JPS63255288A - Fluorine-containing organosilicon compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is lower alkyl; X is F or H; n is 1-4 integer; a is 1-3 integer). USE:An intermediate for producing a fluorine-containing silicone resin, a lubricant for magnetic recording medium and a surface treatment. PREPARATION:For example, hexafluoropropylene oxide is polymerized to give a compound shown by formula II containing acid fluorides at the ends, which is reacted with an alkali metallic fluoride to give a fluoroalcoholate compound. Then this compound is reacted with an allyl halide to give a fluorinated allyl ether shown by formula III, which is reacted with a silane compound shown by formula IV to give a compound shown by formula I.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel fluorine-containing organosilicon compound.

[Conventional technology]

Organosilicon compounds having fluoroalkyl ether groups have surface activity, lubricity, T8 water damage oiliness, etc.
Many of them are useful as surfactants, lubricants, various surface treatment agents, etc. It is also used as a raw material for modified silicone resins having the above-mentioned properties.

Conventionally, as an organosilicon compound having such a fluoroalkyl ether group, for example, the formula (i): [wherein, Rf is the formula: F-(CFCF, O), -CF
- (here CF3CFx, n is an integer of 1 or more), R is an alkyl group, and a is an integer of O to 3 A fluoroalkyl group or a fluoroalkyl ether group represented by the formula (ii) (where m is an integer of 0 or more); R1 and R2 are atoms or -valent groups; and R'', R4 and R5 are non-hydrogen atoms or -valent groups] (Japanese Unexamined Patent Publication No. 57-93988)
; Formula (iii): Rf-C-OCH1CH2CH2-3iC13(iii
) [In the formula, Rf is the same as in formula (i)] (Japanese Patent Application Laid-Open No. 129827/1983), etc. are known.

[Problem that the invention seeks to solve]

However, the compound represented by the formula (i) has a problem in that it is easily hydrolyzed and unstable because fluorine is bonded to the α-position carbon atom of the amide bond.

The compound represented by formula (ii) has fluorine bonded to the β-position carbon atom of a silicon atom, but this structure has a problem of being unstable due to the strong affinity between the silicon atom and the fluorine atom. be. Moreover, as a compound of this formula (ii), a compound in which a small number of R3-R5 (one of which is a chlorine atom) bonded to a silicon atom is not specifically known. It is necessary to conduct the process at 140° C., which has the drawback of requiring a large amount of energy and expensive equipment.

The compound represented by formula (iii) has a problem in that the ester bond is easily hydrolyzed and has low stability because a fluorine atom is bonded to the α-position carbon atom of the ester bond.

Therefore, an object of the present invention is to provide a novel organosilicon compound having a fluoroalkyl ether group that has a stable structure and can be produced by a simple method.

[Means for solving problems]

The present invention solves the above-mentioned problems by the general formula (
■): [In the formula, R is a lower alkyl group, X is a fluorine atom or a hydrogen atom, n is an integer of 1 to 4, and a is 1
The present invention provides a fluorine-containing organosilicon compound represented by:

The fluorine-containing organosilicon compound according to the present invention (hereinafter referred to as the organosilicon compound of the present invention) is an organosilicon compound having a fluoroalkyl ether group, and can be produced, for example, according to the following synthetic route.

[In the formula, R is a lower alkyl group such as a methyl group, ethyl group, or propyl group, preferably a methyl group, X is a fluorine atom or a hydrogen atom, M is an alkali metal, and n is 1 to
an integer of 4, and a is an integer of 1 to 3] The above manufacturing method will be described below in order.

First, a fluorinated allyl ether represented by the formula (■): [where X and n are as described above] obtained as an intermediate is synthesized by the following two methods A and B.

Formula (■) obtained by polymerizing hexafluoropropylene oxide (HFPO) by a known method (Japanese Patent Publication No. 36-20599): shi1'+3 shiP3 [wherein n is as described above] A terminal acid fluoride compound is reacted with an alkali metal fluoride (MP, where M is an alkali metal) to produce a fluoroalcolade represented by the formula (■): [wherein n and M are as described above] , then the fluoroalcolade was converted into an allyl halide (CHz=C
By reacting with HCHJSX (HCHJSX is a halogen atom), a fluorinated allyl ether represented by the formula (I[al [in the formula, n is as described above]) is produced.

In this synthesis method A, the reaction between the terminal acid fluoride compound of formula (II[)- and the alkali metal fluoride is carried out using a solvent such as tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or ethylene glycol dimethyl ether. Grimes, 1,4-dioxane, T)IF.

It is necessary to carry out the process under substantially anhydrous conditions using acetonitrile or the like, for example, in a dry nitrogen atmosphere,
Use sufficiently dried reactants and solvents. The concentration of the re-reacting components in the reaction is such that the molar ratio of the terminal acid fluoride compound of formula (III)/alkali metal fluoride is 1/1.
The molar ratio of alkali metal fluoride/solvent is preferably about 1/2 to 115, and the mixture is heated at 0 to 50°C for about 1 to 20 hours. Usually, the alkali metal fluoride is suspended in a solvent, and the terminal acid fluoride compound (III) is added dropwise together with the solvent if necessary. Examples of the alkali metal fluoride used in this step include cesium, sodium, potassium, and rubidium fluorides.

The above reaction produces a fluoroalcoholade of formula (■) in the reaction mixture, but the next step is to add allyl halides such as allyl bromide, allyl chloride, allyl iodide, etc. to the reaction mixture thus obtained. Bye. This reaction also needs to be carried out under substantially anhydrous conditions and at a temperature of 20 to 100°C.
Press for about 1 to 20 hours. As a result, the compound of formula (na), which is a type of fluoroallyl ether of general formula (If), is produced. The fecal dose of allyl halide may be about 1 to 2 times the molar amount of acid fluoride.

In order to separate the compound of formula (IIa) from the resulting reaction mixture, for example, excess methanol is added to the reaction mixture to methylate the terminal of the unreacted terminal acid fluoride compound represented by formula (I[I). After esterification, the fluorinated allyl ether of formula (IIa) can be obtained by washing with water and distillation.

Synthesis method B: Reduce the terminal acid fluoride compound represented by the above formula (I[) using a reducing agent to produce a terminal methylol compound represented by the formula (■): [wherein n is as described above] , then the terminal methylol compound is reacted with an alkali metal such as K % Na5Li, KOI (, NaOH, LiOH, etc.) to form the formula (■): ' [where n and M are the above-mentioned ] A terminal methylate compound represented by
Allyl halides such as allyl iodide CHz/CHCH,
X to produce a fluorinated allyl ether represented by the formula (Ilb): C, where n is as defined above.

In this synthesis method, the reducing agent used for reducing the terminal fluoride compound of formula (II[) is, for example, L
Examples include metal hydrides such as iH% Man -, LiAlH4, and NaBHn. This reduction reaction is carried out by the method described in U.S. Pat. No. 3,293,306, which is a known method (
fli medium such as dioxane, THF, glyme, etc.; atmosphere: for example, an anhydrous atmosphere such as dry nitrogen).

The reaction between the terminal methylol compound of formula (V) and an alkali metal or alkali metal hydroxide can be carried out using, for example, as a solvent.
Using water, methanol, ethanol, propatool, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and their alkyl ethers, 1 THF, dioxane, etc., 2
What is necessary is to carry out a time window of about 1 to 20 hours at 0 to 100°C. A terminal methylate compound of formula (VI) is thus produced. At this time, it is preferable to use the alkali metal or alkali metal hydroxide in an amount of about 1.5 to 2 times the mole of the terminal methylol compound.

In the next step, the reaction between the terminal methylate compound and the allyl halide, the allyl halide is dissolved in a solvent if necessary and added to the reaction mixture containing the terminal methylate compound of formula (VI) obtained in this manner, and the temperature is maintained at 30 to 100°C. 1 to 20
All you have to do is set the time window to about a certain amount of time.

From the reaction mixture thus obtained, the formula (]Ib
) To separate the fluorinated allyl ether, the reaction mixture may be washed with water, then distilled and fractionated.

Next, the organosilicon compound of the present invention can be prepared by the above-mentioned synthesis methods A and B.
It is obtained by reacting the fluorinated allyl ether represented by 2(n) obtained with a silane compound represented by the formula: HSi (R) z--C1, (where R and a are as described above). It will be done.

It is a reaction, and the charging ratio of the fluorinated allyl ether and silane used may be about 1.0 to 1.2 (molar ratio),
As a catalyst, a platinum-based catalyst, for example, platinum chloride to about 10@-4 mol is added. The reaction conditions may be normal pressure, 60 to 120°C, and about 1 to 4 hours.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

502 g of thoroughly dried cesium fluoride in a flask equipped with a stirrer, thermometer and condenser and saturated with dry nitrogen.
and tetraethylene glycol dimethyl ether 1470
g was charged and stirred at room temperature to suspend. The resulting suspension has the formula C3F? 1000 g of a CFz terminal acid fluoride compound represented by 0CFCOF was added dropwise, and 40
After heating and stirring at 50° C. for 20 hours, 28 g of brominated Lua was added dropwise, followed by heating and stirring at 50° C. for 20 hours. Excess methanol was added to the resulting reaction solution to methyl esterify the unreacted terminal acid fluoride compound, followed by washing several times with water and distillation to obtain a mixture with boiling point: 126-127°C, n: 1.
293, dzs 1.50, 863 g of a colorless and transparent liquid was obtained. From the analysis results below, this liquid has the formula C3FffO
CFCFzOCHICH-CH! A compound having the structure and the same CF.

established. This compound is hereinafter referred to as "fluorinated allyl ether (1)".

01R spectrum: Characteristic absorption 1660cm −' (-Cl(=CHz
)1100~1200cm-' (-CFz-)OGC
-MS spectrum: Molecular weight 392 (M+) 0 elemental analysis: Calculated value: C: 27.57. H: 1.29. F
:62.99.0:8.15 Actual value: C:27.0
3. H:1.31. F:62.05.0:9.61
(*As C9H5F 1sat) In the same manner as in Synthesis Example 1, 334 g of cesium fluoride was suspended in 980 g of tetraethylene glycol dimethyl ether, and the resulting suspension was added with formulas C, F? 1000 g of a terminal acid fluoride compound of 0CFCOF was added dropwise to CF+, and the mixture was heated and stirred at 40°C for 20 hours. Then, 490 g of allyl bromide was added, and the mixture was heated and stirred at 50°C for 20 hours.

Excess methanol was added to the resulting reaction mixture to methyl esterify the unreacted terminal acid fluoride compound, followed by washing several times with water and distillation to reduce the boiling point to 171-172°C.
, n: 1,295, dzs 1.60, 818 g of a colorless and transparent liquid was obtained. Based on the analysis results below, this liquid is
Formula CJ 70CFCF ZOCFCF JCHzCH”C
It was identified as a compound CF3 Ch having a structure of Hz. This compound is hereinafter referred to as "fluorinated allyl ether (2)".

OTR spectrum: Characteristic absorption 1660 rho' (-CH=CH2)11
00-1200 rho' (-CF,-) OGC-MS spectrum: Molecular weight 558 (M") 0 elemental analysis: (%) Calculated value ": C: 25.82. H:0.90. F:
64.67, 0:8.61 Real 1 (Direct: C: 2
5.40. )l:1.21. F: 63.9B,
O: 9.41 (*as C1□HsF++O+) 341 g of sufficiently dried sodium borohydride and 1,4-dioxane 2 were placed in a flask equipped with a bottom flame main stirrer, a temperature needle, and a cooling tube and saturated with dry nitrogen. .5 kg was charged and stirred and suspended at room temperature. While cooling the resulting suspension in a water bath, 2.0 kg of CJtOCFCOF was gradually added to cP.

dripped into. The dropping rate was controlled so that the temperature of the reaction solution was approximately 80°C due to the reaction heat, and after the completion of the dropping, the temperature was further increased to approximately 80°C for 2 seconds.
Heat and stir for hours. After gradually dropping the obtained reaction solution into excess water to decompose excess sodium borohydride, the organic layer (lower layer) separated into two layers was washed several times with a 5% methanol aqueous solution and dehydrated with sodium sulfate. Then, by distillation, the boiling point is 116-118℃, n T : 1.289, d
Liquid terminal methylol compound with zs: 1.66: C:
1662 g of 1F70CFCHzOH was obtained.

CF3 In a flask equipped with a stirrer, thermometer and condenser, add 6
50g, potassium hydroxide 365g, methanol 500g
was added and stirred at room temperature to form a homogeneous solution. After stirring the terminal methylol compound, 780 g of allyl bromide was added dropwise to this homogeneous solution, and the mixture was heated and stirred at 50° C. for 20 hours. The resulting reaction mixture was washed several times with water and then distilled to a boiling point of 130-131°C, n H” 1.30
76, 735 g of clear colorless liquid with d zs 1.43
I got it. This liquid was determined from the following analysis results. This compound is hereinafter referred to as "fluorinated allyl ether (3)".

OIR spectrum: Characteristic absorption 1650cm-' (-CH=C)It)
1100~1200cm-' (-CFt-)OGC-
MS spectrum: Molecular weight 356 (M+) 0 elemental analysis: Calculated value: C: 30.35. H: 1.98. F
: 58.6B, O: 8.99 Actual value: C: 29.
95. H:2.05. F:5B, 04. O:9.
96 (as "CJJl+0□") Sodium borohydride 145 was prepared in the same manner as in Sakusoku Yu biosynthesis example 3.
g was suspended in 2.0 kg of 1.4-dioxane and added dropwise, followed by heating and stirring at about 80° C. for 2 hours.

The resulting reaction solution was dropped into excess water to decompose unreacted sodium borohydride, washed several times with a 5% aqueous methanol solution, dehydrated with sodium sulfate, and then distilled to a boiling point of 155 to 156°C. , nr: 1.292, d
zs: 1.73 liquid terminal methylol compound In the same manner as in Synthesis Example 3, 230 g of water, 130 g of potassium hydroxide,
Add the above dropwise to a homogeneous solution of 200 g of methanol, and add 8
After heating and stirring at 0°C for 20 hours, 188 g of allyl bromide
was added dropwise, and the mixture was heated and stirred at 50°C for 20 hours.

