KR20100131312A - Polyfluorosilsesquioxane and preparation method thereof - Google Patents

Abstract

The present invention relates to a polyfluoro silsesquioxane having a fluoro hydrocarbon side chain and a method for producing the same. Since the polyfluorosilsesquioxane according to the present invention contains a fluorocarbon hydrocarbon as a side chain and has a low dielectric constant, the polyfluorosilsesquioxane may be used as an interlayer insulating film of a semiconductor. Since it can be greatly reduced, it can be used as a material such as an optical waveguide material or a protective coating and a water repellent coating of the optical fiber. Polyfluoro-based silsesquioxanes according to the present invention are synthesized by the method of directly condensation hydrolysis products of fluoro-based silane monomers under a specific catalyst and reaction temperature conditions. According to this method, it is easy to adjust molecular weight and can synthesize polyfluoro silsesquioxane with a small molecular weight distribution. In addition, polyfluorosilsesquioxane having a high regular ladder structure may be selectively synthesized, and various photocuring groups may be introduced during the polymerization process to impart photocuring properties to polyfluorosilsesquioxane.

Description

Fluoroinated Polysilsesquioxane and Method for Preparing the Same

The present invention relates to a polyfluoro silsesquioxane having a fluorohydrocarbon side chain and a method for preparing the same, and more particularly to hydrocondensation of a hydrolyzate of a silane monomer having a fluorohydrocarbon under a specific basic catalyst and reaction temperature conditions. It is synthesize | combined by the method and relates to the polyfluoro silsesquioxane which has a low dielectric constant and high permeability, and its manufacturing method.

Polysilsesquioxane (polysilsesquioxane) is a composite material having a combined characteristics of organic and inorganic materials, has been spotlighted as a photosensitive heat-resistant material. Polysilsesquioxane can be synthesized into a random structure, a partial network structure, a ladder structure, and the like according to the preparation method thereof, and polysilsesquioxane having a ladder structure has better thermal decomposition characteristics than other structures. Known.

In a general method for producing polysilsesquioxanes, oligomers prepared by the sol-gel method using triethoxysilane monomers or by hydrolysis of trichlorosilane or trialkoxysilanes are heated and stored under an alkali metal catalyst. It manufactures together.

The polysilsesquioxane-based polymer has excellent transparency and thermal stability, low moisture absorption and excellent dielectric constant of 3.0 or less, but the dielectric constant must be further lowered for use as an interlayer insulating film of a highly integrated semiconductor.

According to the results of the present inventors, a technique of introducing a fluoro side chain group in order to lower the dielectric constant of polysilsesquioxane has been proposed, but in general, a monomer containing a fluoro group by a polymerization method of a silsesquioxane polymer It has been pointed out that there is a problem that the degree of polymerization of is greatly reduced. Particularly, when synthesized by the sol-gel method, gelation proceeds due to cleavage of the fluorocarbon group during the reaction, and it is difficult to obtain only a ladder-structured polymer, a molecular weight of less than 1,000 and a yield of 10% or less have a problem. .

Therefore, the present inventors have intensively studied to prepare a highly regular ladder-structured polyfluorosilsesquioxane introduced with a fluorohydrocarbon side chain group, and as a result, the hydrolyzate of the fluorohydrocarbonsilane monomer may be converted into lithium hydroxide, sodium hydroxide or Applying a method of condensation polymerization at a temperature of 5 to 85 ° C. using a basic catalyst such as potassium carbonate reduces the dielectric constant and realizes that a polymer having a regular ladder structure can be formed by effective structure control. The present invention has been completed.

Accordingly, an object of the present invention is to provide a ladder-structured polyfluorosilsesquioxane in which a fluorohydrocarbon side chain group is introduced.

It is another object of the present invention to provide a method for efficiently preparing a highly regular polyfluoro-based silsesquioxane using fluorohydrocarbon silane monomers.

According to one embodiment of the present invention, a polyfluoro-based silsesquioxane having a fluorohydrocarbon side chain group and represented by the following Chemical Formula 1 is provided.

