KR20130006394A - Sulfur attached polycyclic polymers with high refractive index and large thermo-optic coefficient - Google Patents

Abstract

PURPOSE: An acryl monomer compound containing sulfide and an acryl derivative compounds induced from the same are provided to ensure high refractive index and to resolve serious optical loss. CONSTITUTION: An acryl monomer compound is denoted by chemical formula 2. An acryl derivative compound of chemical formula 4 is formed from the acryl monomer compounds of chemical formula 2. A method for preparing a polyurethane compound comprises a step of reacting isocyanate or a derivative compound thereof to the compound of chemical formula 2 or 4. The isocyanate compound is toluene diixocyanate(TDI), p-phenylene diisocyanate(PPDI), 1,6-hexamethylene diisocyanate(HDI), 1,5-naphthalene diisocyanate(NDI), or isoprene diisocyanate(IPDI). A method for manufacturing a polyurethane film comprises a step of mixing the compound of chemical formula 4 with a material formed by reaction of the isocyanate compound and a methacrylate-based compound and a step of adding a polymerization initiator. [Reference numerals] (AA,BB) Or

Description

Sulfur Attached Polycyclic Polymers with High Refractive Index and Large Thermo-Optic Coefficient

The present invention relates to a polymer optical device material, and more particularly, by introducing a stable cyclic sulfide in the molecule to induce a high refractive index and to improve the thermal expansion characteristics from the urethane structure to obtain a high refractive index and high thermo-optic characteristics having excellent thermo-optic properties It relates to a polymer optical element material having.

The refractive index of a material is defined by comparing the speed of light as it passes through the medium with the speed in vacuum. If the refractive index of the glass is about 1.5, it means that light passes 1 / 1.5 = 0.67 times slower. These refractive indices are very different depending on the type of medium, inorganic materials vary from very large values to very small values, and even in the case of organic substances having a hydrocarbon backbone structure, there are many differences depending on the molecular structure.

Most materials are not complete insulators and have a low dielectric constant. The interaction of the traveling light by the dielectric results in the dielectric loss of the traveling light, which, together with the light absorption of the material, greatly affects the transparency of the material. The dielectric constant is expressed as a function of the wavelength of the working light, and for materials without absorption, the square of the dielectric constant can be expressed as the refractive index, so the refractive index is also a function of the wavelength. This phenomenon is called dispersion, and the refractive index tends to decrease as the wavelength is longer when ordinary materials do not absorb light in the high frequency region of visible light.

The high refractive material refers to a material that exhibits a high refractive index under conditions where such light absorption does not occur. High refractive materials are widely used in the field of high refractive lenses, including semiconductor processing, display devices, solar cells, lasers, and the widest market.

In the case of spectacle lenses, plastic materials are used as glass substitutes for impact stability and heaviness. The thickness of the lens due to the low refractive index of the organic material is a disadvantage compared to the advantages of being relatively transparent and providing color control and multifunctionality. Although many materials have been developed based on polyacrylate polycarbonate, the refractive index of organic materials has been limited. As the aromatic hydrocarbon showed higher refractive index than the saturated hydrocarbon structure, there were studies on epoxy resins containing bisphenol-like materials, but the refractive index did not exceed 1.6. Although good results were obtained, the instability and derivative formation and other physical properties of halides were not good.

On the other hand, many researches on the induction of high refractive index using sulfur have been conducted, and recently, to domestic research institutes (Chemical Research Institute, Korean Patent No. 10-0515391, Korean Patent No. 10-0573431) and industry (Q & T Co., Ltd.) Improved results were released. A method of forming a urethane resin by introducing a mercaptan derivative in a molecule and thermally curing with an isocyanate and photocuring of sulfur-containing acrylics to produce a material having high heat resistance, high light stability, and high transparency. Could achieve a high value.

However, there was a limit to further refractive index improvement, and it was difficult to increase the main monomolecular content in order to control the solubility of the monomolecule used with the triazine derivative and the physical properties of the formed polymer. This is due to the shortcomings of aromatic sulfides, especially among the single molecules containing sulfur. In addition to spectacle lenses, high refractive index organic polymer materials have recently been used and studied in many areas such as portable camera lenses, telephoto lenses, prisms, optical fibers, recording medium substrates such as optical disks and magnetic disks, and optical products such as color filters and ultraviolet absorption filters.

The development of MR6 and MR174 by Mitsui, Japan, has taken a new leap in new high refractive index applications, and these materials are known to have high refractive indices of 1.60 and 1.74, respectively (WO 2004/056495). Polyurethane material was used to prepare high temperature curing conditions (WO 2007/030353), and polysiloxane obtained through sol-gel reaction of a silicone derivative was used as a main component and metal oxide was introduced as an additive to cure. Oxide and siloxane materials such as titanium, aluminum, and zirconium are formed into a stable material by forming metal bonds into the silicon sites in a high temperature process to become a stable material.These materials increase transparency by increasing transparency in optical devices such as LEDs. An AR-coating application has been proposed to increase the absorption efficiency by inducing efficient emission of light and minimizing the reflection of light on device surfaces such as solar cells.

Research has often been published in which titanium ions have been introduced into organic materials to achieve high refractive indices (J. Appl. Poly. Sci. Vol. 117, 1978 (2010) L. Liu et al.). When titanium was introduced as a method of sol-gel combining alkoxytitanium and alkoxy silane with an organic material and forming a stable titanium-siloxane material through a high temperature reaction, the refractive index was improved as the titanium content was increased to obtain a refractive index increase of up to 2.1. Light loss is rarely observed above 350 nm, so it is a good material that is very transparent in the visible region, but there is a problem that the application is limited due to the reproducibility of the process and the high temperature fixation of 300 ° C or higher (M. Burattini et al. Univ of Rome- Torvergata, 2006).

Development of high refractive materials for sulfide polyurethanes is mentioned in several documents (KR0573431, WO030353). A linear thioether structure was used and photocured acrylic functional groups were introduced at the ends (J. Appl. Pol. Sci. Vol. 91, 2358 (2004), YWQuan et al .; Ind. Eng. Chem. Res. vol. 47, 2155 (2008), A. Nebioglu et al .; EP 0780413A1; EP0802208A1). Cyclic urethane materials of 1,4-dithiane structure have also been published (J. Appl. Pol. Sci. Vol. 68, 1791 (1998) T. Okubo et al.). As optical waveguide optical elements using thermo-optic effects, optical filters, optical attunators, and optical switches require materials with high thermo-optic coefficients to improve device characteristics.

Thermo-optic coefficients (dn / dT) of polyesters, epoxy resins, polyimides, polyamides, polyolefins, etc. are measured to be -2 x 10 ^-4 or less, with slight differences depending on the material, but the values are about the same. . On the other hand, in the case of polyurethane, it is known that the degree of thermal expansion according to temperature is very high due to the hydrogen bonding between molecules, and as a result, the refractive index change (dn / dT) according to temperature is represented as -4 x 10 ^-4 ( Polymer vol. 47, 4893 (2006), Z. Zhang et al.

In order to solve the above problems, the present invention is to obtain a high refractive index organic molecules by covalently bonding a high content of sulfur by using a cyclic structure, high refractive index and excellent thermo-optical properties by introducing high refractive molecules of this structure into polyurethane An object of the present invention is to obtain a polymer optical element material that implements the same.

In addition, an object of the present invention is to reduce the light absorption in the near infrared region generated by hydrogen bonded to nitrogen of the urethane functional group so as to be used as a near infrared optical waveguide material.

It is also an object of the present invention to obtain a partially deuterated polyurethane compound in order to obtain a material suitable for thermo-optical waveguide devices from these thermo-optical properties and high refractive index.

In order to achieve the above object,

It provides a cyclic acrylic monomolecular compound represented by the following formula (1) or (2):

Wherein X and Y are each O or S, and n is 1-4.

In addition, in order to achieve the above object, the present invention

Provided is an acrylic derivative compound formed by being derived from Formula 1 or Formula 2 and represented by Formula 3 or Formula 4.

Wherein X and Y are each O or S, n is 1 to 4, and R represents H or CH ₃ .

In addition, in order to achieve the above another object, the present invention

Provided is a method for preparing a polyurethane compound obtained by reacting at least one compound selected from Formulas 1 to 4 with an isocyanate or derivative thereof.

In addition, in order to achieve the above another object, the present invention

It provides a method for producing a polyurethane film obtained by mixing a material obtained by reacting an isocyanate compound with a methacrylate compound and a compound represented by the following formula (3) or (4), adding a polymerization initiator, and then polymerizing it.

According to the present invention, a cyclic sulfide polyurethane material containing a high content of sulfur, exhibiting a high refractive index and introducing a urethane bonding method in order to increase the thermo-optical effect of the material is prepared. The high thermo-optic effect of the urethane structure is due to the intermolecular hydrogen bonds, but the doubling vibration absorption bands in the near-infrared region due to the bonding of nitrogen and hydrogen can cause light propagation loss in the same region as the optical waveguide material. Deuterium substituted polyurethane materials can have excellent properties as optical waveguides or thermo-optic materials by solving severe light losses.

1A and 1B show the results of infrared absorption spectroscopy of a material according to an embodiment of the present invention.
2A and 2B show the results of infrared spectroscopy of a partially / fully substituted polymer of deuterium according to an embodiment of the present invention.
3 shows the thermo-optical properties of a linear polyurethane film Ka according to one embodiment of the invention.
4 shows thermo-optical properties of a linear polyurethane film Kc according to one embodiment of the invention.
5 illustrates thermo-optic properties of a photocured polyurethane film according to one embodiment of the invention.

The present invention provides a cyclic acrylic monomolecular compound represented by Formula 1 or Formula 2 below:

[Formula 1]

[Formula 2]

Wherein X and Y are each O or S, and n is 1-4.

Formula 1 may be specifically represented by the following formula.

Formula 2 may be specifically represented by the following formula.

An acrylic derivative compound represented by Formula 3 or Formula 4 may be synthesized from Formula 1 or Formula 2.

(3)

[Formula 4]

Wherein X and Y are each O or S, n is 1 to 4, and R represents H or CH ₃ .

Formula 3 may be specifically represented by the following formula.

Wherein n is 1 or 2.

Formula 4 may specifically be represented by the following formula.

According to another aspect of the present invention, there is provided a polyurethane compound obtained by reacting an isocyanate or an isocyanate derivative with at least one compound selected from the formulas (1) to (4). The polyurethane compound may be specifically represented by the following formulas K, L, M, N.

According to another aspect of the present invention, a material obtained by replacing part or all of hydrogen with deuterium (D) in a polyurethane compound obtained by reacting an isocyanate derivative with at least one compound selected from the formulas (1) to (4).

The polyurethane compound obtained by the deuterium substitution may be represented by the following formula.

Polyurethane compounds obtained by deuterium substitution as in the above formula may be applied as a material for reducing the optical waveguide loss in the near infrared region.

The present invention also provides a polyurethane film obtained by mixing a material obtained by reacting an isocyanate compound with a methacrylate compound and a compound represented by the following Chemical Formula 3 or Chemical Formula 4, adding a polymerization initiator, and then polymerizing it.

(3)

[Formula 4]

Wherein X and Y are each O or S, n is 1 to 4, and R represents H or CH ₃ .

Here, it is preferable that the isocyanate compound is a toluene diisocyanate or isoprene diisocyanate material, and the methacrylate compound is preferably 2-hydroxy methacrylate (HEMA).

In addition, hydrogen is substituted with deuterium (D) in a material obtained by reacting an isocyanate compound with a methacrylate-based compound to polymerize it to prepare a deuterated polyurethane film.

The material according to the present invention is intended to increase the refractive index of the material, including sulfur, and to change the carbonyl group to 1,3-dithiane structure in order to increase the content of sulfur covalently bonded in the unit molecule can be introduced. . It is easy to control the refractive index by using not only linear polyurethane but also photocurable polyurethane structure. In addition, by introducing an isotope substitution method to shift the absorption region of the doubling vibration motion region, severe light loss of the polyurethane material can be solved, thereby obtaining excellent properties as an optical waveguide or thermo-optic material.

The present invention relates to a method of inducing high refractive index using only organic materials without using inorganic materials or inorganic mixed materials. The material has excellent thermo-optic properties by increasing the content of covalently bonded stable sulfur in the molecular structure and introducing it into the urethane polymer. Can be obtained.

The scheme for synthesizing the compounds according to the invention is described below.

[Reaction Scheme 1]

Using the material produced by the reaction of cyclopentadiene and maleic anhydride as a starting material, it is reduced to form a diol, which is protected by acetyl to obtain A-1. Synthesizing dialdehyde using ozone treatment or oxidizing agent for double bond and pentacyclic ring reactants such as 1,2-ethanedithiol, 2-mercaptoethanol, ethylene glycol, or more carbon, 1,3-propanedithiol A-2 is obtained by reacting with a hexagonal ring product such as 3-mercapto-1-1-propanol and 1,3-propanediol. Finally, material A is synthesized by a deprotection reaction.

[Reaction Scheme 2]

Substituting or mesylating OH of A material in Scheme 1 with halogen to form an intermediate, reacting with thioacetic acid and deacetylation to synthesize B material, dithiol, as a final material.

According to one embodiment of the present invention, a polyurethane obtained through the reaction of Compound A with isocyanates will be described in the following scheme.

Scheme 3

Various diisocyanate materials include, but are not limited to, toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), 1,6-hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI) ), Isoprene diisocyanate (IPDI), and the like. Catalytic reaction with the diol material A produces a polyurethane. In particular, the material polymerized using IPDI and TDI has a structure of K and L, respectively.

According to one embodiment of the present invention, the polyurethane obtained through the reaction of compound B with isocyanates will be described in the following scheme.

[Reaction Scheme 4]

Various diisocyanate materials include, but are not limited to, toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), 1,6-hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI) ), Isoprene diisocyanate (IPDI), and the like. Catalytic reaction with the diol material A produces a polyurethane. In particular, the material polymerized using IPDI and TDI has a structure of K and L, respectively.

According to another aspect of the present invention, a photocurable urethane acrylic polymer can be synthesized, which will be described in the following scheme.

Scheme 5

Various diisocyanate materials for making photocurable urethane acrylic monomolecules include toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), 1,6-hexamethylene diisocyanate (HDI), 1,5-naphthalene Examples include diisocyanate (NDI) and isoprene diisocyanate (IPDI), and in particular, the substances obtained by reacting with 2-hydroxyethyl methacrylate (HEMA) using IPDI and TDI are monomolecular diacrylates H-1 and H, respectively. Synthesizes -2.

[Reaction Scheme 6]

In order to obtain a photocurable polymer film, E, F, G-1, G-2, G-3, G-4, etc. as a monomolecular acrylic material and various weight ratios of urethane acryl such as H-1 and H-2 And then add 0.1 to 0.5% by weight of the photocuring initiator based on the total monomolecular weight. After applying the mixture thinly on the substrate and then irradiated with ultraviolet (100W) for about 10 minutes under nitrogen conditions to prepare a polymer film. In case of poor solubility, about 50% of solvent is added to the substrate and in this case, the solvent is completely removed by heat treatment after the curing reaction. Various polymer films are prepared from the combination of single molecules E, F, H-1, and H-2, and various films of O, P, Q, and R having different contents are prepared therefrom.

According to another aspect of the present invention, a deuterium-substituted urethane acrylic polymer can be synthesized, which will be described in the following scheme.

[Reaction Scheme 7]

As an experiment to investigate the efficiency of deuterium substitution reaction, the starting material obtained by reacting IPDI and benzyl alcohol is used as a research material, and it is dissolved in THF. Mix 1/4 of D ₂ O / MeOD (1/2, v / v) deuterium solvent with THF in volume ratio and stir vigorously. The solvent is then completely removed and dried to yield deuterium substituted product bound to nitrogen which is then spectroscopically analyzed.

 [Reaction Scheme 8]

This experiment is to find out the effectiveness of deuterium substitution reaction on polyurethane and use Kc as a research material and dissolve it in THF. Mix deuterium (D ₂ O) in 1/4 with THF in volume ratio and stir vigorously. The solvent is then completely removed and dried to obtain a deuterium substituted polymer urethane bound to nitrogen, which is then used for spectroscopic analysis and optical loss measurement.

Scheme 9

In order to proceed with deuterium substitution on the photocurable polyurethane, deuterium substitution is performed on the single molecule urethane acryl. Dissolve H-1 and H-2 in THF, and mix D ₂ O / MeOD (1/2, v / v) deuterium mixed solvent at 1/4 by volume in THF and stir vigorously. The solvent was then completely removed and carefully dried to obtain deuterium substituted monomolecule urethanes I, J bound to nitrogen which were used for film formation.

Example

Example 1

25.9 g (160 mmol) of norbornene anhydride was dissolved in tetrahydrofuran (500 mL), and reacted with LiAlH ₄ (7.2 g) at 0 ° C. for about 1 hour. After stirring for 2 hours at room temperature, 50 mL of ethyl acetate was added thereto. After stirring at room temperature for 1 hour, water and 10% HCl were added to perform a hydrolysis reaction, and extracted with ethyl acetate. The extracted organic layer was treated with MgSO ₄ and concentrated to give acetyl protected product A-1 (95%). A-1 (10 g, 42 mmol) was dissolved in dichloromethane (70 mL) and methanol (70 mL) in a 250 mL two-necked flask and maintained at -75 ° C. About 10% of ozone gas was flowed into the reaction solution for about 1 hour. When the solution began to have a light blue color, the ozone treatment was stopped, and after stirring for 10 minutes, 20 mL of dimethyl sulfide was added thereto, and the reaction temperature was raised to room temperature, followed by stirring for about 12 hours. Water was added, the organic layer extracted with dichloromethane was treated with MgSO ₄ , concentrated, and dialdehyde (A-2, 85%) was separated using silica gel chromatography. For the aldehyde protection reaction, using a 1,2-ethanedithiol (2-mercaptoethanol or ethylene glycol) (10 equiv) and Dean-Stark reflux under toluene solvent containing sulfonic acid (0.05 equiv) catalyst The reaction was time. The obtained material was washed with water, extracted with ethyl acetate and concentrated (85%). This solution was dissolved in methanol / tetrahydrofuran (1/3, v / v) and 2.5 acetyl KOH was added to deacetylate at room temperature (90%).

Ac ; ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; ppm) 4.68 (d, 2H), 3.95-3.60 (m, 6), 3.18 (m, 8H), 2.48-1.88 (m, 4H), 1.42 (m, 2H).

Aa ; ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; ppm) 4.81 (d, 2H), 3.75 (m, 4H), 3.7 (br, 2H, OH), 2.25-1.60 (m, 4H), 1.42 (m, 2H). ¹³ C-nmr (solvent: CDCl ₃ ; ppm) 106.7, 65.3, 62.7, 45.3, 44.5, 29.2.

Ab ; ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; ppm) 5.01 (d, 2H), 4.38 (m, 2H, O-CH 2), 3.70 (m, 6H, CH 2 -O), 3.40 (s, 2H, OH ), 3.0 (s, 4H, S-CH2), 2.40-1.80 (m, 4H), 1.35 (m, 2H). ¹³ C-nmr (solvent: CDCl ₃ ; ppm) 90.7, 71.9, 62.5, 48.6, 46.5, 44.5, 32.7.

Example 2

The substance Ac (6.7 g, 20 mmol) obtained in Example 1 was dissolved in anhydrous dichloromethane (60 mL), triethylamine (6.6 mL) was added, and chloromethanesulphone (5.3 g, 95%) was slowly added at 0 ° C. . After stirring for 30 minutes at room temperature, water was added, extracted with dichloromethane and washed with brine. The solution was concentrated, dissolved in dimethylamide (15 mL) and tritriethylamine (6.6 mL) was added. Thioacetic acid (96%, 3.3 mL) was slowly added to this solution and allowed to react at room temperature for 24 hours. The mixture was diluted with water, extracted with ether, concentrated, dissolved in tetrahydrofuran and methanol (3/1, v / v) again, and water-soluble KOH was added thereto to deacetylate to obtain Bc .

IR (cm ^-1 ): 2750 (SH vibration)

¹ H-nmr (300 MHz; CDCl ₃ ; d ppm) 1.70 (t, SH).

Example 3

2-Hydroxypropane-1,3-dithiol (1.23 g) was dissolved in anhydrous ether (50 mL) and worttriethylamine (4.6 mL) and chlorotrimethylsilane (4.1 mL) were added sequentially at 0 ° C. . After stirring for 10 minutes at room temperature, the solution was purified using water and ether and concentrated. The resulting material was dissolved in anhydrous dichloromethane (30 mL) and 1,4-cyclohexanedione (or 1,3-cyclohexanedione) (0.56 g, 5 mmol) was added and kept at -78 ° C under nitrogen. Into this reactor, trimethylsilyl trifluoromethane sulfonate (TMSOTf), a strong Lewis acid, was added by a catalytic amount (0.22 g), and the temperature was gradually raised to room temperature. Over time, an unknown solid material was produced and the material C-1 to be synthesized was formed. After about 3 hours of stirring at room temperature, water was added to proceed with the desilyl reaction, and then the material was separated (30%). Similarly, 1,3-cyclohexane-dione was used to form product C-2 , and 3- D-1 and D-2 were synthesized using hydroxypropane-1,2-dithiol.

C-1 : ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; d ppm) 3.98 (m, 2H), 3.55 (dd, 2H, OH), 3.18 (br, 4H, S-CH 2), 2.72 (br, 4H, S-CH 2), 2.3 (s, 4H), 2.05 (s, 4H).

D-1 : ¹ H-nmr (300MHz; Solvent: CDCl ₃ ; d ppm) 4.25-3.55 (m, 4H), 3.35 (dd, 2H, OH), 2.99-2.35 (m, 6H, S-CH2, S -CH), 2.1 (s, 6H), 1.80 (m, 2H).

Example 4

Sulfur-containing diol Ac (1.69 g, 5.0 mmol) was dissolved in (20 mL), triethylamine (1.7 mL), methacrylic anhydride (1.7 mL) and a catalytic amount of N, N-dimethylaminopyridine (30 mg) were added. After stirring for 10 hours at room temperature. Diacrylate E (n = 1,85%) was obtained after chromatographic separation using silica.

E (n = 1); ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; ppm) 6.08 (s, 2H), 5.58 (s, 2H), 4.75 (d, 2H), 4.21 (s, 4H), 3.18 (s, 8H), 2.4 ˜2.02 (m, 4H), 1.95 (s, 6H), 1.6 (br, 2H).

G-1 ; ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; ppm) 6.19 (s, 2H), 5.60 (s, 2H), 5.08 (m, 2H), 3.02-2.80 (m, 8H), 2.35 (s, 4H) , 2.0 (s, 4H), 1.96 (s, 6H).

G-3 ; ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; ppm) 6.12 (s, 2H), 5.58 (s, 2H), 4.3 (m, 4H), 4.21 (m, 2H), 3.38 (m, 4H), 2.7 ˜2.3 (m, 8H), 2.0 (s, 6H).

Example 5

Isoprene diisocyanate (IPDI, 1.05 mL) and HEMA (1.37 g) were dissolved in chloroform (25 mL), and a catalytic amount of dibutyltin diaurate was added thereto, followed by stirring at room temperature for 24 hours. After analysis using chromatography, H-1 (2.2 g, 90%) was obtained.

