KR102260650B1 - The fabrication method of linear organic polysilazane using carbon dioxide as solvent and linear organic polysilazane prepared by the same - Google Patents

Abstract

The present invention relates to a method for producing a linear organopolysilazane using a carbon dioxide solvent and a linear organopolysilazane prepared using the same, characterized in that it is prepared by reacting an organosilane compound with ammonia in a liquid carbon dioxide solvent.
The method of the present invention has an advantage of using an environmentally friendly and non-polluting carbon dioxide solvent compared to using an organic solvent, and an organopolysilazane prepared using an organic solvent or an organopolysilazane prepared using a supercritical carbon dioxide solvent. In contrast to the structure in which the glass has a complex mixture of linear and cyclic structures, the organopolysilazane prepared in the liquid carbon dioxide solvent through the method of the present invention is prepared in a linear state and substrate coating is performed using it. There is an advantage that it can be effectively applied as a coating material compared to organopolysilazane in a composite state, in which the coating was not uniform and the surface state was unstable.

Description

The manufacturing method of linear organopolysilazane using carbon dioxide solvent and linear organopolysilazane prepared using same

The present invention relates to a method for preparing a linear organopolysilazane using a liquid carbon dioxide solvent and to a linear organopolysilazane prepared using the same. More particularly, the present invention relates to a method for preparing a linear organopolysilazane by performing an ammonolysis reaction between a silane compound and ammonia in a liquid carbon dioxide solvent, and to a linear organopolysilazane prepared using the same.

Polysilazane (PSZ) is a polymer of the following formula 1 in which silicon and nitrogen atoms are alternately connected to the back bone, and R ₁ , R ₂ , R ₃ is -H or an organic substituent (eg, alkyl).

[Formula 1]

When R ₁ , R ₂ , and R ₃ of polysilazane are all -H, it is called inorganic polysilazane or perhydropolysilazane (PHPS) and is generally a polymer having a hexagonal structure. It is a material that can be decomposed to form an ultra-thin SiO ₂ layer and exhibits hydrophilicity. On the other hand, when the R group is substituted with an organic substituent (generally methyl), it is called organopolysilazane (OPSZ), and when decomposed after surface coating, the R group remains and hydrophobicity is expressed.

Since inorganic polysilazane is finally formed in the form of silica, it is very hard and has excellent electrical insulation, but is brittle, whereas organopolysilazane is flexible. Polysilazane is transparent and has different applications depending on the R group, and can be applied in various ways using various organic substituents. Organopolysilazane has water repellency and high transparency, so it is used for the exterior of home appliances, architectural exteriors, and automobile exteriors (car body). , wheel, glass, glass film coating), inorganic silazane is used for ultra-thin silica coating with high hardness performance (pencil hardness 9H) and high transparency, high hardness coating for display/optical use, ceramic insulation coating, glare Used for anti-glare coatings.

However, as a problem with the synthesis of polysilazane, inorganic polysilazane is gas-gas phase synthesis, which requires know-how skilled in chemical engineering compared to liquid-liquid phase synthesis, and salts (NH ₄ Cl or ⁺ Since the process of removing N(C ₂ H ₅ )HCl ^- ) and hexagonal silazane is involved, the manufacturing process is complicated, and it is not easy to control the polymerization degree of the polymer. On the other hand, since organopolysilazane is generally prepared by using a large amount of an organic or halogen solvent as a polymer polymerization solvent, all of the solvents used have health and safety risks and are harmful to the environment. In particular, petroleum solvents generate flammability and smog, and when a non-volatile solvent such as an aqueous solution is used instead of the volatile solvent, wastewater is generated, and a large amount of time and energy is required for drying after washing. have.

On the other hand, carbon dioxide (CO ₂ ) solvent is environmentally friendly and is used as a non-polluting solvent, but has a problem in dissolving polar or inactive compounds because the solubility is too low compared to other polar solvents. However, silicone-like polymers and partially fluorinated compounds are known to have good solubility in liquid and supercritical carbon dioxide. Carbon dioxide has a low critical temperature (31.1 ℃) and critical pressure (73.8 bar), so it can easily reach liquid and supercritical states. changes to a gaseous state by It is also non-toxic, non-combustible, inexpensive and environmentally friendly. Carbon dioxide transitions to a supercritical state above its critical conditions (TC = 31.1 ℃, PC = 73.8 bar), and has unique properties different from liquids and gases. Supercritical carbon dioxide has a density similar to that of a liquid, but has a low viscosity like a gas and a fast diffusion rate.

The present inventors synthesized inorganic and fluorine-based polysilazanes by applying such an eco-friendly carbon dioxide solvent (Patent Application No. 10-2018-0130375). In general, for a polysilazane synthesized in a solvent known to have a structure in which linear and cyclic structures do not have the structure of the linear are mixed in combination, and their structures and ¹ HNMR spectra were four formulas of the body Comparative Synthesis Example 1 and As shown in FIG. 4 , the structure of polysilazane prepared using supercritical carbon dioxide was also confirmed to have the same structure as that generally synthesized in a solvent.

However, when substrate coating is performed using an organopolysilazane having a structure in which linear and cyclic structures are complexly mixed, the coating is not uniform and the surface state is unstable, resulting in a more unified state of organopolysilazane. The need to synthesize the cup was demanded.

Therefore, the present inventors proceeded to synthesize organopolysilazane using liquid carbon dioxide, not supercritical carbon dioxide, and as a result, linear organopolysilazane having a different structure from that of polysilazane produced in the organic solvent and supercritical carbon dioxide. By confirming that silazane was formed, the present invention could be completed.

Korean Patent Laid-Open Patent No. 10-2015-0115642 (Title of the invention: Method for preparing silazane compound, Applicant: SHIN ETSU CHEM CO LTD, Publication date: October 14, 2015) Republic of Korea Patent No. 10-1517856 (Title of the Invention: Method for producing polysilsesquioxane using carbon dioxide solvent and organic solvent as cosolvent and polysilsesquioxane manufactured using the same, Applicant: Korea Institute of Industrial Technology, Registration date: April 29, 2015) Republic of Korea Patent Registration No. 10-1272841 (Title of the invention: Synthesis and application of superhydrophobic copolymer using carbon dioxide solvent, Applicant: Korea Institute of Industrial Technology, Registration date: June 03, 2013) Japanese Patent No. 4159937 (Title of Invention: Polysilazane Composition, Applicant: AZ ELECTRONIC MATERIALS KK)

An object of the present invention is to provide a method for preparing a linear organopolysilazane using a liquid carbon dioxide solvent and a linear organopolysilazane prepared using the same. More specifically, it is an object of the present invention to provide a method for preparing a linear organopolysilazane by performing an ammonolysis reaction between a silane compound and ammonia in a liquid carbon dioxide solvent, and to provide a linear organopolysilazane prepared using the same. have.

The present invention relates to a method for producing a linear organopolysilazane represented by the following formula (2), characterized in that it is prepared by reacting an organosilane compound with ammonia in a liquid carbon dioxide solvent.

[Formula 2]

(In Formula 2, n is an integer of 1 to 120, and R is a hydrogen atom, a substituted/unsubstituted alkyl group, a substituted/unsubstituted cycloalkyl group, a substituted/unsubstituted alkenyl group, or a substituted/unsubstituted aryl group. selected and at least one R is a hydrogen atom)

The preparation of the organopolysilazane may be more preferably performed including the following steps.

To this end, a first step of injecting the organosilane compound into the reactor and pressurizing;

a second step of injecting carbon dioxide into the reactor and stirring after the organosilane compound is injected;

a third step of additionally injecting liquid ammonia into the reactor after the injection of carbon dioxide;

a fourth step of aging by increasing the reaction temperature and pressure of the reactor after injection of the liquid ammonia; and;

a fifth step of recovering the linear organopolysilazane as a reaction product from the reactor after the aging step;

It is characterized in that it is carried out including

The organosilane compound is selected from R2SiX2, R3SiX, and mixtures thereof, and R is a hydrogen atom, a substituted/unsubstituted alkyl group, a substituted/unsubstituted cycloalkyl group, a substituted/unsubstituted alkenyl group, and a substituted/unsubstituted aryl group. is selected from the group, at least one R is a hydrogen atom, and X may be selected from fluorine, iodine, chlorine and bromine. Specifically, dichloromethylsilane, dichloroethylsilane, dichloropropylsilane, dichloroisobutylsilane, dichloropentylsilane, dichlorohexylsilane, dichlorooctylsilane, dichlorohexadecylsilane, dichlorooctadecylsilane, dichloro(2-phenylethyl)silane , at least from the group consisting of dichloro[2-(7-oxabicyclo[4,1,0]hept-3-yl)ethyl]silane, dichloro(3-cyanopropyltriethoxysilane, dichlorocyclohexylsilane Any one or more may be further selected.

Meanwhile, when the organosilane compound is added, perfluorodichlorosilane may be further added.

In the synthesis of linear organopolysilazane, such an organosilane compound and ammonia are preferably mixed in a volume ratio of 1:2 (v:v) to 1:4 (v:v), where perfluorodichlorosilane is When added, the organosilane compound: perfluorodichlorosilane may be added in a ratio of 1:0.5 (v:w) to 1:2 (v:w).

The pressure in the reactor in the first to third steps is characterized in that it is maintained at 60 to 100 bar, and when it is out of this pressure range, an unreacted raw material sample may be generated, which is not preferable because the reaction yield is lowered.

The reaction temperature of the third step is preferably lower than that of the first to second steps, and preferably, the reaction temperature is maintained at -5 to 5 °C. If the reaction temperature is not maintained at -5 to 5 °C, the liquefied state of carbon dioxide may not be maintained well, and the reaction to the next step may not proceed well.

In addition, maintaining the carbon dioxide in the fourth step in a liquid state rather than a supercritical state may increase the synthesis yield of the linear organopolysilazane.

The reaction temperature of the fourth step is preferably maintained by raising it below the critical temperature of carbon dioxide, 31°C.

The pressure of the reactor in the fourth step is characterized in that it is maintained higher than the reaction pressure in the first to third steps.

In the fifth step, carbon dioxide may be injected into the reactor to recover linear organopolysilazane, and in this case, it is preferable to inject carbon dioxide into the reactor at a rate of 10 to 30 mL/min.

The synthesis of such a linear organopolysilazane may be prepared through a conventional compound synthesis reactor.

In the production method of the present invention, the structure of linear organopolysilazane can be controlled according to the type and amount of the silane compound used. In general, the longer the reaction time and the higher the reaction temperature, the higher the molecular weight. A linear organopolysilazane can be obtained. In particular, since a liquid carbon dioxide solvent is used as a solvent, a linear organopolysilazane with a reaction yield of 90% or more can be obtained by controlling the temperature and pressure thereof.

In addition, the present invention may provide a linear organopolysilazane prepared by the above methods, wherein the linear organopolysilazane has a molecular weight distribution of 10 or less.

The present invention relates to a method for producing a linear organopolysilazane using a carbon dioxide solvent and a linear organopolysilazane prepared using the same, characterized in that it is prepared by reacting an organosilane compound with ammonia in a liquid carbon dioxide solvent.

The method of the present invention has the advantage of using an environmentally friendly and non-polluting carbon dioxide solvent compared to using an organic solvent, and an organopolysilazane prepared using an organic solvent or an organopolysilazane prepared using a supercritical carbon dioxide solvent. In contrast to the structure in which the glass has a complex mixture of linear and cyclic structures, the organopolysilazane prepared in the liquid carbon dioxide solvent through the method of the present invention is prepared in a linear state and substrate coating is performed using it. There is an advantage that it can be effectively applied as a coating material compared to organopolysilazane in a composite state, in which the coating was not uniform and the surface state was unstable.

^{1 is a graph showing the 1} HNMR (CDCl ₃ , 300Hz) spectrum of the organopolysilazane prepared in Synthesis Example 1 of the present invention.
2 is a graph showing the results of molecular weight analysis of the organopolysilazane prepared in Synthesis Example 1 of the present invention using gel permeation chromatography (GPC) analysis.
3 is a graph showing the results of structural analysis of the organopolysilazane prepared in Synthesis Example 1 of the present invention using infrared spectroscopy (FTIR).
^{4 is a graph showing 1} HNMR spectrum of organopolysilazane prepared through a supercritical reaction of a carbon dioxide solvent prepared in Comparative Synthesis Example 1 of the present invention.
5 is a graph showing the results of molecular weight analysis of organopolysilazane prepared in Comparative Synthesis Example 1 of the present invention using gel permeation chromatography (GPC) analysis.

Hereinafter, preferred embodiments 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 so that this disclosure will be thorough and complete, and will fully convey the spirit of the invention to those skilled in the art.

<Synthesis Example 1. Preparation of linear organopolysilazane using carbon dioxide solvent>

In the present invention, the ammonolysis reaction process using a carbon dioxide solvent to prepare the organopolysilazane is represented by Scheme 1 below.

[Scheme 1]

(In Scheme 1, n is an integer of 1 to 120.)

The synthesis process of linear organopolysilazane is as follows.

First, dichloromethylsilane (20ml) was put into a 300mL carbon dioxide reactor, and carbon dioxide was injected using a syringe pump under conditions of 25°C and 80bar, and stirring was performed at the same time as the injection of carbon dioxide at a speed of 80rpm. After that, using a syringe pump, 40 mL of liquid ammonia at 0° C. and 85 bar was injected into the reactor to conduct an ammonolysis reaction, and after the injection of ammonia was completed, the temperature and pressure in the reactor were maintained at 25° C. and 150 bar, respectively. The reaction proceeded for hours. After 2 hours, carbon dioxide at 25° C. and 150 bar was injected into the reactor at a rate of 20 mL/min using a syringe pump, and the vent valve was opened at the same time to recover the synthesized organopolysilazane product in the reactor.

The recovered product was vacuum-dried at room temperature, and the yield was 92% as a viscous, transparent liquid.

¹ H-NMR (CDCl ₃ , 300Hz) results of the synthesized organopolysilazane are shown in FIG. 1 . 1, characteristic peaks of H-Si, CH ₃ -Si and HN appear at 4.74, 0.23 and 0.6 ppm, respectively. In addition, the positions of the characteristic peaks in FIG. 1 are as follows. δ = 4.74 (m, 1H) 0.23 (m, 3H); 0.6 (D, 1H).

=386,

=1760, PDI=4.57로 측정되었다.Next, molecular weight analysis of the synthesized organopolysilazane was performed using gel permeation chromatography (GPC) analysis, and the results are shown in FIG. 2 . Looking at the analysis of Figure 2, the synthesized organic polysilazane is

=386,

= 1760, PDI = 4.57.

In addition, the structure of the synthesized organopolysilazane was analyzed using infrared spectroscopy (FTIR) and shown in FIG. 3 . In FIG. 3 , the NH characteristic peaks ^{appear at 1180 cm -1} and 3385 cm ^-1 , respectively, and CH and Si-H Characteristic peaks appear at ^{2960 cm -1} and 2150 cm ^{-1 , respectively.}

From the above results, it can be confirmed that the following compound of Formula 3 was synthesized as expected in Scheme 1 through this synthesis process.

[Formula 3]

(In Scheme 1, n is an integer of 1 to 120.)

<Comparative Synthesis Example 1. Preparation of organopolysilazane using supercritical carbon dioxide>

When organopolysilazane is synthesized using supercritical carbon dioxide, a compound having a representative structure of Formula 4 is prepared. In order to confirm this, the following synthesis process was performed.

Dichloromethylsilane (20ml) was put into a 300mL carbon dioxide reactor, and carbon dioxide was injected using a syringe pump under the conditions of 25°C and 100bar, and stirring was performed at the same time as the injection of carbon dioxide at a speed of 80rpm. Next, 40 mL of liquid ammonia at 0° C. and 100 bar was injected into the reactor using a syringe pump to proceed with the ammonolysis reaction. Thereafter, after the injection of ammonia was completed, carbon dioxide was additionally injected into the reactor using a syringe pump, and the temperature and pressure were set to 60° C. and 200 bar, respectively, and the reaction was carried out for 2 hours. After 2 hours, the temperature of the reactor was lowered to 25 ° C, and carbon dioxide at 25 ° C and 150 bar was injected at a rate of 20 mL/min using a syringe pump, and the vent valve was opened at the same time to obtain the organopolysilazane product synthesized inside the reactor. recovered.

The recovered product was vacuum-dried at room temperature, and was prepared in a viscous, pale yellow, transparent liquid state, and the yield was 91%.

¹ H-NMR (CDCl ₃ , 300 Hz) results of the synthesized organopolysilazane are shown in FIG. 4 . The characteristic peaks of H-Si and CH ₃ -Si and HN appear at 4.5-5.2, 0.2-0.5 and 0.7-1.4 ppm, respectively. At this time, the positions of the characteristic peaks in FIG. 4 are as follows. δ = 4.5-5.2 (m, 1H) 0.2-0.5 (m, 3H); 0.7 to 1.4 (m, 1H).

=77,

=1745, PDI=22.589로 측정되었다.Next, molecular weight analysis of the synthesized organopolysilazane was performed using gel permeation chromatography (GPC) analysis, and the results are shown in FIG. 5 .

=77,

=1745, PDI=22.589.

Claims (13)

A first step of pressurizing by injecting an organosilane compound into the reactor;
a second step of injecting carbon dioxide into the reactor and stirring after the organosilane compound is injected;
a third step of additionally injecting liquid ammonia into the reactor after the injection of carbon dioxide;
a fourth step of aging by increasing the reaction temperature and pressure of the reactor after the injection of the liquid ammonia; and;
A method for producing a linear organopolysilazane represented by the following formula (2), comprising: a fifth step of recovering the linear organopolysilazane as a reaction product from the reactor after the aging step.
[Formula 2]

(In Formula 2, n is an integer of 1 to 120, and R is a hydrogen atom, a substituted/unsubstituted alkyl group, a substituted/unsubstituted cycloalkyl group, a substituted/unsubstituted alkenyl group, or a substituted/unsubstituted aryl group. selected and at least one R is a hydrogen atom) delete According to claim 1,
The organosilane compound is selected from R2SiX2, R3SiX, and mixtures thereof, and R is a hydrogen atom, a substituted/unsubstituted alkyl group, a substituted/unsubstituted cycloalkyl group, a substituted/unsubstituted alkenyl group, and a substituted/unsubstituted aryl group. A method for producing a linear organopolysilazane, characterized in that selected from the group, at least one R is a hydrogen atom, and X is selected from fluorine, iodine, chlorine and bromine. According to claim 1,
The method for producing a linear organopolysilazane, characterized in that the pressure in the reactor in the first to third steps is 60 to 100 bar. 5. The method of claim 4,
The method for producing a linear organopolysilazane, characterized in that the reaction temperature of the third step is lower than that of the first to second steps. 6. The method of claim 5,
The reaction temperature of the third step is a method for producing a linear organic polysilazane, characterized in that maintained at -5 ~ 5 ℃. According to claim 1,
The method for producing linear organopolysilazane, characterized in that the carbon dioxide in the fourth step is maintained in a liquid state rather than supercritical. 8. The method of claim 7,
The method for producing a linear organopolysilazane, characterized in that the reaction temperature of the fourth step is raised and maintained below the critical temperature of carbon dioxide, 31°C. 8. The method of claim 7,
The method for producing linear organopolysilazane, characterized in that the pressure of the reactor in the fourth step is maintained higher than the reaction pressure in the first to third steps. According to claim 1,
A method for producing a linear organopolysilazane, characterized in that by injecting carbon dioxide into the reactor in the fifth step to recover the linear organopolysilazane. 11. The method of claim 10,
A method for producing a linear organopolysilazane, characterized in that in the fifth step, carbon dioxide is injected into the reactor at a rate of 10 to 30 mL/min. delete delete

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