JP2575858C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION   TECHNICAL FIELD OF THE INVENTION   The present invention provides a novel terminal perfluoroalkylsilane compound, a method for producing the same, and
And a coating agent using the compound.   [Prior art]   A conventional terminal perfluoroalkylsilane compound is produced as follows.
I was For example, C_FourF₉CH = CH_TwoAnd C₈F₁₇CH = CH_TwoPerfluoro like
Alkene compound and HSi (CH_Three) Cl_TwoOr HSiCl_ThreeWith a platinum catalyst
Hydrosilylation reaction, C_FourF₉(CH_Two)_TwoSi (CH_Three) Cl_TwoAnd
C₈F₁₇(CH_Two)_TwoSiCl_ThreeTerminal perfluoroalkylsilane compound was synthesized
It is. The terminal perfluoroalkylsilane compound obtained as described above is
The compound is limited to compounds having 10 or less carbon atoms in a fluoroalkyl group bonded to a child.
The perfluoroalkene compound is an intermediate or a secondary compound in the fluororesin industry.
It can be obtained as a living thing.   On the other hand, a magnetic recording material such as a magnetic disk or a magnetic tape is coated on a magnetic film.
A lubricant is applied, and a lubricating layer is formed on the surface. But coating
The performance as a lubricating layer is reduced due to displacement, scattering, evaporation, etc. due to the movement of the agent.
There is a problem. Therefore, various coating agents with low vapor pressure are used.
However, a similar problem has arisen and the basic solution has not been reached.   [Problems to be solved by the invention]   The inventors of the present invention have found that a compound having a fluoroalkyl group has good lubricity.
On the magnetic film using a perfluoroalkylsilane compound as a coating agent
A study was conducted to form a lubricating layer by applying it to the surface. However, the existing terminal
Even with perfluoroalkylsilane compounds, lubricating effect was not enough
. Also, if the lubricating layer is uneven and pinholes are generated,
There was a drawback. After various investigations on the reasons, the following was clarified.
Was. The terminal perfluoroalkyl silane compound is an inorganic silane compound on the magnetic film.
The coupling is performed to form a monomolecular film. However, the conventional terminal perfluoroalkyl
The silane compound has a carbon atom of a fluoroalkyl group bonded to a silicon atom as described above.
The number is as short as 10 or less. Therefore, even if this is used as a coating agent, a uniform film is formed.
Not done. As a result, the above-mentioned disadvantages, including an insufficient lubrication effect,
It is thought to occur.   Fluoroalkyl bonded to silicon atom of terminal perfluoroalkylsilane compound If the kill group is long enough, it is expected that it is excellent as a coating agent.
However, there is no terminal perfluoroalkylsilane compound that meets such conditions.
Did not exist. Moreover, for synthesizing terminal perfluoroalkylsilane compounds
Conventionally, long-chain perfluoroalkene compounds, which are intermediate materials, exist.
did not exist. In addition, the number of fluorine in the perfluoroalkene compound is also limited.
Only existed.   Available F (CF_Two)_TwoCH_TwoI, F (CF_Two)_TwoCH_TwoCl, F (CF_Two)_ThreeCompare I etc.
Starting material from terminal perfluoroalkyl compound having a short fluoroalkyl group
As a longer chain terminal perfluoroalkyl compound F (CF_Two)_m(CH_Two)_mX¹(T
But X¹Synthesizes I, Br or Cl) and then F (CF_Two)_m(CH_Two)_nMgX¹Become
If the Grignard reagent is synthesized, this and (CH_Three)_pSix^Three _4-p(However, p = 0-2
An integer, X^ThreeIs an I, Br, Cl or alkoxy group) to form a long chain terminal
We predicted that a -fluoroalkylsilane compound could be synthesized and tried it. Only
F (CF_Two)_TwoCH_TwoX¹, F (CF_Two)_ThreeX¹, F (CF_Two)_m(CH_Two)_nX¹From Grignard
Can not be synthesized stably and the terminal par with long-chain fluoroalkyl group
The fluoroalkylsilane compound could not be synthesized.   It is an object of the present invention that a fluoroalkyl group bonded to a silicon atom has a sufficiently long terminal.
It is an object to provide a perfluoroalkylsilane compound.   Also, a product suitable for obtaining such a terminal perfluoroalkylsilane compound.
It is intended to provide a fabrication method.   Furthermore, the use of such terminal perfluoroalkylsilane compounds
The purpose is to provide a coating agent with a long lasting effect
ing.   [Means for Solving the Problems]   The present invention has been made to achieve the above object.   The first invention of the present invention is: General formula F (CF_Two)_m(CH_Two)_nSi (CH_Three)_pX_3-p  ... (1) Is a terminal perfluoroalkylsilane compound represented by the formula: Where m = 1 to 8, n = 9 to 18, p = 0 to 2 each integer, X is a halogen of I, Br or Cl
It is an atom or an alkoxy group.   The second invention of the present invention is directed to the terminal perfluoroalkylsilane compound of the first invention.
X is an alkoxy group, and the alkoxy group is a methoxy group or an ethoxy group
It is characterized by:   The third invention of the present invention is directed to the general formula of the first invention. When m = 1 in (1), the following general formula CF_Three(CH_Two)_nSi (CH_Three)_pX_3-p  ... (2) Ω-trifluoroalkylsilane compound represented by the formula: Where n =
9-18, each integer of p = 0-2, X is a halogen atom of I, Br or Cl,
Or an alkoxy group.   A fourth invention of the present invention is directed to the ω-trifluoroalkylsilane compound of the second invention.
X is an alkoxy group, and the alkoxy group is a methoxy group or an ethoxy group
It is characterized by:   The compound of the first invention of the present invention General formula F (CF_Two)_m(CH_Two)₁X¹    ... (3a) (Wherein, m = 1-8, each integer of 1 = 0-2, X¹Is I, Br or Cl
A perfluoroalkylsilane compound represented by the general formula: X^Two(CH_Two)_qCH = CH_Two    ... (3b) (Where q is an integer of 8 to 17, X^TwoIs a halogen atom of I, Br or Cl)
Grignard reagent synthesized from terminal alkenyl halides represented by X^TwoMg (CH_Two)_qCH = CH_Two  ... (3c) And react with the general formula F (CF_Two)_m(CH_Two)_{1 + q}CH = CH_Two  ... (3d) Synthesizing a terminal perfluoroalkene compound represented by the formula: (3d)
A terminal perfluoroalkene compound represented by the formula: HSi (CH_Three)_pX^Three _3-p  ... (3e) (Where p is an integer of 0 to 2, X^ThreeIs a halogen atom of I, Br or Cl, Or an alkoxy group).
Obtained by a reaction step.   The above hydrosilylation reaction is preferably performed in the presence of a platinum catalyst.
.   The ω-trifluoroalkylsilane compound represented by the above formula (2) of the third invention is
General formula CF_Three(CH_Two)_rCH = CH_Two  ... (4) (Wherein, r = an integer of 7 to 16) and an ω-trifluoroalkene compound represented by the formula:
, General formula HSi (CH_Three)_pX^Three _3-p      ... (3e) Of hydrosilation reaction with hydrogen silane represented by
Is obtained.   According to a fifth aspect of the present invention,Monomolecule chemically bonded to the surface of the substrate by -SiO- bond
A coating agent for forming a film,The following formula F (CF_Two)_m(CH_Two)_nSi (CH_Three)_pX_3-p [Wherein, m = 1-8, m + n = 10-32, p = 0-2 each integer, X is I, Br
Or Cl halogen sourceChild]Perfluoroalkylsilane compound represented by
Is a coating agent for forming a monomolecular film in which is dissolved in an organic solvent.   The perfluoroalkylhalogen compound at the terminal represented by the above formula (3a) is available.
Functional short-chain compounds such as F (CF_Two)_TwoCH_TwoCl (2,2,3,3,3-pentaf
LeOropropyl chloride), F (CF_Two)_TwoCH_TwoI (2,2,3,3,3-pentafluoro
Propyl iodide), F (CF_Two)_ThreeI (perfluoropropyl iodide
C), F (CF_Two)_ThreeCH_TwoBr (2,2,3,3,4,4,4-heptafluorobutyl bromide
Do).   The terminal alkenyl halide represented by the above formula (3b) is, for example, Cl (CH_Two
)_TenCH = CH_Two(11-dodecenyl chloride), Cl (CH_Two)₁₄CH = CH_Two
(15-hexadecenyl chloride), Br (CH_Two)₁₇CH = CH_Two(18-no
Nadecenyl bromide). Hydrogen sila represented by the above formula (3e)
For example, HSiCl_Three(Trichlorosilane), HSi (CH_Three) Cl_Two(Me Tildichlorosilane), HSi (CH_Three)_TwoCl (dimethylchlorosilane), HS
i (OMe)_Three(Trimethoxysilane), HSiCH_Three(OC_TwoH_Five)_Two(Methyldi
Ethoxysilane).   The terminal perfluoroalkyl sila represented by formula (1) produced by each of the above substances
For example, F (CF_Two)_Two(CH_Two)₁₃Si (CH_Three) Cl_Two(14, 14, 15, 15,
15-pentafluoropentadecylmethyldichlorosilane), F (CF_Two)_Two(CH_Two)₁₇
SiCl_Three(18,18,19,19,19-pentafluorononadecyltrichlorosilane
), F (CF_Two)_Three(CH_Two)₁₆Si (OMe)_Three(17, 17, 18, 18, 19, 19, 19-
Heptafluorononadecyltrimethoxysilane).   The Grignard reagent shown in the above (3c) is synthesized as follows. Reaction
When diethyl ether or tetrahydrofuran is prepared as a medium,
Inject gnesium. The terminal alkenyl halide of the formula (3b) is
As they are supplied, they are synthesized. The amount of metallic magnesium is determined by the terminal alkenyl halo.
It is preferred that it is the same molar amount or a slight excess as the genoide.   The synthesized Grignard reagent of the formula (3c) is a terminal perfluoro compound of the formula (3a)
By the Grignard reaction with the alkylsilane compound, the terminal perfluoro compound of the formula (3d) is obtained.
A loalkene compound is synthesized. As above, the reaction solvent diethyl ether
Or perhydroalkylfuran of the formula (3a)
The Grignard reagent and slowly add the Grignard reagent
Go on. Conversely, add the Grignard reagent to the reaction solvent, and add
It is also possible to add a loalkylhalogen compound. In addition, Cu as a catalyst
You may put it. After the reaction, add water to the reaction system to
After dissolving the salt, the organic and aqueous layers are separated. Reaction solvent, etc. from the organic layer
By removing the low boiler of formula (3d), the terminal perfluoroalkene compound of the formula (3d)
Synthesized. Note that distillation purification may be performed as long as distillation is possible.   A terminal perfluoroalkene compound of the formula (3d) and a hydrogen of the formula (3e)
Hydrosilylation reaction with silane is carried out, and the target compound of formula (1)
-Fluoroalkylsilane compound is obtained. As mentioned above, terminal perfluoro
The alkene compound requires a lot of time to synthesize, so that leaving an unreacted substance causes a large loss. Therefore, in order not to leave this at all, excess hydrogen silane is added.
To react. It is preferably carried out in the presence of a platinum catalyst. When the reaction system is normal pressure reaction
Is reacted under reflux. In the case of a pressurized or reduced pressure reaction,
However, industrially, from the viewpoint of economy and safety, the terminal
-Hydrogensilane is continuously supplied to the fluoroalkene compound to cause a reaction.
Preferably. If necessary, n-hexane or toluene inert to the reaction system may be used.
A hydrocarbon solvent such as a hydrocarbon may be used. After the reaction is completed, low levels of unreacted substances and reaction solvent
By removing the boil, the perfluoroalkylsilane compound at the terminal is converted to the formula (1).
Obtained with good purity. Note that distillation purification may be performed as long as distillation is possible.   Coating agent with terminal perfluoroalkylsilane compound obtained above
The following method is preferred for use as First, the terminal perfluoroalkyl
The silane compound to an organic compound such as n-hexane, toluene, chloroform, carbon tetrachloride, etc.
Dissolve in solvent. In this solution, the magnetic disk or magnetic tape
Dip and apply. Apply this solution by spraying or brushing
, Or with a roller. Apply the coating at room temperature or
Drying under heating completes the coating.   In addition, terminal perfluoroalkylsilane compound can be used as coating
This is not only for magnetic recording materials, but also for coatings intended for lubricity and release properties.
Can be used, especially for optical fiber and condenser protection coatings.
Is effective for   FIG. 1 shows an enlarged sectional view of the magnetic disk on which the above-mentioned coating has been completed.
You. As shown in the figure, the magnetic film 5 on the substrate 3 has a terminal perfluoroalkylsilane.
It is covered with a lubricating layer 7 of a compound. Cover the magnetic film 5 with another protective film.
A lubricating layer 7 of a terminal perfluoroalkylsilane compound may be formed thereon.
.   FIG. 2 shows the magnetic film 5 and the lubricating layer 7 of the terminal perfluoroalkylsilane compound.
An enlarged schematic diagram is shown. As shown in the figure, the lubricating layer 7 covering the surface of the magnetic film 5
And a monomolecular film of a terminal perfluoroalkylsilane compound. (1)
formulaToThe Si-X bond of the terminal perfluoroalkylsilane compound shown is hydrolysable InYou. This terminal perfluoroalkylsilane compound isInorganic on magnetic film 5
Fluoroalkyl groups face the surface to form a monolayer for silane coupling
You. In the figure, 7a is a silane coupling portion, and 7b is a fluoroalkyl group portion.
.   Since the fluoroalkyl group having excellent lubricity is directed to the surface, the lubricating layer 7 has lubricity.
It will be excellent. At this time, the fluoro in the terminal perfluoroalkylsilane compound
Since the alkyl group has an appropriate carbon number of 10 to 32, there is no uniform pinhole.
A lubricating layer 7 is formed. When the carbon number is 10 or less, a monomolecular film, that is, a film of the lubricating layer 7 is formed.
Insufficient thickness. If the carbon number is 32 or more, the molecular chain is too long and entanglement may occur.
And the lubricating layer 7 becomes uneven, and the surface becomes less smooth. The magnetic film 5
And the lubrication layer 7 are silane-coupled, so the bond is strong and scattering, evaporation, etc. are reduced.
And the durability is remarkably improved.   【Example】   Example 1   500 ml glass with stirrer, thermometer, reflux condenser and dropping funnel
12.0 g (0.5 mol) of metallic magnesium and tetra
Add 200 ml of hydrofuran. There Cl (CH_Two)₁₄CH = CH_Two(1
129.3 g (0.5 mol) of 5-hexadecenyl chloride) at 50-60 ° C
Over 2 hours. Then, by aging for 1 hour at 60-70 ° C,
ClMg (CH_Two)₁₄CH = CH_TwoWas synthesized.   In the same reactor as above, a glass flask having a capacity of 11 was charged with tetrahydrofuran.
0.5 ml of LiCl, CuCl_Two0.7 g was dissolved and F (C
F_Two)_TwoCH_TwoBr (2,2,3,3,3-pentafluoropropyl bromide) 106.5
g (0.5 mol) was added. After cooling it on ice, add the above Grignard reagent to 20
The solution was dropped at a temperature of 30 ° C. or lower for 1 hour, and aged at 30 ° C. for 1 hour. Note that this reaction solution is
The conversion was 95% as measured by chromatography. In this reaction solution
250 ml of a 5% hydrochloric acid aqueous solution is added and mixed, and formed in the reaction solution.
Dissolve the magnesium salt. The mixture was allowed to stand and separated into an aqueous layer and an organic layer.
Take out the layers. After removing the solvent tetrahydrofuran from the organic layer, vacuum 95% pure F (CF_Two)_Two(CH_Two)₁₅CH = CH_Two(18,
18,19,19,19-pentafluorononadecene) was obtained in 85% yield.   The obtained F was placed in a glass flask having a capacity of 100 ml in the same reactor as above.
(CF_Two)_Two(CH_Two)₁₅CH = CH_Two35.6 g (0.1 mol) and H_TwoPtCl₆・
6H_Two0.04 g of a 20% isopropyl alcohol solution of O was charged. H there
SiCl_Three(Trichlorosilane) 27.1 g (0.2 mol) at 100 to 110 ° C
For 5 hours. Thereafter, aging was performed at 120 ° C. for 3 hours. This reaction solution
By simple distillation under vacuum, 96% pure F (CF_Two)_Two(CH_Two)₁₇SiCl_Three(
18, 18, 19, 19, 19-pentafluorononadecyltrichlorosilane)
The yield was 83%.   Example 2   In a glass flask having a capacity of 11 in the same reactor as in Example 1, tetrahydro
ClMg in the same manner as in Example 1 except that the amount of furan was increased to 400 ml.
(CH_Two)₁₄CH = CH_TwoWas synthesized.   Then, the Grignard reagent is cooled on ice, and F (CF_Two)_ThreeI (purf
Luoropropyl iodideDo) 148.0 g (0.5 mol) was added dropwise over 1 hour
And aged at 30 ° C. for 1 hour. This reaction solution was measured by gas chromatography.
However, the conversion was 98%. Then magnesium produced in the same manner as in Example 1.
Dissolve and separate the salt. Distillation in vacuum after removing low boilers from organic layer
97% pure F (CF_Two)_Three(CH_Two)₁₄CH = CH_Two(17, 17, 18, 18, 19
, 19,19-heptafluorononadecene) in 88% yield.   Next, the F (CH) obtained above was placed in the same 100 ml reaction vessel as in Example 1._Two
)_Three(CH_Two)₁₄CH = CH_Two39.2 g (0.1 mol) and H_TwoPtCl₆・ 6H_TwoO
Of a 20% isopropyl alcohol solution was charged. HSi (O
Me)_Three(Trimethoxysilane) 18.3 g (0.15 mol)
The mixture was added dropwise at 6 ° C. over 6 hours. Then, it was aged at 120 ° C. for 5 hours. This reaction
The liquid is subjected to simple distillation under vacuum to obtain 95% pure F (CF_Two)_Three(CH_Two)₁₆Si (
OMe)_Three(17,17,18,18,19,19,19-heptafluorononadecyltrimeth
Xysilane) was obtained. The yield was 83%.   Example 3   In the same reactor as in Example 1, a reactor having a capacity of 300 ml was prepared, and Cl (CH_Two)₁₄C
H = CH_TwoCl (CH) instead of (15-hexadecenyl chloride)_Two)_TenCH =
CH_TwoUsing 101.3 g (0.5 mol) of (11-dodecenyl chloride)
ClMg (CH_Two)_TenCH = CH_TwoWas synthesized.   200 ml of tetrahydrofuran was placed in the same 11 reactors as above, and LiCl
0.5 g, CUCl_Two0.7 g was dissolved and F (CF_Two)_TwoCH_Two106.5 g of Br (
0.5 mol) was added. After cooling it on ice, the above Grignard reagent was cooled to 20 ° C or lower.
The mixture was added dropwise for 1 hour under the conditions and aged at 30 ° C. for 1 hour. This reaction solution is subjected to gas chromatography.
The reaction rate was 96% as measured by luffy. Next, generate as in the first embodiment.
The dissolved magnesium salt is dissolved and separated. After removing low boilers from the organic layer, vacuum
98% pure F (CF_Two)_Two(CH_Two)₁₁CH = CH_Two(
14,14,15,15,15-pentafluoropentadecene) was obtained in a yield of 87%
.   Next, the F (CF) obtained above was placed in the same 100 ml reaction vessel as in Example 1._Two
)_Two(CH_Two)₁₁CH = CH_Two30.0 g (0.1 mol) and H_TwoPtCl₆・ 6H_TwoO
Of a 20% isopropyl alcohol solution was charged. HSi (C
H_Three) Cl_Two(Methyldichlorosilane) 23.0 g (0.2 mol) in 100 to 11
It was added dropwise at 0 ° C. over 5 hours. Thereafter, aging was performed at 120 ° C. for 4 hours. This anti
The reaction solution was subjected to simple distillation under vacuum to obtain 97% pure F (CF_Two)_Two(CH_Two)₁₃Si
(CH_Three) Cl_Two(14,14,15,15,15-pentafluoropentadecylmethyldic
Lorosilane) was obtained. The yield was 83%.   Example 4   In the same reactor as in Example 1, a reaction vessel having a capacity of 11 was charged with tetrahydrofuran.
Was increased to 400 ml and Cl (CH_Two)₇CH = CH_Two(8-Nonenylchlorai
C) using 80.3 g (0.5 mol) of the raw material in the same manner as in Example 1.
H_Two)₇CH = CH_TwoWas synthesized.   Then, the Grignard reagent is cooled on ice, and F (CF_Two)_FourI (purf
173.0 g (0.5 mol) of fluorobutyl iodide) was added dropwise over 1 hour. At 30 ° C. for 1 hour. This reaction solution was measured by gas chromatography.
The roller conversion was 98%. Next, a magnesium salt produced in the same manner as in Example 1.
Is dissolved and separated. After removing low-boiling substances from the organic layer, distillation in vacuum
98% pure F (CF_Two)_Four(CH_Two)₇CH = CH_Two(10, 10, 11, 11, 12, 1
2,13,13,13-Nonafluorotridecene) was obtained in 90% yield.   Next, in the same 100 ml reactor as in Example 1, the F (CF_Two)_Four
(CH_Two)₇CH = CH_Two34.4 g (0.1 mol) and H_TwoPtCl₆・ 6H_TwoO 2
0.05 g of a 0% isopropyl alcohol solution was charged. HSiCl there_Three2
0.3 g (0.15 mol) was added dropwise at 100 to 110 ° C over 6 hours. That
Thereafter, aging was performed at 120 ° C. for 3 hours. Purification by vacuum distillation of this reaction solution
97% F (CF_Two)_Four(CH_Two)₉HSiCl_Three(10, 10, 11, 11, 12, 12, 13, 1
3,13-nonafluorotridecyltrichlorosilane) was obtained. 87% yield
Met.   Example 5   In the same formulation as in Example 4, Cl (CH_Two)₁₃CH = CH_Two(14-pentadecenyl
Chloride) as a raw material was 122.3 g (0.5 mol) of ClMg (CH_Two)₁₃C
H = CH_TwoWas synthesized.   F (CF) was introduced into this Grignard reagent under the same conditions as in Example 4._Two)_FourI 173.0
g (0.5 mol) was dripped and aged. This reaction solution is measured by gas chromatography.
As a result, the conversion was 98%. Next, magnesi produced in the same manner as in Example 1
Um salt is dissolved and separated. After removing low-boiling substances from the organic layer, perform distillation under vacuum.
And 97% pure F (CF_Two)_Four(CH_Two)₁₃CH = CH_Two(16, 16, 17, 17,
18,18,19,19,19-nonafluorononadecene) were obtained in 88% yield.   Next, the F (CF) obtained above was placed in the same 100 ml reaction vessel as in Example 1._Two)_Four
(CH_Two)₁₃CH = CH_Two42.8 g (0.1 mol) and H_TwoPtCl₆・ 6H_TwoO 2
0.05 g of a 0% isopropyl alcohol solution was charged. HSiCl there_Three2
7.1 g (0.2 mol) was added dropwise at 100 to 110 ° C. over 6 hours. afterwards
At 120 ° C. for 4 hours. The reaction solution is distilled in vacuum to obtain a purity of 9%.
6% F (CF_Two)_Four(CH_Two)₁₅SiCl_Three(16, 16, 17, 17, 18, 18, 19, 19, 19-nonafluorononadecyltrichlorosilane) was obtained. The yield is 85%
Was.   Example 6   According to the same formulation as in Example 4, 0.5 mol of ClMg (CH_Two)₇CH = C
H_TwoWas synthesized.   Next, as in Example 1, the Grignard reagent was ice-cooled, and F (
CF_Two)₈273.0 g (0.5 mol) of I (perfluorooctyl iodide)
Was added dropwise over 1 hour and aged at 30 ° C. for 1 hour. This reaction solution is subjected to gas chromatography.
The reaction rate was 97% as measured by luffy. Then, the raw material was produced in the same manner as in Example 1.
The formed magnesium salt is dissolved and separated. After removing low boilers from the organic layer,
98% pure F (CF_Two)₈(CH_Two)₇CH = CH_Two(Ten
, 10,11,11,12,12,13,13,14,14,15,15,16,16,17,17,17-hepta
Decafluoroheptadecene) was obtained in 90% yield.   Next, the F (CF) obtained above was placed in the same 100 ml reaction vessel as in Example 1._Two)₈
(CH_Two)₇CH = CH_Two42.8 g (0.1 mol) and H_TwoPtCl₆・ 6H_TwoO 20
0.05 g of a% isopropyl alcohol solution was charged. HSiCl there_Three27
. 1 g (0.2 mol) was added dropwise at 100 to 110 ° C over 6 hours. afterwards,
Aged at 120 ° C. for 4 hours. The reaction solution is distilled in vacuum to obtain a purity of 97.
% Of F (CF_Two)₈(CH_Two)₉SiCl_Three(10, 10, 11, 11, 12, 12, 13, 13, 14
, 14,15,15,16,16,17,17,17-heptadecafluoroheptadecyl trichloro
Rosilane) was obtained. The yield was 86%.   Example 7   In a glass flask having a capacity of 300 ml in the same reactor as in Example 1, CF was added._Three
(CH_Two)₁₆CH = CH_Two(19,19,19-trifluorononadecene) 0.5 mol
H_TwoPtCl₆・ 6H_TwoCharge 0.05 g of 20% isopropyl alcohol solution of O
I do. The temperature was raised to 100 ° C, and HSiCl_Three0.75 mol from 100 to 110
The mixture was added dropwise over 5 hours in a temperature range of ° C. Thereafter, aging was performed at 120 ° C. for 2 hours. This
After cooling the reaction mixture, gas chromatography using a silicone-based capillary column
Measured by CF_Three(CH_Two)₁₆CH = CH_TwoPeak has disappeared Was confirmed. Next, after distilling the reaction solution, the boiling point was 220 ° C./mmHg and C
F_Three(CH_Two)₁₈SiCl_Three(19,19,19-trifluorononadecyltrichlorosila
) Was obtained. The yield was 82%. Obtained CF_Three(CH_Two)₁₈SiCl_ThreeIs
, Mass spectrum (MS), nuclear magnetic resonance (NMR) and infrared absorption spectrum (I
R) confirmed the structure. Each data is as follows. Mass spectrum (MS): m / Z (spectral intensity ratio) * 371 (3) * 231 (4) * 217 (6) * 203 (7) * 189 (10) * 175 (14) * 133 (16) 97 (22) 91 (23)    85 (43) 83 (33) 71 (63)    69 (47) 57 (100) 55 (72)    43 (73) 41 (57)   * Marked peak is chlorine³⁷Accompany the Cl isotope peak.   Nuclear magnetic resonance (NMR): δ (ppm)   CF_Three− (CH_Two)₁₇-CH_Two-SiCl_Three            (A) (b)   a: 1.20 to 2.0 ppm (M)   b: 3.12 ppm (T)   Infrared absorption spectrum (IR): cm^-1   2920, 2850, 1470, 690   Example 8   In the same manner as in Example 7, CF was added to the reaction vessel._Three(CH_Two)₈CH = CH_Two(11, 11, 11-
Trifluoroundecene) 0.5 mol and H_TwoPtCl₆・ 6H_Two20% isopro of O
0.05 g of a pill alcohol solution was charged. The temperature is raised to 100 ° C and HSi
Cl_Three0.75 mol was added dropwise in a temperature range of 100 to 110 ° C over 5 hours. So
This was subjected to gas chromatography measurement in the same manner as in Example 7 to find that CF_Three(CH_Two)₈
CH = CH_TwoPeak had disappeared. Then, when the reaction solution is distilled, the boiling point becomes
120 ° C / mmHg and CF_Three(CH_Two)_TenSiCl_Three(11,11,11-Triflu
Orundecyl trichlorosilane) was obtained. The yield was 90%. Obtained CF_Three(CH_Two)_TenSiCl_ThreeThe structure was confirmed by the same means as in Example 7.
Each data is as follows. Mass spectrum (MS): m / Z (spectral intensity ratio) * 259 (8) * 217 (4) * 203 (12) * 189 (12) * 175 (30) * 133 (34)    91 (38) 85 (28) 71 (40)    69 (26) 57 (64) 55 (62)    43 (100) 41 (66) 39 (20)   * Marked peak is chlorine³⁷Accompany the Cl isotope peak.   Nuclear magnetic resonance (NMR): δ (ppm)   CF_Three− (CH_Two)₉-CH_Two-SiCl_Three            (A) (b)   a: 1.20 to 1.63 ppm (M)   b: 3.10 ppm (T)   Infrared absorption spectrum (IR): cm^-1   2930, 2860, 1470, 1215, 1180, 770, 720, 690   【The invention's effect】   As described above, according to the present invention, a fluoroalkyl bonded to a silicon atom
Providing terminal perfluoroalkylsilane compounds with a sufficiently long group by an accurate manufacturing method
Can now be offered. This terminal perfluoroalkylsilane compound
A coating agent that has a sufficient lubrication effect and has a long lasting effect
It is. This coating agent can be used for a wide range of applications.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an enlarged sectional view of an example using the coating agent of the present invention, and FIG. 2 is an enlarged schematic view of the same example of use. 3 Substrate 5 Magnetic film 7 Lubricating layer 7a Silane coupling part 7b Fluoroalkyl group part

Claims (1)

(1) General formula F (CF ₂ ) _m (CH ₂ ) _n Si (CH ₃ ) _p X _3-p [wherein, m = 1 to 8, n = 9 to 18, p = Each integer of 0 to 2, X is I, Br or C
l halogen atom or alkoxy group]. (2) A terminal perfluoroalkylsilane compound, wherein the alkoxy group according to claim 1 is a methoxy group or an ethoxy group. (3) In the general formula described in claim 1, m = 1, and the general formula CF ₃ (CH ₂ ) _n Si (CH ₃ ) _p X _3-p [where n = 9 to 18, p is an integer of 0 to 2, and X is a halogen atom of I, Br or Cl, or an alkoxy group]. (4) The ω-trifluoroalkylsilane compound, wherein the alkoxy group according to claim 3 is a methoxy group or an ethoxy group. (5) Forming a monomolecular film by chemically bonding to the surface of the base material through a -SiO- bond.
A fit of the coating agent, the general formula _{F (CF 2) m (CH} 2) n Si (CH 3) p X 3-p [ wherein, m = 1~8, m + n = 10~32, p = 0 X is I, Br
Monomolecular film forming coating agent characterized in that a terminal perfluoroalkyl silane compound was dissolved in an organic solvent represented by or Cl halogen atom.