H-1 ; ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; ppm) 6.18 (s, 2H), 5.58 (s, 2H), 4.8-4.6 (br, 2H, NH), 4.35 (m, 8H), 3.8 (m, 1H), 2.98 (s, 2H), 2.00 (s, 6H), 1.92-1.60 (6m, 6H), 1.0 (s, 6H), 0.95 (s, 3H).

Example 6

Sulfur-containing diol Ac (1.69 g, 5.0 mmol) and isoprene diisocyanate (IPDI, 1.05 mL) were dissolved in chloroform (25 mL), charged with a catalytic amount of dibutyltin diaurate, and then stirred at room temperature for 24 hours. Thereafter, the mixture was stirred for 2 hours at 60 ° C. and slowly dropped in methanol to precipitate the polymer. The obtained polymer was filtered and then dissolved in chloroform to be precipitated in methanol to obtain a purified polymer Kc (2.1 g).

Kc ; ¹ H-nmr (300 MHz; Solvent: CDCl ₃ ; ppm) 4.78 (br, 2H), 4.41 (m, 4H)-4.00 (m, 10H), 3.23 (b, 2H, OH), 3.7 (br, 2H, OH), 2.40-1.650 (m, 4H), 1.42 (m, 2H).

Example 7

Diacrylates containing sulfur (E, F, G-1, G-2, G-3, G-4) and urethane functional groups (H-1, H) to form a photocurable film -2) Mix the two materials in a constant weight ratio (2/8, 5/5, 8/2) and dilute the photocuring initiator (Irgcure 819) using 0.2% per total weight of acrylic single molecule and trichloropropane solvent. (50% wt / wt) then carefully mix for 1 hour. The resulting mixture was removed from the undissolved particles using a disk-type polymer filter PTFE (0.2um). The filtered liquid was blocked at light at room temperature and left for about 2 hours to remove bubbles. A thin film was formed by rotational molding on the silicon substrate and irradiated with ultraviolet (100 W) for 10 minutes under nitrogen conditions. The cured thin film was heat-treated in a vacuum oven (100 ° C./vacuum) for 1 hour to prepare films (O, P, Q, R).

Example 8

As the experiment for the urethane hydrogen substitution reaction conditions and assay, the same experiment as in Scheme 7 was performed. 1.0 g of the material obtained by reacting IPDI with benzyl alcohol was completely dissolved in THF (tetrahydrofuran, 6 mL), and deuterium water (1 mL) and methanol (2 mL) were added thereto, followed by vigorous stirring for 2 hours. Then 10 mL of toluene was added to the solution, anhydrous MgSO ₄ (2 g) was added thereto, followed by stirring for 10 minutes to remove solids by a filter. The resulting solution was vacuum distilled to remove all solvents and analyzed.

Example 9

Urethane High Polymer Kc (0.5 g) was completely dissolved in THF (4 mL), and deuterium water (1 mL) and methanol (2 mL) were added thereto, followed by vigorous stirring for 2 hours. Then 50 mL of toluene was added and anhydrous CaCl ₂ (granule, 3g) was added thereto, followed by stirring for 10 minutes to remove solids by a filter. The resulting solution was vacuum distilled to remove all solvents and analyzed.

Evaluation and Results

infrared ray Absorption Spectroscopy

Infrared absorption spectroscopic analysis was performed to verify urethane hydrogen substitution, and the results are shown in FIGS. 1A and 1B. 1A and 1B, NH is reduced and ND is clearly shown in infrared analysis. In addition, the result of partial / complete substitution of deuterium was verified, and the results are shown in FIGS. 2A and 2B. Referring to Figures 2a and 2b, it was demonstrated that the complete substitution reaction took place as the NH gradually decreased and the ND absorption band appeared completely.