<Formula 1>

In Chemical Formula 1,

R ₁ and R ₂ are each independently selected from the group consisting of a fluoroaromatic group, a fluoroalkyl group, an allyl group, a vinyl group, an epoxy group, a methacryl group and an acryl group, and at least one of R ₁ and R ₂ is fluoro Aromatic group or fluoroalkyl group, n is an integer of 5 to 10,000.

In an embodiment of the invention, the polyfluorosilsesquioxane may have a number average molecular weight (Mn) in the range of 1,000 to 100,000. In addition, the polyfluorosilsesquioxane may be a homopolymer or copolymer having a regular ladder structure.

According to one embodiment of the present invention, comprising the polycondensation of the hydrolyzate of the silane monomer represented by the formula (2) at a temperature of 5 ~ 85 ℃, of the polyfluoro-based silsesquioxane represented by the following formula (1) A manufacturing method is provided.

<Formula 2>

<Formula 1>

In Chemical Formula 1 or 2, R is R ₁ or R ₂ ; R ₁ and R ₂ are each independently selected from the group consisting of fluoroaromatic groups, fluoroalkyl groups, allyl groups, vinyl groups, epoxy groups, methacryl groups and acryl groups, and at least one of R ₁ and R ₂ is fluorine; A ro aromatic group or a fluoroalkyl group; X ₁ , X ₂ and X ₃ are each independently a halogen atom, an alkoxy group or a hydroxy group; n is an integer from 5 to 10,000.

In an embodiment of the invention, the polycondensation reaction is carried out under a basic catalyst of lithium hydroxide, sodium hydroxide or potassium carbonate.

According to the production method of the present invention, since the gelation due to the structural defects and random structure of the oligomer is not formed, it is possible to synthesize polyfluorosilsesquioxane, which is soluble in general general organic solvents, has excellent heat resistance and excellent optical properties. have. In addition, according to the production method of the present invention, a fine refractive index can be controlled through copolymerization of a fluoro monomer and a hydrocarbon monomer, and a photocuring group can be introduced into the polymer to impart photocuring properties to the polymer.

In addition, the polyfluorosilsesquioxane of the present invention can be used as a material such as heat-resistant coating and heat-resistant coating, optical fiber protective coating, optical waveguide material, interlayer insulating film, resist material.

Hereinafter, a polyfluorosilsesquioxane and a manufacturing method thereof according to one embodiment of the present invention will be described in detail.

According to one embodiment of the present invention, there is provided a polyfluoro silsesquioxane represented by the following formula (1) having a fluorohydrocarbon side chain group.

<Formula 1>

R ₁ and R ₂ are each independently selected from the group consisting of a fluoroaromatic group, a fluoroalkyl group, an allyl group, a vinyl group, an epoxy group, a methacryl group and an acryl group, and at least one of R ₁ and R ₂ is fluoro Aromatic group or fluoroalkyl group, n is an integer of 5 to 10,000.

In the present specification, the "aromatic group" may include an aryl group such as a phenyl group and a tolyl group, or a heteroaryl group containing a hetero atom such as nitrogen, oxygen, or sulfur.

In the present specification, the "fluoroaromatic group" means that some or all of the hydrogen atoms of the aromatic group is substituted with a fluoro atom.

In the present specification, the "alkyl group" is a C1-C24 side chain or crushed alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, cyclopropyl group, cyclophene C3-C10 cycloalkyl groups, such as a methyl group and a cyclohexyl group, C2-C10 alkenyl groups, such as an allyl group and a vinyl group, or a C3-C10 cycloalkenyl group containing a double bond, etc. can be included. .

In the present specification, the "fluoroalkyl group" means that some or all of the hydrogen atoms of the alkyl group are substituted with fluoro atoms.

In the present specification, allyl groups, vinyl groups, epoxy groups, methacryl groups, and acrylic groups introduced as photocuring groups are functional groups which can be cured by light and heat, and these may be ones or all of hydrogen atoms substituted with fluoro atoms. have.

The polyfluorosilsesquioxane represented by Formula 1 according to the present invention may be a homopolymer or a copolymer.

In the polyfluorosilsesquioxane represented by Formula 1 according to an embodiment of the present invention, R ₁ and R ₂ are each independently a fluorophenyl group substituted with 1 to 5 fluoro atoms, 1 to fluoro atoms 49 substituted fluoroalkyl group having 1 to 24 carbon atoms, allyl group, vinyl group, epoxy group, methacryl group and acryl group, at least one or more of R ₁ and R ₂ is preferably a fluorophenyl group Can be.

In the polyfluorosilsesquioxane represented by Formula 1 according to the embodiment of the present invention, More preferably, R ₁ and R ₂ are each independently a pentafluorophenyl group, trifluoromethyl group, tridecafluoro -1,1,2,2tetrahydrooctyl, allyl group, vinyl group, epoxy group, methacryl group and acryl group, and at least one of R ₁ and R ₂ is pentafluorophenyl group or tridecafluoro -1,1,2,2tetrahydrooctyl.

Polyfluoro-based silsesquioxane represented by the formula (1) according to the present invention has a number average molecular weight (Mn) of approximately 1,000 to 100,000, the molecular weight distribution (Mw / Mn) range of 1 to 8.

Polyfluoro-based silsesquioxane represented by the formula (1) according to the present invention is a polymer having a high regular ladder structure, because the gelation does not occur during the polymerization process, a general organic solvent, for example, toluene xylene, benzene and chlorobenzene Such as aromatic hydrocarbons, methylene chloride, chloroform, dichloroethylene, trichloroethylene and trichloroethane, such as halogenated hydrocarbons, tetrahydrofuran (THF), 1,4-dioxane, diethyl ether and dibutyl ether The solubility of ketones such as ethers, acetone, methyl ethyl ketone and methyl ether ketone, esters such as butyl acetate, ethyl acetate and methyl acetate, and general organic solvents such as dimethylformamide is very excellent.

Since the polyfluorosilsesquioxane represented by Chemical Formula 1 according to the present invention has a low dielectric constant by introducing a fluorohydrocarbon group into a side chain, it can be used as a material of an interlayer insulating film of a semiconductor. Furthermore, since the polyfluorosilsesquioxane does not absorb the wavelength of the optical communication region (1330-1550 nm), it is possible to greatly reduce the light loss rate, and thus may be used as a material such as an optical waveguide material or a protective coating material and a water repellent coating material of an optical fiber. Can be. In addition, the polyfluorosilsesquioxane represented by Chemical Formula 1 may have photocuring properties by various photocuring groups introduced during the polymerization process.

The present invention provides a method for producing polyfluorosilsesquioxane represented by Chemical Formula 1 by condensation polymerization of a hydrolyzate of a silane monomer represented by Chemical Formula 2.

<Formula 2>

In Formula 2, R is R ₁ or R ₂ of Formula 1, and X ₁ , X ₂ and X ₃ are each independently a halogen atom, an alkoxy group or a hydroxy group.

According to one embodiment of the present invention, a method for preparing a polyfluoro silsesquioxane represented by Chemical Formula 1 may be briefly represented by the following Scheme 1.

<Scheme 1>

In Scheme 1, R, R ₁ , R ₂ , X ₁ , X _2, and X ₃ are as defined above, respectively.

According to the preparation method according to Scheme 1, the hydrolyzate of the fluorohydrocarbon silane monomer represented by the formula (2) is poly-condensation of the polyfluoride represented by the polycondensation at 5 ~ 85 ℃ temperature, preferably 20 ~ 70 ℃ The ro-based silsesquioxane can be produced. In addition, the polycondensation reaction is preferably carried out under a basic catalyst such as lithium hydroxide, sodium hydroxide or potassium carbonate.

The silane monomer represented by Formula 2 used in the preparation method according to the present invention is a known compound [A. WITTINGHAM et al ., J. Organometallic Chem ., 13, 125 (1968); H. BECKERS et al. , J. Organometallic Chem. 316, 41 (1986); J. Frohn et al. , J. Organometallic Chem. 506, 155 (1996); EC Lee et al., Polymer Journal , 29, 678 (1997), which can be easily synthesized by known methods.

In the process of preparing a single polymer of polyfluorosilsesquioxane represented by Chemical Formula 1, the concentration of the fluorohydrocarbon silane monomer may be appropriately selected according to the number average molecular weight of the desired polymer. In addition, even when forming a copolymer of the polyfluoro-based silsesquioxane represented by the formula (1), the concentration and mixing ratio of each of the silane monomers can be appropriately selected.

The concentration of the basic catalyst is preferably adjusted to 0.001% by weight to 10% by weight relative to the concentration of the fluorohydrocarbon silane monomer.

Method for producing a polyfluoro silsesquioxane according to an embodiment of the present invention, in the presence of a basic catalyst such as lithium hydroxide (LiOH), sodium hydroxide (NaOH) or potassium carbonate (K ₂ CO ₃ ), 5 ~ 85 ℃ By carrying out the polycondensation reaction at a temperature of, it is possible to prevent gelation due to cleavage of the fluorohydrocarbon group. Therefore, according to the production method of the present invention, it is possible to produce a polyfluoro silsesquioxane represented by the formula (1) having a high regular ladder structure, and having a number average molecular weight in the range of approximately 1,000 to 100,000. In addition, according to the production method of the present invention, the polyfluoro silsesquioxane represented by the formula (1) can be synthesized in a yield of 30% or more.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the protection scope of the present invention. In addition, the following comparative examples are only intended for the purpose of contrast with the following examples.

Example 1

Trichloropentafluorophenylsilane (Cl ₃ SiC ₆ F ₅ ) used as a monomer in this embodiment was analyzed by ¹⁹ F NMR, ²⁹ Si NMR, ¹ H NMR, and ¹³ C NMR, respectively. 4 is shown.

Polyaromatic fluorosilsilsesquioxane homopolymers using trichloropentafluorophenylsilane monomers were synthesized as follows.

A dropping funnel was connected to a 50 ml one-necked round bottom flask and a 500 ml three-necked round bottom flask, each equipped with a magnetic stirring device, and then flame-dried while passing dried nitrogen. In a nitrogen atmosphere, 10 g (about 5 mL) of trichloropentafluorophenylsilane was placed in a 50 mL one-necked round bottom flask and stirred well. 300 ml of distilled water was added to a 500 ml three-necked round-bottom flask, and the mixture was waited until the temperature of the distilled water reached about 3 ° C. using an ice bath, followed by vigorous stirring. The hydrolysis reaction proceeded while bringing down. After the addition was completed, the mixture was stirred for about 20 minutes and the hydrolysis reaction was completed. After storing for about 24 hours at 0 ~ 3 ℃ the precipitate produced was filtered to obtain 7.46 g (yield 74.6%) of hydrolyzate.

The polycondensation reaction of the hydrolyzate was carried out as follows. A flame dried three neck 100 mL round bottom flask was equipped with a Dean-Stark tube. After dissolving 7.0 g of the obtained hydrolyzate in 50 ml of toluene, 7.0 mg (0.1 wt.%) Of lithium hydroxide (LiOH) catalyst was added thereto, and the resultant was polycondensed at 70 ° C. for 48 hours. Thereafter, the reaction solution was added dropwise to an excess of hexane, and then stirred for about 1 hour to filter the resulting precipitate to obtain 2.89 g (yield 41.3%) of the reaction product as a white powder. The reaction product was vacuum dried at 110 ° C. for 10 hours and used as analytical sample. The number average molecular weight (Mn) of the produced polymer was 17,303, and the molecular weight distribution was 2.34.

The resulting polymer was analyzed by ¹⁹ F NMR, solid state ²⁹ Si NMR (Spuls method), FT-IR, and optical properties were analyzed by UV-vis and Near IR. The analysis results are shown in FIGS. 5 to 9, respectively.

The presence of F-2,6, F-4, F-3,5 was confirmed from the ¹⁹ F NMR analysis spectrum shown in FIG. From the ²⁹ Si NMR analytical spectra shown in FIG. 6, it was confirmed that the structure of the polymer was a highly regular ladder structure. In the FT-IR analysis spectrum shown in FIG. 7, corresponding peaks of the Si-Ph groups were detected at 1630, 1510, 1480, and 790 cm ⁻¹ , respectively, and C = CF binding stretching was detected at 1290 cm ⁻¹ , and the terminal silas The characteristic peaks of the Nol (Si-OH) groups were detected at 910 cm ^-1 . However, double bands of Si-O-Si bonds, which may be one criterion for determining the regularity of the polymer structure, should be observed at 1140 cm ^-1 and 1040 cm ^-1 of the FT-IR spectrum shown in FIG. In this region, the CF stretching peak and the aromatic CF stretching peak were observed together at 1100 and 1060 cm ⁻¹ , respectively, so that double bands of Si—O—Si bonds could not be observed accurately.

According to the UV-vis analysis spectrum shown in Figure 8 it was confirmed that the transmittance of more than 90% in the 330 ~ 700 nm wavelength region. In addition, in the Near IR analysis spectrum shown in FIG. 9, it was also confirmed that the optical loss ratio was low in the wavelength region of 1330 nm and 1550 nm compared to polymethyl methacrylate (PMMA) and polystyrene (PS).

Example 2

The polyaromatic fluorosilsesquioxane copolymer using the trichloropentafluorophenylsilane monomer and the trifluoromethyl trichlorosilane monomer was synthesize | combined by the following method. The polymerization process of the silane monomers was basically carried out according to Example 1 above.

A dropping funnel was connected to a 50 ml one-necked round bottom flask and a 500 ml three-necked round bottom flask, each equipped with a magnetic stirring device, and then flame dried while passing dried nitrogen. In a nitrogen atmosphere, 10 g (0.033 mol) of trichloropentafluorophenylsilane and 7.38 g (0.036 mol) of trifluoromethyltrichlorosilane were placed in a 50 ml one-necked round bottom flask and stirred well. 300 ml of distilled water was added to a 500 ml three-necked round bottom flask, and the mixture was waited until the temperature of the distilled water reached about 3 ° C. using an ice bath. Proceeded. After the addition was completed, the mixture was stirred for about 20 minutes and the hydrolysis reaction was completed. After storing for about 24 hours at 0 ~ 3 ℃ the precipitate formed was filtered to give 14.1 g (81.0% yield) of the hydrolyzate.

Dean-Stark tubes were installed in a flame-dried three-necked 100 mL round bottom flask for the polycondensation reaction. After dissolving 7.0 g of the obtained hydrolyzate in 50 ml of toluene, 7.0 mg (0.1 wt.%) Of sodium hydroxide (NaOH) catalyst was added thereto, and condensation polymerization was carried out at 70, 90, and 120 ° C. for 24 hours. Gelling advanced at the polymerization temperatures of 90 and 120 ° C. and could not be filtered. The reaction solution reacted at 70 ° C. was added dropwise to excess hexane, followed by stirring for about 1 hour, and the resulting precipitate was filtered to obtain 6.16 g (yield 88%) of the reaction product as a white powder. The reaction product was vacuum dried at 110 ° C. for 10 hours and used as analytical sample. The number average molecular weight (Mn) of the produced polymer was 13,250, and the molecular weight distribution was 1.976.

Example 3

The polyaromatic fluorosilsesquioxane copolymer using the trichloropentafluorophenylsilane monomer, the trichlorophenylsilane monomer, and the 3-trichlorosilylpropyl methacrylate monomer for the introduction of a photocuring group was synthesized as follows. . The polymerization process of the silane monomers was basically carried out according to Example 1 above.

A dropping funnel was connected to a 50 ml one-necked round bottom flask and a 500 ml three-necked round bottom flask, each equipped with a magnetic stirring device, and then flame dried while passing dried nitrogen. 6.0 ml of trichloropentafluorophenylsilane, 3.97 g (0.02 mol) of trichlorophenylsilane, and 5.23 g (0.02 mmol) of 3-trichlorosilylpropyl methacrylate in a 50 ml single round bottom in a nitrogen atmosphere. Put into flask and stirred well. 300 ml of distilled water was added to a 500 ml three-necked round bottom flask, and the mixture was waited until the temperature of the distilled water reached about 3 ° C. using an ice bath. The reaction proceeded. After the addition was completed, the mixture was stirred for about 20 minutes and the hydrolysis reaction was completed. After storing for about 24 hours at 0 ~ 3 ℃ the precipitate formed was filtered to obtain 9.2 g of hydrolyzate.

Dean-Stark tubes were installed in a flame-dried three-necked 100 mL round bottom flask for polymerization. After dissolving 7.0 g of the obtained hydrolyzate in 50 ml of toluene, 7.0 mg (0.1 wt%) of lithium hydroxide (LiOH) catalyst was added thereto, and the resultant was polycondensed at 70, 90, and 120 ° C. for 24 hours. At the polymerization temperature of 90 and 120 degreeC, gelatinization advanced and it could not filter. The reaction solution reacted at 70 ° C. was added dropwise to excess hexane, and then stirred for about 1 hour to filter the resulting precipitate to obtain 7.8 g (yield 75%) of the reaction product as a white powder. The reaction product was vacuum dried at 110 ° C. for 10 hours and used as analytical sample. The number average molecular weight (Mn) of the produced polymer was 8,000, and the molecular weight distribution was 2.12.

Structure analysis of the resulting polymer was analyzed by ¹ H NMR, the analysis results are shown in FIG.

^{In the 1} H NMR spectrum, the Si-Ph group showed a broad peak at delta of 7.9 to 6.4 ppm, and the double bond peak of the acrylic monomer was identified as two peaks at δ 5 to 6 ppm and δ 3 to 4 A wide range of CH ₂ peaks were detected at ppm, δ 1.8 ppm, δ 1.3 ppm and δ 0.4 ppm, respectively. The peak shown at δ 7.26 ppm is the characteristic peak of chloroform (CDCl ₃ ) used as a solvent for NMR measurement.

Example 4

Tridecafluoro-1,1,2,2tetrahydrooctyl-trimethoxy silane (0.2 mol) and phenyltrimethoxy silane (0.2 mol) as silane monomers were mixed in a nitrogen atmosphere to prepare a monomer mixture for copolymerization. It was. Potassium carbonate (0.2 g), a reaction catalyst, was dissolved in distilled water (24 g) to prepare an aqueous catalyst solution. Then, tetrahydrofuran (40 g) was added and stirred for 20 minutes to prepare a reaction solvent.

The monomer mixture prepared in advance was added dropwise to the reaction solvent controlled at 25 ° C. and stirred. After completion of the dropwise reaction, the reaction was started, samples were taken at regular intervals for analysis, and gel permeation chromatography (Gel Permeation Chromatography) analysis was performed based on the point at which the molecular weight no longer increased. When the stirring was stopped and visually observed, it was confirmed at this point that the layer separation clearly occurred. The organic layer was separated, washed with neutrality, and the solvent was evaporated to recover the polyfluorosilsesquioxane copolymer. The recovered copolymer was purified by reprecipitation 2-3 times in hexane. The molecular weight (Mw) (based on polystyrene, measured by GPC) of the polyfluoro-based silsesquioxane copolymer produced according to the present example was 6,400.

The structural analysis of the resulting copolymer was analyzed by ¹ H NMR, ²⁹ Si-NMR, and the analysis results are shown in FIGS. 11 and 12, respectively. Referring to the ¹ H NMR analysis spectrum shown in Figure 11, the Si-CH ₂ peak was detected at δ 0.5 ~ 0.7ppm, CH ₃ peak at δ 0.9 ~ 1.1 ppm, CH ₂ peak at δ 1.4 ~ 1.6 ppm, respectively Detected. In the analysis spectrum by ²⁹ Si-NMR shown in FIG. 12, the CH ₂ -Si (O) _3/2 peak was detected at δ −61 to −73 ppm.

In addition, the polyfluoro-based silsesquioxane copolymer polymerized in this example was analyzed by a thermogravimetric analyzer (TGA) method, and the results are shown in FIG. 13. Referring to FIG. 13, it was found that there is no thermal decomposition of the produced copolymer even at 350 ° C. or higher, and from this result, it is completely in the form of a ladder silsesquioxane without loss of the three-dimensional network structure due to incomplete condensation polymerization. It can be seen that condensation polymerization has been achieved.

Example   5 to Example  8

The amount of water, organic solvent, and catalyst in the aqueous solution was fixed, and the amounts of tridecafluoro-1,1,2,2tetrahydrooctyl-trimethoxy silane and phenyltrimethoxy silane monomers are shown in Table 1. In a different manner, the polymerization reaction of polyfluorosilsesquioxane was carried out in the same manner as in Example 4. The molecular weight of the polyfluorosilsesquioxane copolymer obtained from the polymerization reaction was measured by GPC as in Example 4, which is shown in Table 1.

TABLE 1

Example Tridecafluor 1,1,2,2tetrahydrooctyl-tree
Methoxy silane (mol) Phenyltrimethoxy silane (mol) Molecular weight of copolymer Molecular weight distribution 5 0.16 0.24 6,500 1.7 6 0.12 0.28 7,000 1.8 7 0.08 0.32 6,800 2.2 8 0.04 0.36 7,900 2.4

As shown in Table 1, a polyfluoro-based silsesquioxane copolymer having various molecular weights depending on the amount of tridecafluoro-1,1,2,2tetrahydrooctyl-trimethoxy silane and phenyltrimethoxy silane monomers Can be prepared.

Comparative example

A polyaromatic fluorosilsesquioxane homopolymer was prepared using trichloropentafluorophenylsilane monomer by the method shown in Example 1 above. However, potassium hydroxide (KOH) was used as a catalyst used during the polymerization process.

The polymerization process of the silane monomers was basically carried out according to Example 1 above.

The polymerization reaction was equipped with a Dean-Stark tube in a flame dried 100 ml three neck round bottom flask. After dissolving 7.0 g of the obtained hydrolyzate in 50 ml of toluene, 7.0 mg (0.1 wt.%) Of potassium hydroxide (KOH) catalyst was added thereto, and then, polycondensation was carried out at 70, 90, and 120 ° C. for 24 hours. At the polymerization temperature of 90 and 120 degreeC, gelatinization advanced and it could not filter. The reaction solution reacted at 70 ° C. was added dropwise to excess hexane, and then stirred for about 1 hour to filter the resulting precipitate to obtain 0.2 g of a white powder reaction product (yield 2.86%). The reaction product was vacuum dried at 110 ° C. for 10 hours and used as analytical sample. The number average molecular weight (Mn) of the produced polymer was 6,907, and the molecular weight distribution was 1.71.

1 is a ¹⁹ F NMR spectrum of trichloropentafluorophenylsilane used in Example 1 of the present invention.

2 is a ²⁹ Si NMR spectrum of trichloropentafluorophenylsilane used in Example 1 of the present invention.

3 is a ¹ H NMR spectrum of trichloropentafluorophenylsilane used in Example 1 of the present invention.

Figure 4 is a ¹³ C NMR spectrum of the trichloropentafluorophenylsilane used in Example 1 of the present invention.

5 is a ¹⁹ F NMR spectrum of a polyaromatic fluorosilsesquioxane (PFPSQ) polymerized by the preparation method according to Example 1 of the present invention.

6 is a solid state ²⁹ Si NMR spectrum of polyaromatic fluorosilsesquioxane polymerized according to Example 1 of the present invention.

