KR100944211B1 - Perfluorinated multi-acrylates with cyclic siloxane and method of preparing the same and the photo-curable components containing them - Google Patents

Abstract

The present invention relates to a siloxane-containing perfluorinated polyhydric acrylic compound and a method for producing the same, and a photopolymerization composition containing the same. Specifically, the siloxane-containing perfluorinated polyhydric acrylic compound represented by the following formula (1) has excellent light transparency and a birefringence ratio. The present invention relates to a siloxane-containing perfluorinated polyhydric acrylic compound having a low and excellent thermal stability, a method for preparing the same, and a photopolymerization composition containing the same.

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group of (C1-C3), R _f is -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- , or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p, q are integers from 1 to 12 , r, v are integers of 1-30.

Siloxane, perfluorinated, polyacrylic, ultraviolet, light irradiation, photopolymerization, photocuring, film

Description

Peroxinated multi-acrylates with cyclic siloxane and method of preparing the same and the photo-curable components containing them}

The present invention relates to a siloxane-containing perfluorinated polyhydric acrylic compound and a method for producing the same, and a photopolymerization composition containing the same, and specifically, a siloxane-containing perfluorinated polyvalent acrylic compound having excellent light transparency, low birefringence, and excellent thermal stability; It relates to a preparation method thereof and a photopolymer composition containing the same.

The optical material for optical waveguide is a core material applied to optical interconnection devices, optical splitters, optical couplers, thermo-optic switches, and variable attenuators, as well as optical devices related to wavelength division multiplexing systems, which are absolutely necessary for the implementation of next-generation integrated information networks. The polymer material for optical waveguide device should have excellent optical transparency in the wavelength band of 1.3 ~ 1.55 sm, low birefringence, high thermal and environmental stability, and coating property. Compared to inorganic materials and semiconductor materials, organic polymer materials can be easily synthesized by controlling the characteristics of materials by controlling the molecular structure, and have excellent processability, mass production at low cost, fast response speed, and excellent thermal-light characteristics. Do. However, due to the large thermal instability and the optical propagation loss, the application to the optical waveguide device is limited. In particular, the optical propagation loss needs to be greatly reduced. Polymeric materials generally have an inherent absorption region due to vibration in the molecular structure in the infrared region. In particular, the vibration absorption loss in the near-infrared region by C-H (or O-H, N-H) coupling is due to the second and third harmonic oscillations, which is the main cause of light loss of the polymer material in the 1.3 to 1.55 m wavelength range. This problem of optical loss can be solved by substituting C-H bonds with fluorine (C-F) to increase the converted mass, thereby shifting harmonic back vibrations to longer wavelengths and consequently minimizing light absorption in the optical communication wavelength range. In addition, the introduction of the fluoro group not only lowers the light loss but also increases the hydrophobicity of the film, thereby lowering the moisture permeability, increasing the chemical resistance and improving the wear resistance.

The research direction of the existing polymer materials for optical devices is to design the molecular structure to have a high Tg to give heat resistance as a basic guideline. Based on this, a fluorine-substituted polyimide material having a very high Tg and excellent thermal stability was developed by Nippon Telegraph and Telephone Corporation (NTT), Japan (T. Matsuura, et. Al. Macromoleculaes , 26, 419 (1993). S. Ando, et.al. Macromoleculaes, 25, 5858 (1992)) Polyarylene ether in Dow Chemical has a high Tg of more than 400 ° C and excellent thermal stability and light loss of 0.25 dB / cm or less. The compound was developed. This polymer has a thermosetting structure, a method of forming perfluorocyclobutane by heating. (K. Petermann, et.al., Electron. Lett., 33, 518 (1997)) The Electronics and Telecommunications Research Institute (ETRI) is a polyarylene-substituted fluorine-substituted polyarylene by replacing acetylene at both ends of the polymer backbone. Developed ether. This material has a light propagation loss of less than 0.5 dB / cm and a birefringence of about 0.003. (HJ Lee, et . Al. , J. Polym. Sci., Poly. Chem., 37, 2355 (1999)) According to Gemfire's findings (HS Lackritz, et. Al., US 6 236 774). When the polymer material having a high Tg is used in optical devices such as thermo-optic switches, it is known that it affects the long-term use fastness. In other words, repeated heating and cooling for a few milliseconds in the temperature range of about 100 ℃ (ie driving the device) is a pair of thermal stress in the polymer film, and in the long term, the heat history ( thermal hysteresis) behavior and degraded device performance over initial performance. Therefore, in order to solve the accumulated thermal stress, it is proposed in a preferred direction to design a molecular structure so that the Tg of the polymer film is lower than the device driving temperature, and to design a crosslinked structure to have a mesh structure for numerical stability. That is, the molecular structure is designed to form a network structure by optical crosslinking, to maintain morphological stability and to have a Tg lower than room temperature so that local free movement of molecular structures is possible at room temperature. The perfluorinated polyalkyl ether structure is a fluorine-substituted form in the polyalkyl ether structure. Corning has developed a polyhydric acrylic compound in which a perfluorinated polyalkyl ether structure is connected to a triazine compound and the like, and the Tg of the photocurable films of the compounds showed much lower values than room temperature. (LW Shacklette, et.al., Adv. Func. Mater., 13, 453 (2003)) On the other hand, polysiloxane-based polymers have high flexibility, low glass transition temperature, and low optical loss in optical communication wavelength bands. Most likely. Japan's NTT has also reported the development of a disiloxane-substituted polysiloxane material. (T. Matsuura, et.al., Electron. Lett., 29, 269 (1993))

Conventionally, in order to design to have a high Tg, it is generally designed to contain aromatic structures such as polyimide and polyarylene ether. It is common to represent ^three or more ^values to the application of the optical device as a birefringence index 10 is required to lower to ^-4 or less, most of the polarization dependence increases birefringence for the aromatic polymer 10, as in the case of polyimide.

In order to solve the above problems, an object of the present invention is a molecular design so as to contain an aliphatic perfluorinated structure in the siloxane structure instead of an aromatic structure, excellent light transparency, low birefringence and excellent thermal stability siloxane-containing perfluorinated polyvalent It is to provide an acrylic compound, a method for producing the same, and a photopolymerization composition containing the same.

In addition, another object of the present invention is to provide a photocurable film having improved numerical stability, heat resistance, and chemical resistance through rapid curing by introducing a polyvalent acrylic structure having an acryl group introduced at the terminal.

In order to achieve the above object, the present invention provides a siloxane-containing perfluorinated polyhydric acrylic compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group of (C1-C3), R _f is -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- , or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p, q are integers from 1 to 12 , r, v are integers of 1-30.

The present invention also provides a method for preparing a siloxane-containing perfluorinated polyhydric acrylic compound prepared by reacting a siloxane-containing perfluorinated alkyl alcohol compound of formula 2 with acryloyl chloride of formula 3 under an amine base.

[Formula 2]

Wherein R ₂ is an alkyl group of (C1-C3),

R _f is -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- , or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers of 1 to 12, and r and v are integers of 1 to 30.

[Formula 3]

In the above formula, R ₁ is a hydrogen atom or a methyl group.

In addition, the present invention is 10 to 99% by weight of siloxane-containing perfluorinated polyhydric acrylic compound;

Perfluorinated mono- or divalent acrylic compound-based perfluorinated acrylic compound; And 0.01 to 5 parts by weight of the photoinitiator based on 100 parts by weight of the total perfluorinated acrylic compound.

In addition, the present invention provides a film prepared by irradiating ultraviolet to the photopolymer composition.

Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

The siloxane-containing perfluorinated polyhydric acryl-based compound represented by the following Chemical Formula 1 of the present invention has excellent optical transparency in the optical communication wavelength band, low polarization dependency, and has perfluorofluorinated aliphatic chains connected to the siloxane structure to improve device reliability. In order to form a crosslinked structure by photocuring, an attempt was made to develop a novel compound having an acryl group bonded thereto and a photopolymerization composition containing the same.

Therefore, it has a structure in which hydrogen is substituted with fluorine to improve light transparency, an aliphatic chain structure is used instead of aromatics to reduce polarization dependence, and a perfluorinated polyether structure is connected to the siloxane compound to have a low Tg. In order to secure numerical stability, heat resistance, and chemical resistance, a polyvalent acrylic structure in which an acryl group is introduced at an end may be introduced to form a network structure by light irradiation.

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group of (C1-C3), it is more preferable that R ₂ is a methyl group.

The R _f is obtained from a commercially available perfluorinated alkyl diol, for example, -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- Or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers from 1 to 12, and r and v are from 1 to 30 Is an integer.

The siloxane-containing perfluorinated polyhydric acrylic compound represented by Chemical Formula 1 may be polymerized by light as a monomer capable of photopolymerization to obtain a polymer thin film having excellent light transparency, which is very advantageous for manufacturing a thin film for an optical device using ultraviolet light. In particular, the compound of Chemical Formula 1 may be substituted with a fluorine group to minimize light loss due to C-H absorption, thereby minimizing light loss. In addition, the compound represented by Formula 1 has a low polarization dependence by containing only an aliphatic compound instead of an aromatic compound, and contains a siloxane compound and a fluorine-substituted alkyl oxide structure, and thus has a low Tg to easily remove residual thermal stress generated when the device is driven. The long-term reliability of the device can be improved.

The siloxane-containing perfluorinated polyhydric acrylic compound represented by Chemical Formula 1 according to the present invention is prepared by carrying out the synthesis process shown in Scheme 1 below.

As shown in Scheme 1 below, the fluorinated diol compound of formula 6 and allyl bromide of formula 7 are reacted under a base such as sodium hydroxide or potassium hydroxide to replace one hydroxy group with an allyl group.

Scheme 1

R _f is -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- , or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers of 1 to 12, and r and v are integers of 1 to 30.

The fluorinated diol compound of Chemical Formula 6 is not only a fluorinated diol such as octafluorohexanediol, but also a fluorolink compound provided by Solvay Solexis having the general formula of Formula 8 below, dodecafluorooctane Diols, fluorinated triethylene glycol, fluorinated tetraethylene glycol, diol compounds of tetrafluoroethylene oxide-difluoromethylene oxide copolymers, and the like.

[Formula 8]

HO-CH ₂ CF ₂ O (-CF ₂ F ₂ O) _n- (CF ₂ O) _m -CF ₂ CH ₂ -OH

In the formula, m, n is an integer of 1 to 30.

The allyl alcohol of Chemical Formula 5 obtained in Scheme 1 is reacted with tetraalkyl cyclotetrasiloxane of Chemical Formula 4, preferably tetramethyl cyclotetrasiloxane, under a platinum catalyst, to give a compound in which four perfluorinated alkyl alcohols are bonded to the siloxane core structure. Get Acryloyl chloride is reacted with the compound thus obtained under an amine base to finally prepare a siloxane-containing perfluorinated polyvalent acrylic compound of Formula 1 as shown in Scheme 2 below.

Scheme 2

In the above formula, in which R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group of (C1-C3), more preferably a methyl group. In addition, R _f is -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- , or -CH ₂ CFO- (CF ₂ CF ₂ O) _r -(CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers of 1 to 12, and r and v are integers of 1 to 30.

The photopolymerization composition of the present invention is one or more perfluorinated monofluoride monovalent or one or more siloxane-containing perfluorinated polyhydric acrylic compound selected from the formula (1) for controlling the viscosity, photopolymerization rate and mechanical, refractive index, optical properties of the cured film It comprises a bivalent acrylic compound and a photoinitiator. The perfluorinated monovalent or divalent acrylic compound may be selected from among commercially available compounds or known compounds, and representative examples thereof may be selected from the following Chemical Formulas 9 to 15 or mixtures thereof.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

The photopolymerization composition of the present invention may include a perfluorinated acrylic compound and a photoinitiator, wherein the perfluorinated acrylic compound is 10 to 99% by weight, preferably 30 to 90% by weight, and perfluorinated siloxane-containing perfluorinated polyvalent acrylic compound of Formula 1 It may consist of 1 to 90% by weight, preferably 10 to 70% by weight of the monovalent or divalent acrylic compound.

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group of (C1-C3), it is more preferable that R ₂ is a methyl group.

The R _f is obtained from a commercially available perfluorinated alkyl diol, for example, -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- Or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers from 1 to 12, and r and v are from 1 to 30 Is an integer.

The photoinitiator may be a photoinitiator such as an ultraviolet photoinitiator of Shivagaigi Co., Ltd., such as Irgacure369, and a benzoyl radical generating initiator such as 2,2-dimethoxy-2-phenylacetophenone, and the siloxane-containing perfluorinated polyhydride of Chemical Formula 1 0.01 to 5 parts by weight of a photoinitiator may be included with respect to 100 parts by weight of the total content of the perfluorinated acrylic compound consisting of an acryl-based compound and a perfluorinated monovalent or divalent acrylic compound, preferably 0.1 to 3 parts by weight. It is good to achieve the purpose.

When the siloxane-containing perfluorinated polyhydric acrylic compound of Formula 1 is less than 10% by weight, transparency or thermal stability may be lowered when the film is to be described later, and when it exceeds 99% by weight, a synergistic effect by an excessive amount may be exhibited. Without waste of raw materials. Moreover, when the said photoinitiator is less than 0.01 weight part, there exists a possibility that photocuring may not be carried out at the time of ultraviolet irradiation, and when it exceeds 5 weight part, there exists a possibility that transparency may rather fall.

The photopolymerizable composition containing the perfluorinated monovalent or divalent acrylic compound selected from the siloxane-containing perfluorinated polyhydric acrylic compound of the formula (1), the formulas (9) to (15) or a mixture thereof, and a photoinitiator is itself a method of spin coating. UV light can be used to produce a film having excellent light transparency, or a solvent such as propylene glycol monomethyl ether acetate, cyclohexanone, or cyclopentanone. The solution prepared by dissolving 1 to 40 parts by weight based on 100 parts by weight of the photopolymerization composition may be spin-coated and irradiated with UV light to prepare a film having excellent light transparency.

 [Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group of (C1-C3), it is more preferable that R ₂ is a methyl group.

The R _f is obtained from a commercially available perfluorinated alkyl diol, for example, -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- Or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers from 1 to 12, and r and v are from 1 to 30 Is an integer.

As described above, the siloxane-containing perfluorinated polyhydric acrylic compound and the photopolymerization composition of the present invention are cured rapidly by irradiating light such as ultraviolet rays to provide a polymer photocurable film having excellent optical transparency in the optical communication wavelength band and low birefringence. There is an effect that can be easily manufactured.

In addition, the film made of the siloxane-containing perfluorinated polyvalent acrylic compound and the photopolymerization composition of the present invention is a material that can be used as a core or cladding material of various optical devices such as an optical switch, a variable optical attenuator, and an optical waveguide.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example  One

[1-1] Synthesis of Compound (1)

In a three-necked flask, fluorinated triethylene glycol (10 g, 34 mmol) was dissolved in tetrahydrofuran (20 ml), sodium hydroxide (34 mmol) was added thereto, and allyl bromide (51.0 mmol) was slowly added thereto, followed by 15 at room temperature. Reaction was time. After the reaction, excess sodium hydroxide and bromo sodium were filtered off, and then tetrahytrofuran was removed under reduced pressure. After extraction with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate and separated by column chromatography (ethyl acetate / hexane = 1: 5) to give a colorless liquid with a yield of 48%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 5.94-5.81 (m, 1H), 5.36-5.26 (m, 2H), 4.16-4.14 (d, J = 5.7 Hz, 2H), 3.93-3.87 (t , 2H), 3.85-3.79 (t, 2H) 3.43 (-OH, 1H).

[1-2] Synthesis of Compound (2)

In a three-necked flask, 2,4,6,8-tetramethyl cyclosiloxane (2.66 mmol) was dissolved in toluene (10 ml), and Pt (0) catalyst was added thereto and stirred for 30 minutes. Compound (1) (4 g, 11.97 mmol) was dissolved in toluene (5 ml) and slowly added dropwise to the reaction. The mixture was refluxed at 90 ° C. for 15 hours in a nitrogen atmosphere, cooled to room temperature, and stirred with activated carbon. After filtration and evaporation under reduced pressure, the residue was separated by column chromatography (ethyl acetate / hexane = 1: 1) to give a colorless liquid with a yield of 68%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 3.85-3.79 (t, 8H), 3.75-3.69 (t, 8H), 3.51-3.46 (t, 8H), 1.54-1.49 (q, 8H), 0.47 -0.42 (t, 8 H), 0.00 (s, 12 H).

[1-3] Synthesis of Compound (3)

Compound (2) (1.8 mmol) was dissolved in dichloromethane in a three neck flask and cooled to 0 ° C. Triethylamine (10.8 mmol) was slowly added dropwise, stirred for 30 minutes, and then acryloyl chloride (10.8 mmol) was slowly added dropwise and reacted at room temperature for 15 hours. The precipitate was filtered, extracted with ethyl acetate, and then the organic layer was dried over MgSO ₄ and separated by column chromatography (ethyl acetate / hexane = 1: 3) to give a colorless liquid with a yield of 42%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 6.46-6.41 (d, J = 17.1 Hz, 4H), 6.14-6.05 (q, 8H), 5.91-5.87 (d, J = 10.5 Hz, 4H), 4.49-4.43 (t, 8H), 3.74-3.68 (t, 8H), 3.50-3.45 (t, 8H), 1.59-1.49 (q, 8H), 0.48-0.43 (t, 8H), 0.00 (s, 12H ).

1 shows a nuclear magnetic resonance spectroscopy graph of compound (3) according to Example 1 of the present invention.

Example  2

[2-1] Synthesis of Compound (4)

In a three-necked flask, fluorinated tetraethylene glycol (10 g, 24.38 mmol) was dissolved in tetrahydrofuran (15 ml), sodium hydroxide (24.38 mmol) was added thereto, and allyl bromide (36.58 mmol) was slowly added dropwise, followed by 15 at room temperature. Reaction was time. After the reaction, excess sodium hydroxide and bromo sodium were filtered off, and then tetrahytrofuran was removed under reduced pressure. After extraction with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate and separated by column chromatography (ethyl acetate / hexane = 1: 5) to give a colorless liquid at a yield of 40%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 5.94-5.81 (m, 1H), 5.35-5.26 (m, 2H), 4.16-4.14 (d, J = 5.7 Hz, 2H), 3.94-3.89 (t , 2H), 3.85-3.79 (t, 2H) 2.88 (-OH, 1H).

[2-2] Synthesis of Compound (5)

In a three-necked flask, 2,4,6,8-tetramethyl cyclosiloxane (3.115 mmol) was dissolved in toluene (10 ml), and then Pt (0) catalyst (1.5 ml) was added thereto and stirred for 30 minutes. Compound (4) (6.17 g, 13.70 mmol) was dissolved in toluene (20 ml) and slowly added dropwise to the reaction. The mixture was refluxed at 90 ° C. for 15 hours in a nitrogen atmosphere, cooled to room temperature, and stirred with activated carbon. After filtration and evaporation under reduced pressure, the residue was separated by column chromatography (ethyl acetate / hexane = 1: 3) to give a colorless liquid at 62% yield.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 3.87-3.80 (t, 8H), 3.75-3.68 (t, 8H), 3.51-3.46 (t, 8H), 1.59-1.49 (q, 8H), 0.48 -0.42 (t, 8 H), 0.00 (s, 12 H).

[2-3] Synthesis of Compound (6)

Compound (5) (1.86 mmol) was dissolved in tetrahydrofuran in a three neck flask and cooled to 0 ° C. Triethylamine (8.38 mmol) was slowly added dropwise, stirred for 30 minutes, and then acryloyl chloride (8.38 mmol) was slowly added dropwise and reacted at room temperature for 15 hours. The precipitate was filtered, extracted with ethyl acetate, and then the organic layer was dried over MgSO 4 and separated by column chromatography (ethyl acetate / hexane = 1: 3) to give a colorless liquid with a yield of 48%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 6.47-6.41 (d, J = 17.1 Hz, 4H), 6.14-6.15 (q, 8H), 5.92-5.87 (d, J = 10.5 Hz, 4H), 4.49-4.43 (t, 8H), 3.74-3.68 (t, 8H), 3.50-3.45 (t, 8H), 1.58-1.49 (q, 8H), 0.47-0.43 (t, 8H), 0.00 (s, 12H ).

2 shows a nuclear magnetic resonance spectroscopy graph of compound (6) according to Example 2 of the present invention.

Example  3

[3-1] Synthesis of Compound (7)

In a three-necked flask, fluorolink D10 (25 g, 25.0 mmol) was dissolved in tetrahydrofuran (20 ml) and ethoxynonafluorobutane (5 ml), followed by sodium hydroxide (25.0 mmol) and allyl bromide (37.5 mmol). ) Was slowly added dropwise and reacted at room temperature for 15 hours. After the reaction, excess sodium hydroxide and bromo sodium were filtered off, and then tetrahytrofuran was removed under reduced pressure. After extraction with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate and separated by column chromatography (ethyl acetate / hexane = 1: 5) to give a colorless liquid with a yield of 44%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 5.91-5.82 (m, 1H), 5.34-5.25 (m, 2H), 4.14-4.13 (d, J = 5.7 Hz, 2H), 3.94-3.89 (t , 2H), 3.83-3.76 (t, 2H) 2.23 (-OH, 1H).

[3-2] Synthesis of Compound (8)

In a three-necked flask, 2,4,6,8-tetramethyl cyclosiloxane (4.47 mmol) was dissolved in toluene (10 ml), and Pt (0) catalyst (1.5 ml) was added thereto, followed by stirring for 30 minutes. Compound (7) (21 g, 20.13 mmol) was dissolved in toluene (20 ml) and ethoxynonafluorobutane (20 ml) and slowly added dropwise to the reaction. The mixture was refluxed at 90 ° C. for 15 hours in a nitrogen atmosphere, cooled to room temperature, and stirred with activated carbon. After filtration and evaporation under reduced pressure, the residue was separated by column chromatography (ethyl acetate / hexane = 1: 3) to give a colorless liquid with a yield of 50%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 3.88-3.79 (t, 8H), 3.75-3.67 (t, 8H), 3.49-3.46 (t, 8H), 1.59-1.49 (q, 8H), 0.48 -0.42 (t, 8 H), 0.00 (s, 12 H).

[3-3] Synthesis of Compound (9)

Compound (8) (2.14 mmol) was dissolved in tetrahydrofuran (35 ml) and ethoxynonafluorobutane (5 ml) in a three neck flask and cooled to 0 ° C. Triethylamine (10.23 mmol) was slowly added dropwise, stirred for 30 minutes, and then acryloyl chloride (10.23 mmol) was slowly added dropwise and reacted at room temperature for 15 hours. The precipitate was filtered off, extracted with ethyl acetate, and then the organic layer was dried over MgSO 4 and separated by column chromatography (ethyl acetate / hexane = 1: 7) to give a colorless liquid having a yield of 55%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 6.47-6.41 (d, J = 17.1 Hz, 4H), 6.14-6.05 (q, 8H), 5.90-5.87 (d, J = 10.5 Hz, 4H), 4.49-4.42 (t, 8H), 3.74-3.68 (t, 8H), 3.50-3.45 (t, 8H), 1.58-1.53 (q, 8H), 0.49-0.44 (t, 8H), 0.00 (s, 12H ).

3 shows a nuclear magnetic resonance spectroscopy graph of compound (9) according to Example 3 of the present invention.

Example  4

[4-1] Synthesis of Compound (10)

Dodecafluorooctanediol (10 g, 27.62 mmol) was dissolved in tetrahydrofuran (15 ml) in a three necked flask, sodium hydroxide (27.62 mmol) was added dropwise and allyl bromide (41.43 mmol) was slowly added dropwise at room temperature. The reaction was carried out for 10 hours. After the reaction, excess sodium hydroxide and bromo sodium were filtered off, and then tetrahytrofuran was removed under reduced pressure. After extraction with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate and separated by column chromatography (ethyl acetate / hexane = 1: 10) to give a colorless liquid with a yield of 57%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 5.94-5.81 (m, 1H), 5.35-5.26 (m, 2H), 4.15-4.13 (d, J = 5.7 Hz, 2H), 3.94-3.89 (t , 2H), 3.85-3.79 (t, 2H) 2.38 (-OH, 1H).

[4-2] Synthesis of Compound (11)

In a three-necked flask, 2,4,6,8-tetramethyl cyclosiloxane (3.12 mmol) was dissolved in toluene (10 ml) and Pt (0) catalyst (1.5 ml) was added thereto and stirred for 30 minutes. Compound (10) (5.64 g, 14.0 mmol) was dissolved in toluene (20 ml) and slowly added dropwise to the reaction. The mixture was refluxed at 90 ° C. for 15 hours in a nitrogen atmosphere, cooled to room temperature, and stirred with activated carbon. After filtration and evaporation under reduced pressure, the residue was separated by column chromatography (ethyl acetate / hexane = 1: 3) to give a colorless liquid at a yield of 65%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 3.85-3.82 (t, 8H), 3.75-3.68 (t, 8H), 3.51-3.46 (t, 8H), 1.56-1.51 (q, 8H), 0.48 -0.42 (t, 8 H), 0.00 (s, 12 H).

[4-3] Synthesis of Compound (12)

Compound (11) (2.0 mmol) was dissolved in tetrahydrofuran in a three neck flask and cooled to 0 ° C. Triethylamine (9.0 mmol) was slowly added dropwise, stirred for 30 minutes, and then acryloyl chloride (9.0 mmol) was slowly added dropwise and reacted at room temperature for 13 hours. The precipitate was filtered off, extracted with ethyl acetate, and then the organic layer was dried over MgSO 4 and separated by column chromatography (ethyl acetate / hexane = 1: 3) to give a colorless liquid with a yield of 53%.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 6.47-6.41 (d, J = 17.1 Hz, 4H), 6.14-6.05 (q, 8H), 5.91-5.87 (d, J = 10.5 Hz, 4H), 4.49-4.43 (t, 8H), 3.74-3.68 (t, 8H), 3.50-3.45 (t, 8H), 1.58-1.49 (q, 8H), 0.47-0.43 (t, 8H), 0.00 (s, 12H ).

Example  5

2 parts by weight of Compound (3) (0.5 g) synthesized in Example 1 and IRGACURE 369 were dissolved in propylene glycol methyl ether acetate (2 ml) based on 100 parts by weight of Compound (3) synthesized in Example 1. Samples were prepared by filtration with a 0.2 μm syringe filter. After coating the UV-ozone treated silicon wafer by spin coating method, the solvent was removed by drying at 90 ° C. hot plate for 5 minutes and then drying at 90 ° C. vacuum oven for 10 minutes. Irradiated with ultraviolet light for 25 minutes with a medium-pressure mercury lamp (output: 80 W), and then cured for 30 minutes at 130 ℃ vacuum oven to obtain a film. The refractive index and the optical loss of the prepared film were measured at 1550 nm with a prism coupler, and the values of the refractive index of 1.39 and the optical loss of 0.12 dB / cm were obtained.

Example  6

(0.05 g)와 IRGACURE 369를 실시예 2에서 합성한 화합물(6)과

100중량부에 대하여 2중량부를 프로필렌글리콜메틸에테르아 세테이트 (2 ml)에 녹인 후 0.2 μm 실린지 필터로 여과하여 샘플을 준비하였다. UV-오존 처리한 실리콘 웨이퍼에 스핀코팅법으로 코팅한 후 90 ℃ 핫플레이트에서 5 분간 건조 후 90 ℃ 진공오븐에서 10 분간 건조하여 용매를 제거하였다. Medium-pressure mercury lamp (출력: 80 W)로 분간 자외선를 조사하여 광경화 시킨 후 130 ℃ 진공오븐에서 30 분간 건조하여 필름을 얻었다. 제조된 필름의 굴절율 및 광손실을 프리즘 커플러로 1550 nm로 측정하였으며 굴절률 1.39 와 광손실 0.10 dB/cm의 값을 얻었다.Compound (6) synthesized in Example 2 (0.45 g) and

(0.05 g) and IRGACURE 369 synthesized in Example 2,

A sample was prepared by dissolving 2 parts by weight in propylene glycol methyl ether acetate (2 ml) based on 100 parts by weight and filtering with a 0.2 μm syringe filter. After coating the UV-ozone treated silicon wafer by spin coating method, the solvent was removed by drying at 90 ° C. hot plate for 5 minutes and then drying at 90 ° C. vacuum oven for 10 minutes. After irradiating with UV light for a minute with a medium-pressure mercury lamp (output: 80 W), the film was dried for 30 minutes in a vacuum oven at 130 ℃. The refractive index and the optical loss of the prepared film were measured at 1550 nm with a prism coupler, and the values of the refractive index of 1.39 and the optical loss of 0.10 dB / cm were obtained.

Example  7

(0.05 g)와

(0.05 g)와 IRGACURE 369를 상기 실시예 3에서 합성한 화합물 (9),

및

100중량부에 대하여 2 중량부를 프로필렌글리콜메틸에테르아세테이트 (2 ml)에 녹인 후 0.2 μm 실린지 필터로 여과하여 샘플을 준비하였다. UV-오존 처리한 실리콘 웨이퍼에 스핀코팅법으로 코팅한 후 90 ℃ 핫플레이트에서 5 분간 건조 후 90 ℃ 진공오븐에서 10 분간 건조하여 용매를 제거하였다. Medium-pressure mercury lamp (출력: 80 W)로 분간 자외선를 조사하여 광경화 시킨 후 130 ℃ 진공오븐에서 30 분간 건조하여 필름을 얻었다. 제조된 필름의 굴절율 및 광손실을 프리즘 커플러로 1550 nm로 측정하였으며 굴절률 1.34와 광손실 0.07 dB/cm의 값을 얻었다.Compound (9) (0.4 g) synthesized in Example 3;

(0.05 g) and

(0.05 g) and IRGACURE 369 synthesized in Example 3, (9),

And

A sample was prepared by dissolving 2 parts by weight in propylene glycol methyl ether acetate (2 ml) based on 100 parts by weight and filtering with a 0.2 μm syringe filter. After coating the UV-ozone treated silicon wafer by spin coating method, the solvent was removed by drying at 90 ° C. hot plate for 5 minutes and then drying at 90 ° C. vacuum oven for 10 minutes. After irradiating with UV light for a minute with a medium-pressure mercury lamp (output: 80 W), the film was dried for 30 minutes in a vacuum oven at 130 ℃. The refractive index and the optical loss of the prepared film were measured at 1550 nm with a prism coupler, and the values of the refractive index of 1.34 and the optical loss of 0.07 dB / cm were obtained.

Example  8

(0.05 g)과 IRGACURE 369를 실시예 4에서 합성한 화합물(12) 및

100중량부에 대하여 2 중량부를 프로필렌글리콜메틸에테르아세테이트 (2 ml)에 녹인 후 0.2 μm 실린지 필터로 여과하여 샘플을 준비하였다. UV-오존 처리한 실리콘 웨이퍼에 스핀코팅법으로 코팅한 후 90 ℃ 핫플레이트에서 5 분간 건조 후 90 ℃ 진공오븐에서 10 분간 건조하여 용매를 제거하였다. Medium-pressure mercury lamp (출력: 80 W)로 분간 자외선를 조사하여 광경화 시킨 후 130 ℃ 진공오븐에서 30 분간 건조하여 필름을 얻었다. 제조된 필름의 굴절율 및 광손실을 프리즘 커플러로 1550 nm로 측정하였으며 굴절률 1.39 와 광손실 0.14 dB/cm의 값을 얻었다.Compound (12) synthesized in Example 4 (0.45 g) and

(0.05 g) and IRGACURE 369 synthesized in Example 4 (12) and

A sample was prepared by dissolving 2 parts by weight in propylene glycol methyl ether acetate (2 ml) based on 100 parts by weight and filtering with a 0.2 μm syringe filter. After coating the UV-ozone treated silicon wafer by spin coating method, the solvent was removed by drying at 90 ° C. hot plate for 5 minutes and then drying at 90 ° C. vacuum oven for 10 minutes. After irradiating with UV light for a minute with a medium-pressure mercury lamp (output: 80 W), the film was dried for 30 minutes in a vacuum oven at 130 ℃. The refractive index and the optical loss of the prepared film were measured at 1550 nm with a prism coupler, and the values of the refractive index of 1.39 and the optical loss of 0.14 dB / cm were obtained.

1 is a nuclear magnetic resonance spectroscopy graph of compound (3) according to Example 1 of the present invention.

2 is a nuclear magnetic resonance spectroscopy graph of compound (6) according to Example 2 of the present invention.

3 is a nuclear magnetic resonance spectroscopy graph of the compound (9) according to Example 3 of the present invention.

Claims (12)

A siloxane-containing perfluorinated polyhydric acrylic compound of the formula (1). [Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group of (C1-C3), R _f is -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- , or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers of 1 to 12, and r and v are integers of 1 to 30. The method of claim 1, A siloxane-containing perfluorinated polyvalent acryl-based compound wherein R ₂ is a methyl group. A method for preparing a siloxane-containing perfluorinated polyhydric acrylic compound prepared by reacting a siloxane-containing perfluorinated alkyl alcohol compound of Formula 2 with acryloyl chloride of Formula 3 under an amine base. [Formula 2]

Wherein R ₂ is an alkyl group of (C1-C3), R _f is -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- , or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers of 1 to 12, and r and v are integers of 1 to 30. [Formula 3]

In the above formula, R ₁ is a hydrogen atom or a methyl group. The method of claim 3, Formula 2 is a method for producing a siloxane-containing perfluorinated polyvalent acryl-based compound prepared by reacting tetraalkyl cyclotetrasiloxane of Formula 4 with the allyl alcohol of Formula 5 under a platinum catalyst. [Formula 4]

[Formula 5]

Wherein R ₂ is an alkyl group of (C1-C3), R _f is -CH _2- (CF ₂ ) _p -CH _2- , -CH _2- (CF ₂ OCF ₂ ) _q -CH _2- , or -CH ₂ CFO- (CF ₂ CF ₂ O) _r- (CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers of 1 to 12, and r and v are integers of 1 to 30. The method according to claim 3 or 4, A method for producing a siloxane-containing perfluorinated polyvalent acrylic compound, wherein R ₂ is a methyl group. The method of claim 4, wherein The allyl alcohol is a method of preparing a siloxane-containing perfluorinated polyhydric acryl-based compound prepared by reacting a fluorinated diol compound represented by the following Chemical Formula 6 with allyl bromide represented by the following Chemical Formula 7 under a base. [Formula 6] HO-R _f -OH Wherein R _f is —CH ₂ — (CF ₂ ) _p —CH ₂ —, —CH ₂ — (CF ₂ OCF ₂ ) _q —CH ₂ —, or —CH ₂ CFO— (CF ₂ CF ₂ O) _r -(CF ₂ O) _v -CF ₂ CH _2- , where p and q are integers of 1 to 12, and r and v are integers of 1 to 30. [Formula 7]

The method of claim 6, The fluorinated diol compound may be a diol compound of octafluorohexanediol, dodecafluorooctanediol, fluorinated triethylene glycol, fluorinated tetraethylene glycol, tetrafluoroethylene oxide-difluoromethylene oxide copolymer, Method for producing a siloxane-containing perfluorinated polyhydric acrylic compound selected from Fluorolink compound represented by the formula (8) and mixtures thereof. [Formula 8] HO-CH ₂ CF ₂ O (-CF ₂ F ₂ O) _n- (CF ₂ O) _m -CF ₂ CH ₂ -OH In the formula, m, n is an integer of 1 to 30. 10 to 99% by weight of the siloxane-containing perfluorinated polyvalent acrylic compound of claim 1; Perfluorinated mono- or divalent acrylic compound-based perfluorinated acrylic compound; And A photopolymerization composition comprising 0.01 to 5 parts by weight of the photoinitiator based on 100 parts by weight of the total perfluorinated acrylic compound. The method of claim 8, The perfluorinated monovalent or divalent acrylic compound is selected from the formulas 9 to 15 or mixtures thereof. [Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

A film prepared by irradiating ultraviolet light to the photopolymerizable composition of claim 8. The method of claim 10, The photopolymerization composition is a film prepared by further comprising 1 to 40 parts by weight of the solvent with respect to 100 parts by weight of the photopolymerization composition. The method of claim 11, Wherein said solvent is selected from flophylene glycol monomethyl ether acetate, cyclohexanone, cyclopentanone, or mixtures thereof.

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