The resulting reaction mixture was washed several times with water and then distilled to a boiling point of 172° C., n, 1.3044, dzs 1
．． 268 g of a colorless and transparent liquid of No. 54 was obtained. The compound,
Hereinafter, it will be referred to as "fluorinated allyl ether (4)". This liquid has the formula C3F tOcFcF zOcFcHJCI (zcH-
It was identified as a compound CF:l CF3 having the structure of Ctl t.

OIR spectrum: Characteristic absorption 1650■-' (-CH=CHz)11
00~1200cm-' (-CFz-)OGC-MS
Spectrum: Molecular weight 522 (M”) 0 Elemental analysis: Calculated value: C: 27.60. H: 1.35. F
:61.85. O: 9.20 Actual value: C: 26.
95. H:1.41. F261.20.0:10.
44 (as *C+tHtF+703) H silicon compound preparation Example 1 2 equipped with a stirrer, thermometer, reflux condenser and dropping funnel
In the flask of No. 1, the fluorinated polymer ether (1)
392g and 0.02g of chloroplatinic acid were charged and heated to 70°C.
dichloromethylsilane (HSi(C
lh)C1z) 140g was added dropwise. The dropping speed is
The temperature of the reaction solution was controlled to be about 100°C due to the heat of reaction. After completion of the dropwise addition and reaction, the temperature was further increased for 30 minutes at 70°C.
After stirring for a minute, the boiling point is 63-64"C/
448 g of a colorless and transparent liquid product of 1 wHg was obtained.

The product has a boiling point of 213°C/atmospheric pressure, n: 1.3
432, dzs 1.49, and from the following analysis results, 2:CJtOCFCFzO(C)Iz) zsic1
□It was identified as a compound having the structure of CF 3 Cl 3 .

“H-NMR: δ (ppm) 4.09 (t, 2H, (1)), 1.99 (m,
2H, (21).

1.25 (m, 2H, (3)), 0.85 (s,
3) (, (4)) However, (1) to (4) each mean each proton shown in the following formula.

Elemental analysis (%) CHF OCI Si Calculated value: 23.68 1.79 48.70 6.31
13.98 5.54 Actual value: 23.15 1.84
47.95 7.00 14.25 5.81 Example 2 In Example 1, 589 g of the fluorinated allyl ether (3) was used instead of the fluorinated allyl ether (1), and 140 g of dichloromethylsilane was changed to 230 g. The synthesis was performed using Boiling point 90-91℃/5 mH by distillation
662 g of a colorless and transparent liquid product were obtained. The product had a boiling point of 221-bl.44, and was identified as a compound having the structure of formula: from the analysis results below.

'H-NMR: δ (ppm) 4.02 (d, 2H, (11), 3.63 (t,
2H, +2) Ll, 89(m, 2H, (3)),
1.25(m, 2H, (41)0.86(s, 3
8. <5)) However, (1) to (5) each mean each proton shown in the following formula.

'-(5) Elemental analysis (%) CHF OCI Si calculated value: 25
．． 49 2.36 44.35 6.79 15.05
5.96 Actual value: 24.92 2.42 43.89
7.19 15.36 6.22 Examples 3 to 10 In Example 1, synthesis was carried out using the compounds shown in Table 1 instead of the fluorinated allyl ether (1) and dichloromethylsilane. Furthermore, the obtained organosilicon compounds, as well as their analytical values and characteristic values are shown in Table 2.

Table 1 [Effects of the Invention] Since the bond between the fluoroalkyl ether group and the silicon atom is stable, the organosilicon compound of the present invention is very stable, with the main skeleton hardly being hydrolyzed.

The organosilicon compound of the present invention is useful as an intermediate used in the production of various compounds and resins. For example, the organosilicon compound of the present invention can be used to derive a novel fluorine-containing silicone resin by hydrolysis, condensation, or other known techniques. This new fluorine-containing silicone resin can exhibit excellent heat resistance, chemical resistance, weather resistance, and surface properties. Further, the organosilicon compound of the present invention can be reacted with various alcohols and amines to derive a silicon compound having an alkoxy group or an amino group. This compound exhibits both the lubricity, water repellency, oil repellency, and interfacial properties of the fluoroalkyl ether group, and the hydrolyzability and adhesive properties of the alkoxy group and amino group on the silicon atom, and is capable of magnetic recording. It is useful as a lubricant for media and various surface treatment agents.

Claims (1)

[Claims] General formula▲ Numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R is a lower alkyl group, X is a fluorine atom or a hydrogen atom, n is an integer from 1 to 4, a is 1
is an integer of ~3] A fluorine-containing organosilicon compound represented by: