbon atoms) or the following formula: (However, R ″ is an alkyl group or an aryl group having 1 to 8 carbon atoms, R ″ ′ is an alkylene group or an arylene group having 1 to 6 carbon atoms, and n is an integer of 0 to 10.) 1 carbon atom which may intervene one or more of the groups shown
The organic fluorine compound according to claim 1, which is an alkylene group, a cycloalkylene group, an arylene group, or a group in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms. 3. Rf is a group represented by the following formula: The organic fluorine compound according to claim 1 or 2, which is selected from the group consisting of: