KR20220074611A - Fluorine-based organopolysilazane and method for manufacturing the same - Google Patents

Abstract

(상기 화학식 1에서,
상기 x 및 y는 ¹H-NMR로 측정된 각 반복단위의 몰%로, x는 50 내지 80 몰%, y는 20 내지 50 몰%이며, 이때 x+y=100 몰%이고,
상기 n는 0 내지 7의 정수이며,
상기 R₁ 및 R₂는 서로 독립적으로 수소, 탄수소 1 내지 10의 알킬기, 탄소수 2 내지 10의 알케닐기, 탄소수 5 내지 20의 사이클로알킬기 또는 탄소수 6 내지 20의 아릴기이다.) The present invention relates to a fluorine-based organopolysilazane comprising a repeating unit satisfying the following formula (1), and a method for preparing the same.
[Formula 1]

(In Formula 1,
Wherein x and y are mol% of each repeating unit measured by ¹ H-NMR, x is 50 to 80 mol%, y is 20 to 50 mol%, where x+y=100 mol%,
Wherein n is an integer of 0 to 7,
R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)

Description

Fluorine-based organopolysilazane, and manufacturing method thereof {Fluorine-based organopolysilazane and method for manufacturing the same}

The present invention relates to a fluorine-based organopolysilazane and a method for preparing the same.

Polysilazane is a polymer material having -(SiR ₂ -NR)- as a basic unit. When heated, it is converted into silica or silica material. Since the silica material thus formed has excellent insulation properties, it is mainly used in electrical and electronic fields as insulating films. is being used In addition, since polysilazane forms a SiO ₂ layer upon hydrolysis reaction with water, the surface coated with polysilazane may react with moisture in the air to form a highly durable film.

Polysilazane can be prepared by various methods using a wide range of starting materials. In general, polysilazane prepared from ammonia is an ammonolysate, and polysilazane prepared from an amino compound other than ammonia containing an NH ₂ group. The glass is known as an aminolysate.

As a method for producing polysilazane by ammoxidation process, U.S. Patent No. 4,395,460 discloses a process for producing polysilazane by reacting a chlorodisilane solution dissolved in an inert solvent with ammonia gas, and Korean Patent Publication No. 4,395,460. No. 10-2007-0040422 discloses a method for preparing an ammoxidation product including polysilazane by introducing a halosilane having one or more Si-H bonds into an excess of anhydrous liquid ammonia.

In addition, an amino decomposition process such as a method of reacting an amine with a silicon halide such as SiCl ₄ , SiH ₂ Cl ₂ or synthesizing polysilazane by dehydrogenation of a silane compound and an amine compound using a transition metal complex catalyst Methods are also proposed by However, although general polysilazane prepared by the conventional method exhibits water repellency due to the methyl functional group, there is a problem in that it is vulnerable to contamination due to excessive lipophilicity due to the methyl functional group.

In order to improve this, polysilazane introduced with fluorine that does not get wet in both water and oil has been proposed, and in Japanese Patent Publication No. 2010-043251, a branched phase mainly represented by -CF(CF ₃ )-CF ₂ O- Perfluoropolyether-modified polysilazane obtained by silanization of perfluoropolyether of as a raw material is disclosed. Further, Japanese Patent Publication No. 2012-257650 discloses a perfluoropolyether-modified silazane having linear (CF ₂ O) _p (CF ₂ CF ₂ O) _q in the main chain structure. However, in the above case, too, there is a problem in that it does not have sufficient wiping properties and oil repellency.

In addition, as the technology application range of polysilazane is expanded not only in the electrical and electronic fields, but also in the medical and aerospace industries, it is necessary to improve water and oil repellency and excellent anti-icing effect and durability compared to the prior art. .

US registered patent US4395460 Republic of Korea Patent Publication No. 10-2007-0040422 Japanese Patent Publication No. 2010-043251 Japanese Patent Publication No. 2012-257650

In order to solve the above problems, the present invention provides a fluorine-based organopolysilazane that is not easily contaminated, and that is easy to remove even if contaminated, and a method for manufacturing the same, characterized by improved water and oil repellency characteristics aim to Another object of the present invention is to provide a fluorine-based organopolysilazane having excellent anti-freezing effect and durability, and a method for manufacturing the same.

To achieve the above object, it relates to a fluorine-based organopolysilazane comprising a repeating unit satisfying the following formula (1) of the present invention.

[Formula 1]

(In Formula 1,

Wherein x and y are mol% of each repeating unit measured by ¹ H-NMR, x is 50 to 80 mol%, y is 20 to 50 mol%, where x+y=100 mol%,

Wherein n is an integer of 0 to 7,

R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)

In one aspect, in Formula 1, x is 65 to 75 mol%, and y is 25 to 35 mol%, wherein x + y = 100 mol%, and n is an integer of 5 to 7, characterized in that may be doing

In one aspect, the fluorine-based organopolysilazane may have a water contact angle of 173 to 180° and an oil contact angle of 150 to 160°.

In one aspect, the fluorine-based organopolysilazane may be characterized in that it has an ice adhesion strength of 35 to 100 kPa.

In addition, another aspect of the present invention may be characterized in that it comprises; synthesizing a fluorine-based organopolysilazane satisfying the following formula (1).

[Formula 1]

(In Formula 1,

Wherein x and y are mol% of each repeating unit measured by ¹ H-NMR, x is 50 to 80 mol%, y is 20 to 50 mol%, where x+y=100 mol%,

Wherein n is an integer of 0 to 7,

R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)

The fluorine-based organopolysilazane according to the present invention is a fluorine-based organopolysilazane synthesized with perfluorodecyldichlorosilane and halosilane. Since the water and oil repellency properties of the organopolysilazane are improved, it may be free from contamination or the contamination may be easily removed. In addition, since the surface energy of the fluorine-based organopolysilazane is lowered, anti-freezing power and durability may be excellent.

1 is a fluorine-based organopolysilazane (FPSZ _S ) and organopolysilazane (OPSZ) Hydrogen atomic nuclear magnetic resonance ( ¹ H NMR) spectra.
FIG. 2 is a scanning electron microscope (SEM) photograph of Example 1 and Comparative Example 1. FIG.

Hereinafter, the fluorine-based organopolysilazane according to the present invention and a method for manufacturing the same will be described in detail. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

Polysilazane exhibits water-repellent performance due to the methyl functional group, but has a problem in that it is vulnerable to contamination due to excessive lipophilicity due to the methyl functional group. In order to improve this, polysilazane introduced with fluorine that does not wet with water and oil has been proposed, but polysilazane to which fluorine is introduced also has a problem in that it does not have sufficient wiping properties and oil repellency.

Accordingly, the present inventors have repeatedly studied to develop a fluorine-based organopolysilazane that exhibits improved water and oil repellency properties and excellent anti-freeze and durability compared to the prior art. It has been found that the above object can be achieved when the content of decyldichlorosilane is mixed in an appropriate ratio, and thus the present invention has been completed.

In detail, the fluorine-based organopolysilazane according to an embodiment of the present invention may include a repeating unit satisfying the following formula (1).

[Formula 1]

(In Formula 1,

Wherein x and y are mol% of each repeating unit measured by ¹ H-NMR, x is 50 to 80 mol%, y is 20 to 50 mol%, where x+y=100 mol%,

Wherein n is an integer of 0 to 7,

R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)

More preferably, in the fluorine-based organopolysilazane, in Formula 1, x is 65 to 75 mol%, and y is 25 to 35 mol%, wherein x+y=100 mol%, and n is It may be characterized as an integer of 5 to 7. By satisfying this, excessive lipophilicity due to the methyl functional group is lowered and the oleophobicity is increased due to the fluoro functional group, thereby improving oil repellency compared to the prior art.

As a specific example, the fluorine-based organopolysilazane satisfying Chemical Formula 1 may be characterized by a water contact angle of 173 to 180° and an oil contact angle of 150 to 160°, and more preferably, a number of 173 to 180°. It may be characterized by a contact angle and an oil contact angle of 150 to 155°. As described above, since both the water contact angle and the oil contact angle are high, they are not easily contaminated or can be easily removed even if they are contaminated.

In addition, by satisfying Chemical Formula 1, anti-freezing power and durability may be further improved. As a specific example, the fluorine-based organopolysilazane may have an ice adhesion strength of 35 to 100 kPa, and more preferably, an ice adhesion strength of 35 to 75 kPa. have.

In addition, another aspect of the present invention may be characterized in that it comprises; synthesizing a fluorine-based organopolysilazane satisfying the following formula (1).

[Formula 1]

(In Formula 1,

Wherein x and y are mol% of each repeating unit measured by ¹ H-NMR, x is 50 to 80 mol%, y is 20 to 50 mol%, where x+y=100 mol%,

Wherein n is an integer of 0 to 7,

R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)

In detail, the method for preparing the fluorine-based organopolysilazane includes: (step 1) dissolving perfluorodichlorosilane and halosilane in a basic solvent to prepare a mixed solution, followed by stirring; (Step 2) injecting ammonia gas into the mixed solution and stirring; (Step 3) removing the precipitated salt and residual solvent; and (Step 4) aging the final product to produce a fluorine-based organopolysilazane.

In one embodiment of the present invention, in step 1, the perfluorodichlorosilane is (3,3,3-trifluoropropyl)dichloromethylsilane, 3,3,4,4,5,5,5,- It may be at least one selected from the group consisting of heptafluoropentylmethyldichlorosilane and 1H,1H,2H,2H-perfluorodecylmethyldichlorosilane, particularly preferably 3,3,4,4,5,5,5 ,-heptafluoropentylmethyldichlorosilane and 1H,1H,2H,2H-perfluorodecylmethyldichlorosilane. By using an appropriate amount of this, a fluorine-based organopolysilazane having a water contact angle of 173 to 180° and an oil contact angle of 150 to 160°, and ice adhesion strength of 35 to 100 kPa can be synthesized.

In addition, in one embodiment of the present invention, in the first step, the halosilane is dichlorosilane, methyldichlorosilane, ethyldichlorosilane, ethyldiiodosilane, ethyldifluorosilane, dichloromonofluorosilane, propyldibromosilane , isopropyldichlorosilane, isobutyldichlorosilane, isoamyldichlorosilane, benzyldichlorosilane, propenyldichlorosilane, naphthyldichlorosilane, phenyldichlorosilane, diethylchlorosilane, methylethylchlorosilane, vinylmethylchlorosilane, phenyl Methylchlorosilane, dibenzylchlorosilane, p-chlorophenylmethylchlorosilane, n-hexyldichlorosilane, cyclohexyldichlorosilane, dicyclohexylchlorosilane, di-isobutylchlorosilane, p-tolyldichlorosilane, di-p -Tolylchlorosilane, p-styryldichlorosilane, and ethynyl dichlorosilane may be one or more selected from the group consisting of.

In addition, in one embodiment of the present invention, in the first step, the basic solvent is trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, pyridine, picoline, dimethylaniline, trimethylphosphine, dimethylethylphosphine. , methyldiethylphosphine, triethylphosphine, trimethylarsine, trimethylstipine, trimethylamine, triethylamine, and triazine may be one or more selected from the group consisting of.

Hereinafter, the organopolysilazane according to the present invention and a method for preparing the same will be described in more detail through examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Further, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention. In addition, the unit of additives not specifically described in the specification may be weight %.

[Characteristic evaluation method]

1) Measurement of structural properties

Dichloro(1H,1H,2H,2H-perfluorodecyl)methylsilane (DCFMS) and dimethyldichlorosilane in the fluorinated organopolysilazanes (FPZ _S ) using Gel Permeation Chromatography (GPC) The relative molar mass of (dichloromethylsilane, DCMS) was measured. A Tosoh EcoSEC HLC-8320 GPC instrument was used, and the results are shown in Table 1 below.

¹ Using H-NMR (Nuclear Magnetic Resonance) spectra and Fourier-Transform Infrared Spectrometer (FT-IR), the structural properties of fluorine-based organopolysilazanes (FPSZ _S ) and organopolysilazanes (OPSZ) were measured measured. A 300 MHz Brucker spectrometer and a Nicolet 6700 FT-IR spectrometer were used, and the results are shown in Table 1 and FIG. 1 below.

2) Measurement of hydrophilicity and lipophilicity

Using Smart Drop (Femtobiomed, Korea), the static contact angle of 5 μL of water and hexadecane drops from the surface coated with the fluorine-based organopolysilazane (FPSZ _S ) and organopolysilazane (OPSZ) was measured. The results are shown in Table 1 below.

3) shape investigation

The surface coated with the fluorine-based organopolysilazane (FPSZ _S ) and organopolysilazane (OPSZ) was observed using a scanning electron microscope (SEM, JEOL JSM-6500F, Tokyo, Japan). A Hitachi S4800 field scanning electron microscope operating at an acceleration voltage of 10 keV was used, and the results are shown in FIG. 3 .

4) Anti-freeze and durability evaluation

It was performed using the measuring device described in the paper [Langmuir 34 (2018) 13821-13827]. Using a probe having a diameter of 0.8 cm of a force transducer (Imada, model ZP, 44), the probe was propelled in the vertical direction of the ice column to determine the ice adhesion strength of Examples 1 to 4 and Comparative Examples 1 and 6 to 8 below. measured. It was allowed to melt at room temperature and then dried at 120° C. for 2 hours for the test cycle. Ice-melting test cycle was performed 40 times, and the measured ice adhesion strength was compared to evaluate anti-freezing properties and durability. The results are shown in Table 1 below.

[Example 1]

dichloro(1H,1H,2H,2H-perfluorodecyl)methylsilane (DCFMS) was prepared through hydrosilylation reaction. 0.01 mol (4.46 g) 1H,1H,2H-perfluoro-1- in the presence of 2 wt% platinum(0)-1,3-divinyl-1,1,3,3-tetra-methyldisiloxane complex solution in nitrogen atmosphere A reaction mixture of decene and 0.01 mol (1.15 g) dimethyldichlorosilane (DCMS) was stirred at room temperature for 48 hours. DCFMS was obtained with a yield of 93% by weight of a clear liquid product by vacuum distillation at a boiling point of 55-56 °C.

The obtained DCFMS 4.21 g (7.50 mmol) and DCMS 22.9 g (200.26 mmol) were put into a reactor together with anhydrous pyridine (100 mL) and stirred at 0°C. While maintaining the solution temperature at 0° C., ammonia gas was injected into the solution and bubbling, followed by stirring for 3 hours. After that, the injection of ammonia gas was blocked and further stirring was performed at room temperature for 24 hours. After the reaction was completed, the ammonium chloride salt precipitated in the reactant was removed through a filter, and the remaining pyridine was removed by vacuum distillation to obtain a fluorine-based organopolysilazane.

Thermal polymerization was performed to increase the molecular weight of the fluorine-based organopolysilazane. It was heated to 120 °C and stirred for 24 hours.

[Example 2, and Comparative Examples 1 to 10]

It proceeded in the same manner as in Example 1 except that the molar ratios of DCFMS and DCMS were changed. As shown in Table 1 below, DCFMS and DCMS were added according to the molar ratio.

The organic-inorganic composites prepared in Examples 1 to 2 and Comparative Examples 1 to 10, respectively, were evaluated according to the characteristic evaluation method, and the results are shown in Table 1 below.

DCFMS (mol %) Contact angle (°) ² Ice adhesion strength (kPa) ² Sample input cost measurement ratio ¹ hexadecane water water 1st 40th 1st 40th Example 1 30 26.7 150 176 168 73 83 Example 2 35 31 152 177 174 37 46 Comparative Example 1
(OPSZ) 0 0 wet 166.5 159 338 failure Comparative Example 2 0.25 0.2 166.5 - - - Comparative Example 3 0.5 0.4 167.5 Comparative Example 4 1.5 1.3 167 Comparative Example 5 4.5 4.1 167.5 Comparative Example 6 10 7.5 59.5 170.5 160 295 305 Comparative Example 7 15 12 75 172 161.5 150 180 Comparative Example 8 20 15 85 175.5 161.5 80 105 Comparative Example 9 60 55.9 149 175 164 150 225 Comparative Example 10 100 100 149 175 160 250 352 It is a value measured by 1: ¹ H-NMR.
2: Values measured on rough Al substrates coated with OPSZ and FPSZs.

As can be seen from Table 1, it can be seen that the contact angle with water and the contact angle with hexadecane of Examples 1 to 2 are improved compared to Comparative Examples 1 to 10. In the case of Examples 1 and 2, the contact angle with water was increased to 176 ° or more. In addition, the contact angle with hexadecane of Examples 1 and 2 was increased to 150° or more. In particular, the contact angle with hexadecane of Example 2 was increased by up to 92.5° compared to Comparative Examples 6 to 10. The contact angle with water was increased by up to 10.5° compared to Comparative Examples 1 to 10. In addition, Example 2 exhibited a high water contact angle of 174° even after 40 ice-melting test cycles. Through this, it can be seen that Example 2 exhibits the best water and oil repellency properties.

In addition, the ice adhesion strength of Example 2 was 37 kPa. This may mean that Example 2 has a lower surface energy than Comparative Examples 1 and 6 to 10, and the lower the surface energy, the better hydrophobicity may be exhibited. In addition, Example 2 exhibited a low ice adhesion strength of 46 kPa even after 40 ice-melting test cycles, and the difference between before and after the ice-melting test was the smallest. Through this, it was found that Example 2 showed the best water and oil repellency properties and had excellent durability.

As such, it was clearly confirmed that when polysilazane contained 20 to 50 mol% of perfluorodecyldichlorosilane compared to halosilane, water and oil repellency properties could be greatly improved. In particular, when Example 2 is used as a surface treatment agent, both water and oil repellency properties are excellent, so that it is not easily contaminated by external substances and can easily remove a contaminant.

On the other hand, Figure 1 is a fluorine-based organopolysilazane (FPSZ _S ) and organopolysilazane (OPSZ) ¹ H NMR spectra show that the peaks of b (2.1 ppm) and c (0.88 ppm) are related to the methylene group of the fluoromethyl silane (FMS) moiety in DCFMS. In addition, it can be seen that the peak of a (4.4 to 4.8 ppm) is related to the silane (Si-H) proton in DCMS. It can be seen that the (0.2 to 0.4 ppm) peak of d is related to hydrogen bonding to carbon atoms in Si-CH ₃ . It can be seen that the intensity of a decreases as the intensity of the methylene protons (b and c) increases. As the strength of a is lowered, the lipophilicity due to the methyl functional group may decrease. In Examples 1 to 2, since the strength of a was lower than Comparative Examples 1 to 10, it may mean that the lipophilicity due to the methyl functional group was reduced to exhibit improved oleophobicity.

In addition, as described in Table 1, the contact angles of water and hexadecane of Examples 1 to 2 and Comparative Examples 1 to 10 coated on a rough surface Al substrate were measured using Smart Drop. Prior to contact angle measurement, Al rough substrates were prepared. The Al substrate was degreased by sonication with acetone and ethanol. The washed Al plates were nicknamed by immersing them in 2.5 M hydrogen chloride at room temperature for 10 min. After rinsing the substrate with deionized water, it was soaked in boiling water for 30 min and then dried at 120 °C for 2 h. Mineral spirit (10wt% solution) of fluorine-based polysilazane was used for dip coating. Using an EF-4100 dip coater (EFlex, Korea), it was carried out for a soaking time of 10 seconds at a hoisting speed of 0.5 mm/sec. Thereafter, the coated substrate was dried at 150° C. for 48 hours.

At room temperature, 5 μL of water and hexadecane drops were placed on the coated rough surface Al substrate and the angle was measured by the fixed drop method. The contact angle value was expressed as the average value of the values measured once each at 5 points on each surface.

The contact angle with water of Comparative Example 1 (OPSZ) was 166.5°. On the other hand, in the case of Example 2, the water contact angle increased by 10.5°, indicating 177°. In addition, in Comparative Examples 1 to 5, it was impossible to measure the hexadecane contact angle. It can be seen that the fluorine concentration is not sufficient to exhibit oil repellency. On the other hand, the contact angle with hexadecane of Example 2 was 152°, and Example 2 showed the best hydrophobicity and oleophobicity.

In addition, as described in Table 1, the contact angle and ice adhesion strength of Examples 1 to 2 and Comparative Examples 1 and 6 to 10 coated on a rough surface Al substrate were measured, and the contact angle measurement was measured in the same manner as above. did. Prior to measuring the ice adhesion strength, a measuring device was prepared. As for the measuring device, the contents described in the paper [Langmuir 34 (2018) 13821-13827] may be referred to. 1 mL of deionized water was filled into a bottomless cuvette (1 cm x 1 cm x 3 cm) and placed on the coated surface. The water column of the cuvette was completely frozen at -20 °C (4 hours, 25-35% relative humidity or less). Using a probe with a diameter of 0.8 cm of a force transducer (Imada, model ZP, 44), the probe was propelled in the vertical direction of the ice column to measure the ice adhesion strength. The shear stress required to separate the ice column from the surface was also measured. The measured maximum strength was converted to the ice adhesion strength using Relation 1. The ice adhesion strength value was expressed as the average value of the results of 5 repeated experiments.

[Relational Expression 1]

τ = F / A

(In the above relation 1,

τ is the ice adhesion strength, F is the critical force, and A is the contact zero of the ice substrate interface.)

The ice column was allowed to melt at room temperature and then dried at 120 °C for 2 h for the test cycle. After the ice-melting test cycle was performed 40 times, the ice adhesion strength was obtained in the same manner as above.

Comparative Example 1 (OPSZ) exhibited a high ice adhesion strength of 338 kPa. On the other hand, Example 2 shows an ice adhesion strength of 37 kPa, which is 301 kPa lower than Comparative Example 1. This may mean that Example 2 has a lower surface energy than Comparative Examples 1 and 6 to 10. The lower the surface energy, the better the hydrophobicity can be exhibited. In addition, Example 2 showed a low ice adhesion strength of 46 kPa even after 40 cycles of the ice-melting test, so that the difference between before and after the ice-melting test was the smallest.

Although the present invention has been described with reference to specific matters and limited examples as described above, these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention belongs to Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (5)

A fluorine-based organopolysilazane comprising a repeating unit satisfying the following formula (1).
[Formula 1]

(In Formula 1,
Wherein x and y are mol% of each repeating unit measured by ¹ H-NMR, x is 50 to 80 mol%, y is 20 to 50 mol%, where x+y=100 mol%,
Wherein n is an integer of 0 to 7,
R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
The method of claim 1,
In Formula 1, x is 65 to 75 mol%, y is 25 to 35 mol%, wherein x+y = 100 mol%, and n is an integer of 5 to 7, fluorine-based organopolysilazane.
The method of claim 1,
The fluorine-based organopolysilazane has a water contact angle of 173 to 180° and an oil contact angle of 150 to 160°.
The method of claim 1,
The fluorine-based organopolysilazane has an ice adhesion strength of 35 to 100 kPa.
A method for producing a fluorine-based organopolysilazane, comprising: synthesizing a fluorine-based organopolysilazane satisfying the following formula (1).
[Formula 1]

(In Formula 1,
Wherein x and y are mol% of each repeating unit measured by ¹ H-NMR, x is 50 to 80 mol%, y is 20 to 50 mol%, where x+y=100 mol%,
Wherein n is an integer of 0 to 7,
R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)

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