7 is an FT-IR spectrum of a polyaromatic fluorosilsesquioxane polymerized according to Example 1 of the present invention.

8 is a UV-vis spectrum of polyaromatic fluorosilsesquioxane polymerized according to Example 1 of the present invention.

9 is Near IR spectrum of the polyaromatic fluorosilsesquioxane polymerized according to Example 1 of the present invention.

10 is a ¹ H NMR spectrum of the polyfluorosilsesquioxane copolymer polymerized according to Example 3 of the present invention.

11 is a ¹ H NMR spectrum of a polyfluorosilsesquioxane copolymer polymerized according to Example 4 of the present invention.

12 is a ²⁹ Si NMR spectrum of a polyfluoro-based silsesquioxane copolymer polymerized according to Example 4 of the present invention.

13 is a thermogravimetric analyzer (TGA) curve of a polyfluoro-based silsesquioxane copolymer polymerized according to Example 4 of the present invention.

Claims (9)

A polyfluoro silsesquioxane which has a fluorohydrocarbon side chain group and is represented by following General formula (1). <Formula 1>

In Chemical Formula 1, R ₁ and R ₂ are each independently selected from the group consisting of a fluoroaromatic group, a fluoroalkyl group, an allyl group, a vinyl group, an epoxy group, a methacryl group and an acryl group, and at least one of R ₁ and R ₂ is fluoro An aromatic group or a fluoroalkyl group, n is an integer of to. The method of claim 1, The R ₁ and R ₂ are each independently a fluorophenyl group substituted with 1 to 5 fluoro atoms, a fluoroalkyl group having 1 to 24 carbon atoms substituted with 1 to 49 fluoro atoms, allyl group, vinyl group, epoxy group, meta Polyfluoro-based silsesquioxane selected from the group consisting of a krill group and an acrylic group, wherein at least one of R ₁ and R ₂ is a fluorophenyl group. 3. The method of claim 2, R ₁ and R ₂ are each independently composed of a pentafluorophenyl group, trifluoromethyl group, tridecafluoro-1,1,2,2tetrahydrooctyl, allyl group, vinyl group, epoxy group, methacryl group and acryl group A polyfluoro-based silsesquioxane selected from the group wherein at least one of R ₁ and R ₂ is a pentafluorophenyl group or tridecafluoro-1,1,2,2tetrahydrooctyl. The method according to any one of claims 1 to 3, The allyl group, vinyl group, epoxy group, methacryl group and acryl group, wherein a part or all of the hydrogen atoms are each substituted with a fluoro atom, polyfluoro-based silsesquioxane. The method according to any one of claims 1 to 3, A polyfluoro silsesquioxane, characterized by a number average molecular weight (Mn) of 1,000 to 100,000. The method according to any one of claims 1 to 3, Polyfluoro-based silsesquioxane, characterized in that the homopolymer or copolymer having a regular ladder structure. A method for producing a polyfluoro-based silsesquioxane represented by the following formula (1) comprising condensation polymerization of a hydrolyzate of a silane monomer represented by the formula (2) at a temperature of 5 to 85 ° C. <Formula 2>

<Formula 1>

In Chemical Formula 1 or 2, R is R ₁ or R ₂ , R ₁ and R ₂ are each independently selected from the group consisting of a fluoroaromatic group, a fluoroalkyl group, an allyl group, a vinyl group, an epoxy group, a methacryl group and an acryl group, and at least one of R ₁ and R ₂ is fluoro An aromatic group or a fluoroalkyl group, X ₁ , X ₂ and X ₃ are each independently a halogen atom, an alkoxy group or a hydroxy group, n is an integer from 5 to 10,000. The method of claim 7, wherein The polycondensation reaction is carried out under a basic catalyst of lithium hydroxide, sodium hydroxide or potassium carbonate. The method of claim 7, wherein A method of producing a polyfluoro silsesquioxane having a number average molecular weight (Mn) of 1,000 to 100,000 and having a regular ladder structure.

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