KR20190142995A - Fluorine-based organic polysilazane or preparation methode thereof - Google Patents

Abstract

The present invention relates to a fluorine-based organic polysilazane or a method for manufacturing the same. More specifically, the present invention relates to: a polysilazane in which lyphophilic property is removed by introducing a fluorinated alkyl group; and a method for manufacturing the same. In order to achieve the object, the present invention is to manufacture the fluorine-based organic polysilazane by ammonolysis of perfluorodichlorosilane and halosilane under ammonia gas.

Description

Fluorine-based organic polysilazane or preparation method thereof {Fluorine-based organic polysilazane or preparation methode}

The present invention relates to a fluorine-based organopolysilazane or a method for preparing the same, and more particularly, to a polysilazane or a method for preparing the lipophilic by introducing an alkyl fluoride group.

Polysilazane is a polymer material having-(SiR ₂ -NR)-as a basic unit, and when heated, it is converted into a silica or silica material.Since the silica material is excellent in insulation, it is mainly used in electrical and electronic fields as an insulating film. It is used. In addition, since the polysilazane forms a SiO ₂ layer during the hydrolysis reaction with water, the surface coated with the polysilazane may form a highly durable film by reacting with moisture in the air.

Polysilazanes can be prepared in a variety of ways using a wide range of starting materials. Polysilazanes, which are generally made from ammonia, are ammonolysates, polysilas made from amino compounds other than ammonia containing NH ₂ groups. Cups are known as aminolysates.

As a method for preparing polysilazane by ammonolysis, US Pat. No. 4,395,460 discloses a process for preparing polysilazane by reacting a chlorodisilane solution dissolved in an inert solvent with ammonia gas. 10-2007-0040422 discloses a process for preparing ammonolysis products comprising polysilazane by introducing an excess of anhydrous liquid ammonia having one or more Si—H bonds into an excess of anhydrous liquid ammonia.

In addition, amino decomposition processes such as a method of synthesizing polysilazane by reacting an amine with a silicon halide such as SiCl ₄ , SiH ₂ Cl ₂ , or dehydrogenation of a silane compound with an amine compound using a transition metal complex catalyst The methods by are also proposed.

로 표시되는 분지상의 퍼플루오로폴레에테르를 원료로서 실란잔화한 퍼플루오로폴리에테르 변성 폴리실라잔이 개시되어 있다. 또한, 일본 특허공보 제2012-257650호에 직쇄상의 (CF₂O)_p(CF₂CF₂O)_q를 주쇄 구조에 갖는 퍼플루오로폴리에테르 변성 실라잔이 개시되어 있다.However, the general polysilazane prepared by the conventional method shows a water repellent performance due to the methyl functional group, but has a disadvantage of being vulnerable to contamination due to excessive lipophilic due to the methyl functional group. In order to improve this problem, polysilazane in which fluorine is introduced that does not get wet with both water and oil is proposed, and Japanese Patent Publication No. 2010-043251 is mainly proposed.

Disclosed is a perfluoropolyether-modified polysilazane obtained by silanicating a branched perfluoropolyether represented as a raw material. Also, Japanese Patent Publication No. 2012-257650 discloses a perfluoropolyether modified silazane having linear (CF ₂ O) _p (CF ₂ CF ₂ O) _q in a main chain structure.

However, the above case also does not have sufficient pollution wipeability and oil repellency. Accordingly, the present inventors have developed a polysilazane and a method for preparing the polysilazane, which have a property of removing lipophilic group and removing the lipophilic property of the polysilazane so that it is not easily contaminated or easy to remove the contamination. .

United States Patent US4395460 Republic of Korea Patent Publication No. 10-2007-0040422 Japanese Patent Publication No. 2010-043251 Japanese Patent Publication No. 2012-257650

The technical problem to be achieved by the present invention is to provide a fluorine-based organic polysilazane or a method for preparing the same by combining perfluorodichlorosilane and methyldichlorosilane.

However, these problems are exemplary, and the technical idea of the present invention is not limited thereto.

The organic polysilazane according to the technical idea of the present invention for achieving the above technical problem is characterized in that the fluorine-based organic polysilazane having a structure of formula (1).

[Formula 1]

In this case, n is an integer of 0 to 7, and x and y are an integer of 1 to 120.

In addition, the number average molecular weight (Mn) of the fluorine-based organopolysilazane of the present invention is characterized in that 1,000 to 50,000.

로 표시되는 분지상의 반복 단위를 갖는 실라잔을 나타내고, 특허문헌 4는 직쇄상의 (CF₂O)_p(CF₂CF₂O)_q 구조를 갖는 실라잔을 나타내는 것인 반면, 본 발명은 (CH₂)₂(CF₂)_nCF₃를 구조로 갖는 것으로서, 에테르기를 포함하지 않는다.On the other hand, Patent Documents 3 and 4 do not have a specific disclosure about the fluorine-based organopolysilazane introduced with an alkyl fluoride group containing no oxygen as shown in Formula 1, the Patent Document 3 is mainly

While a silazane having a branched repeating unit represented by is represented, Patent Document 4 shows a silazane having a linear (CF ₂ O) _p (CF ₂ CF ₂ O) _q structure, while the present invention It has (CH ₂ ) ₂ (CF ₂ ) _n CF ₃ as a structure and does not contain an ether group.

 In addition, the present invention can be produced as a repeating unit for both the silazane and alkyl fluoride group, while Patent Documents 3 and 4, only the perfluoroether can be adjusted as a repeating unit, the present invention is due to the difference in the structure of the Patent Document 3 and It provides a fluorine-based organopolysilazane and a method for producing the same having an excellent effect on the water repellent and oil repellent properties.

The fluorine-based organopolysilazane of the present invention can be prepared by ammonolysis of perfluorodichlorosilane and halosilane under ammonia gas.

At this time, the halosilane preferably contains at least one Si-H bond, for example, dichlorosilane, methyldichlorosilane, ethyldichlorosilane, ethyldioodosilane, ethyldifluorosilane, dichloromonofluoro Silane, propyldibromosilane, isopropyldichlorosilane, isobutyldichlorosilane, isoamyldichlorosilane, benzyldichlorosilane, propenyldichlorosilane, naphthyldichlorosilane, phenyldichlorosilane, difetylchlorosilane, methylethylchlorosilane, Vinylmethylchlorosilane, phenylmethylchlorosilane, dibenzylchlorosilane, p-chlorophenylmethylchlorosilane, n-hexyldichlorosilane, cyclohexyldichlorosilane, dicyclohexylchlorosilane, di-isobutylchlorosilane, p-tolyl In the group consisting of dichlorosilane, di-p-tolylchlorosilane, p-styryldichlorosilane, ethynyl dichlorosilane Selected may be more than one kind.

In addition, the perfluorodichlorosilanes are (3,3,3-trifluoropropyl) dichloromethylsilane, 3,3,4,4,5,5,5, -heptafluoropentylmethyldichlorosilane and 1H, It is preferably one kind selected from the group consisting of 1H, 2H, 2H-perfluorodecylmethyldichlorosilane.

When the perfluorodichlorosilane is (3,3,3-trifluoropropyl) dichloromethylsilane, the fluorine-based organopolysilazane has a structure of Formula 2 below.

[Formula 2]

When the perfluorodichlorosilane is 3,3,4,4,5,5,5, -heptafluoropentylmethyldichlorosilane, the fluorine-based organopolysilazane has a structure of Formula 3 below.

[Formula 3]

When the perfluorodichlorosilane is 1H, 1H, 2H, 2H-perfluorodecylmethyldichlorosilane, the fluorine-based organopolysilazane has a structure of Formula 4 below.

[Formula 4]

The present invention provides a method for preparing fluorine-based organopolysilazane according to Scheme 1 below.

Scheme 1

The method of preparing the fluorine-based organopolysilazane includes, in detail, (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; includes.

In this step, the basic solvent is trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, pyridine, picoline, dimethylaniline, trimethylphosphine, dimethylethylphosphine, methyldiethylphosphine, triethyl It is preferable that it is at least 1 type selected from the group which consists of a phosphine, a trimethyl arsine, a trimethyl styrene, a trimethylamine, a triethylamine, and a triazine.

In the second step, ammonia gas is preferably injected at a rate of 10 to 30 ml / min.

Stirring in steps 1 and 2 is preferably carried out at a temperature in the range of -10 ~ 10 ℃.

In addition, the stirring in the second step is preferably carried out in the range of 24 to 48 hours. If the agitation time is less than 24 hours, the ammonia decomposition reaction may not be sufficiently made, and if it exceeds 48 hours, the progress of the ammonolysis reaction over time is not preferable.

In step 4, the aging is preferably performed for 24 to 48 hours in the temperature range of 70 ~ 80 ℃.

Since the fluorine-based organopolysilazane provided by the present invention includes an alkyl fluoride group, the lipophilic is removed so that it is not easily contaminated or the contamination is easily removed.

Hereinafter, a preferred embodiment of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, it is provided to fully convey the spirit of the present invention to those skilled in the art so that the contents introduced herein are thoroughly and completely.

Preparation Example 1

According to Scheme 2, fluorine-based organopolysilazane was prepared.

Scheme 2

In detail, 6 ml of dichloromethylsilane and 3.5 g of (3,3,3-trifluoropropyl) dichloromethylsilane [(3,3,3-trifluoropropyl) Dichloromethylsilane] were added to a reactor with 65 ml of pyridine and 0 ° C. Stirred at. Ammonia gas was then injected into the solution at a rate of 20 ml / min while maintaining the temperature of the solution at 0 ° C. and stirred for 3 hours while bubbling. After the injection of ammonia gas was cut off and further stirring was continued for 24 hours at 0 ℃. After completion of the reaction, the salt precipitated in the reaction was removed through a filter, and the remaining pyridine was removed by vacuum distillation. The final product was aged for 24 hours at a temperature of 70 ℃ to increase the molecular weight to obtain a fluorine-based polysilazane, ¹ H-NMR (CDCl ₃ , 300Hz) of the fluorine-based polysilazane was measured, and the results are as follows. It was like

delta = 4.4 to 5 (m, 1H); 2.1 (m, 2 H); 0.8 (m, 2 H); 0.1 to 0.4 (m, 3H)

Preparation Example 2

First, according to Scheme 3-1, 3,3,4,4,5,5,5, -heptafluoropentylmethyldichlorosilane (3,3,4,4,5,5,) as perfluorodichlorosilane 5-heptafluoropentylmethyldichlorosilane) was prepared.

Scheme 3-1

In detail, 19.6 g of 3,3,4,4,5,5,5-heptafluoropent-1-ene (3,3,4,4,5,5,5-Heptafluoropent-1-ene) And 11 g of dichloromethylsilane were added to the reactor together with 100 ml of tetrahydrofuran and stirred. Subsequently, 10 drops of Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution was added to the platinum catalyst and stirred at room temperature for 24 hours. After completion of the reaction, the reaction product was vacuum distilled to prepare 3,3,4,4,5,5,5-heptafluoropentylmethyldichlorosilane, and the 3,3,4,4,5,5,5- ¹ H-NMR (CDCl ₃ , 300 Hz) of heptafluoropentylmethyldichlorosilane was measured, and the results were as follows.

delta = 2.30 (m, 2H); 1.39 (m, 2 H); 0.89 (s, 3H)

Next, according to Scheme 3-2, a fluorine-based organic polysilazane was prepared through the 3,3,4,4,5,5,5-heptafluoropentylmethyldichlorosilane prepared above.

Scheme 3-2

In detail, 17.9 g of 3,3,4,4,5,5,5-heptafluoropentylmethyldichlorosilane and 6 ml of dichloromethylsilane were added to a reactor together with 60 mL of pyridine and stirred at 0 ° C. Ammonia gas was then injected into the solution at a rate of 20 ml / min while maintaining the temperature of the solution at 0 ° C. and stirred for 3 hours while bubbling. After the injection of ammonia gas was cut off and further stirring was continued for 24 hours at 0 ℃. After completion of the reaction, the salt precipitated in the reaction was removed through a filter, and the remaining pyridine was removed by vacuum distillation. The final product was aged for 24 hours at a temperature of 70 ℃ to increase the molecular weight to obtain a fluorine-based polysilazane, ¹ H-NMR (CDCl ₃ , 300Hz) of the fluorine-based polysilazane was measured, and the results are as follows. It was like

delta = 4.4 to 5 (m, 1H); 2.1 (m, 2 H); 0.8 (m, 2 H); 0.1 to 0.4 (m, 3H)

Preparation Example 3

First, according to Scheme 4-1, 1H, 1H, 2H, 2H-perfluorodecylmethyldichlorosilane (1H, 1H, 2H, 2H-Perfluorodecylmethyldichlorosilane) was prepared as perfluorodichlorosilane.

Scheme 4-1

In detail, 44.6 g of 1H, 1H, 2H-Perfluoro-1-decene and 11 g of dichloromethylsilane were added to a reactor with 100 ml of tetrahydrofuran and stirred. It was. Subsequently, 10 drops of Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution was added to the platinum catalyst and stirred at room temperature for 24 hours. After the reaction was completed and the reaction product was vacuum distilled 1H, 1H, 2H, 2H- perfluoro decyl methyl dichloro silane were prepared, the 1H, 1H, 2H, 2H- ^{perfluoro-decyl-methyl-1} H- of dichloro silane NMR (CDCl ₃ , 300 Hz) was measured, and the results were as follows.

delta = 2.30 (m, 2H); 1.39 (m, 2 H); 0.89 (s, 3H)

Next, according to Scheme 4-2, fluorine-based organopolysilazane was prepared through 1H, 1H, 2H, 2H-perfluorodecylmethyldichlorosilane prepared above.

Scheme 4-2

In detail, 32.3 g of 1H, 1H, 2H, 2H-perfluorodecylmethyldichlorosilane and 6 ml of dichloromethylsilane were added to a reactor together with 100 mL of pyridine and stirred at 0 ° C. Ammonia gas was then injected into the solution at a rate of 20 ml / min while maintaining the temperature of the solution at 0 ° C. and stirred for 3 hours while bubbling. After the injection of ammonia gas was cut off and further stirring was continued for 24 hours at 0 ℃. After completion of the reaction, the salt precipitated in the reaction was removed through a filter, and the remaining pyridine was removed by vacuum distillation. The final product was aged for 24 hours at a temperature of 80 ℃ to increase the molecular weight to obtain a fluorine-based polysilazane, ¹ H-NMR (CDCl ₃ , 300 Hz) of the fluorine-based polysilazane was measured, and the results are as follows. It was like

delta = 4.4 to 5 (m, 1H); 2.1 (m, 2 H); 0.8 (m, 2 H); 0.1 to 0.4 (m, 3H)

Experimental Example  1. Wetting

으로 이루어진 퍼플루오로 폴리에테르 변성 폴리실라잔(비교예 1) 및 특허문헌 4의 제조방법을 참고하여 F(CF₂O)_p(C₂F₄O)_q-CF₂CH₂OC₃H₆-SiNH_1.5 95몰% 및 F(CF₂O)_p(C₂F₄O)_q-CF₃ 5몰% (이때, q/p = 0.9, p+q ≒ 1.7)로 이루어진 퍼플루오로폴리에테르 변성 폴리실라잔(비교예 2)을 준비하였다.In order to evaluate the wettability of the fluorine-based polysilazane of the present invention with reference to the manufacturing method of Patent Document 3

F (CF ₂ O) _p (C ₂ F ₄ O) _q -CF ₂ CH ₂ OC ₃ H ₆ with reference to the perfluoro polyether modified polysilazane (Comparative Example 1) and the manufacturing method of Patent Document 4 Perfluoropolyether consisting of 95 mol% of SiSiH _1.5 and ₅ mol% of F (CF ₂ O) _p (C ₂ F ₄ O) _q -CF ₃ (where q / p = 0.9, p + q ≒ 1.7) Modified polysilazane (Comparative Example 2) was prepared.

Preparation Examples 1 to 3 and Comparative Examples 1 to 2 were dissolved in α, α, α-Trifluorotoluene at a concentration of 5%, respectively, and then dip coated by supporting the washed slide glass in a mixed solution, followed by coating the coated slide glass at 80 ° C. After drying for 24 hours in the oven was measured water contact angle and oil contact angle, the results are summarized in Table 1 below.

Condition Contact angle (°) water Oil Preparation Example 1 118 84 Preparation Example 2 117 86 Preparation Example 3 119 85 Comparative Example 1 114 78 Comparative Example 2 115 74

With reference to Table 1, in the case of Preparation Examples 1 to 3 it can be seen that the contact angle with the oil is high compared to Comparative Examples 1 and 2, through which it was confirmed that the oil repellency is significantly improved. In the case of using the polysilazane prepared in Preparation Examples 1 to 3 as a surface treatment agent, both water repellency and oil repellency are not easily contaminated and it was confirmed that the contamination is easily removed.

Claims (10)

Fluorine-based organopolysilazane having the structure of Formula 1 below.
[Formula 1]

Said is an integer of n = 0-7 and an integer of x and y = 1-120. The method of claim 1,
The fluorine-based organopolysilazane is a fluorine-based organopolysilazane, characterized in that the perfluorodichlorosilane and halosilane is prepared by combining. The method of claim 1,
The fluorine-based organopolysilazane is fluorine-based organopolysilazane, characterized in that represented by one species selected from the group consisting of
[Formula 2]

[Formula 3]

[Formula 4]

A method for producing fluorine-based organopolysilazane, wherein ammonia decomposition of perfluorodichlorosilane and halosilane is carried out under ammonia gas to produce organopolysilazane having the structure of formula (1).
[Formula 1]

Said is an integer of n = 0-7 and an integer of x and y = 1-120. The method of claim 4, wherein
The perfluorodichlorosilanes are (3,3,3-trifluoropropyl) dichloromethylsilane, 3,3,4,4,5,5,5, -heptafluoropentylmethyldichlorosilane and 1H, 1H, A method for producing a fluorine-based organopolysilazane, characterized in that one selected from the group consisting of 2H, 2H-perfluorodecylmethyldichlorosilane. The method of claim 4, wherein
The halosilane is dichlorosilane, methyldichlorosilane, ethyldichlorosilane, ethyldioodosilane, ethyldifluorosilane, dichloromonofluorosilane, propyldibromosilane, isopropyldichlorosilane, isobutyldichlorosilane, isoamyldichloro Silane, benzyldichlorosilane, propenyldichlorosilane, naphthyldichlorosilane, phenyldichlorosilane, difetylchlorosilane, methylethylchlorosilane, vinylmethylchlorosilane, phenylmethylchlorosilane, dibenzylchlorosilane, p-chlorophenylmethyl Chlorosilane, n-hexyldichlorosilane, cyclohexyldichlorosilane, dicyclohexylchlorosilane, di-isobutylchlorosilane, p-tolyldichlorosilane, di-p-tolylchlorosilane, p-styryldichlorosilane, ethynyl Method for producing fluorine-based organopolysilazane, characterized in that at least one member selected from the group consisting of dichlorosilane. The method of claim 4, wherein
The ammonia gas is a method of producing a fluorine-based organopolysilazane, characterized in that injected at a rate of 10 to 30 ml / min. The method of claim 4, wherein
The ammonolysis reaction is a method for producing a fluorine-based organopolysilazane, characterized in that performed for 24 to 48 hours at a temperature of -10 ~ 10 ℃. The method of claim 4, wherein
The perfluorodichlorosilane and halosilane is dissolved in a basic solvent and the method for producing a fluorine-based organopolysilazane characterized in that the reaction. The method of claim 9,
The basic solvent is trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, pyridine, picoline, dimethylaniline, trimethylphosphine, dimethylethylphosphine, methyldiethylphosphine, triethylphosphine, trimethylar Method for producing a fluorine-based organic polysilazane, characterized in that at least one selected from the group consisting of shin, trimethyl styrene, trimethylamine, triethylamine, triazine.