Refractive index  And Thermo-optics  effect

The refractive indices at 850, 1310 and 1550 nm and the thermo-optic effect were measured for Ka and Kc in K, a linear polyurethane molecule. The refractive index was measured for each wavelength using a prism coupling method (prism coupler and loss measuring system, Ceron, PCA-2000). The temperature of the sample is gradually changed from room temperature to high temperature to obtain a graph of refractive index change by temperature as shown in FIGS. 3, 4 and 5, and then the thermo-optic effect is obtained by obtaining dn / dT from the slope of the conversion graph expressed by the linear equation. Decided.

In order to obtain a photocurable polymer film, the monomolecular acrylic material E and the urethane acrylic monomolecule H-1 were mixed at a weight ratio of 2: 8, 4: 6, and 6: 4, respectively. 0.3 wt% of the photoinitiator was added to the entire monomolecular material, and the ultraviolet ray (100W) was irradiated under nitrogen filling conditions for 10 minutes to complete the polymer film, and the refractive index and the thermo-optic effect of the polymer film obtained therefrom were measured.

The refractive index and thermo-optical measurement results of the linear polyurethanes Ka and Kc and the photocurable polyurethane (E / H-1) are summarized in Table 1 and shown in FIGS. 3 to 5.

Polymers  n _{TE ( TM )} - dn Of dT 850 nm 1310 nm 1550 nm Ka 1.5028
(1.5026) 1.4975
(1.4975) 1.4962
(1.4962) 2.4 * 10 ^-4 Kc 1.5538
(1.5537) 1.5477
(1.5476) 1.5463
(1.5463) 3.6 * 10 ^-4 E / H-1 (2/8) 1.5161
(1.5162) 1.5111
(1.5112) 1.5098
(1.5098) 1.9 * 10 ^-4 E / H-1 (4/6) 1.5359
(1.5358) 1.5305
(1.5305) 1.5293
(1.5293) 2.4 * 10 ^-4 E / H-1 (6/4) 1.5436
(1.5437) 1.5384
(1.5382) 1.5373
(1.5372) 2.0 * 10 ^-4

The material according to the present invention is intended to increase the refractive index of the material, including sulfur, and introduced a method of changing the carbonyl group to 1,3-dithiane structure to increase the content of sulfur covalently bonded in the unit molecule.

A cyclic sulfide polyurethane material was prepared, including a high content of sulfur, exhibiting a high refractive index and introducing a urethane bonding method to increase the thermo-optic effect of the material. By employing not only linear polyurethane but also a photocurable polyurethane structure, a method of easily controlling the refractive index was selected.

Ka, a linear polyurethane material, contains monomolecules cyclized with O, O, and Kc is a material containing S, S. The refractive index of Kc is measured at various wavelengths. In addition, it can be seen that the refractive index is gradually improved as the content of the E single molecule containing sulfur increases with the content of E and H-1 in the photocured film.

Table 2 is described in the prior art (Polymer 47, 4893 (2006) Zhang et al.) As a comparative data showing the thermo-optical properties of various polymers, and is incorporated into the specification of the present invention.

Referring to Table 2, it can be seen that the urethane material of the present invention shows a high thermo-optical effect compared to various conventional materials.

The high thermo-optic effect of the urethane structure is due to the intermolecular hydrogen bonds, but the double vibration absorption band in the near infrared region by the nitrogen-hydrogen bond can cause light propagation loss in the same region as the optical waveguide material. This phenomenon is caused by the doubled vibration absorption loss caused by the carbon-hydrogen bond, so that the hydrogen bond is still present to overcome this, but isotope substitution method was introduced to move the absorption region of the double vibration vibration region. As a result, the deuterium substituted polyurethane material has excellent properties as an optical waveguide or thermo-optic material by solving severe light loss.

The present invention described above is not limited to the above-described embodiments and reaction schemes, and various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention.

Claims (10)

Acrylic monomolecular compound represented by the following formula (2):
(2)

Wherein X and Y are each O or S, and n is 1-4.
The method of claim 1,
The compound is an acrylic monomolecular compound, characterized in that one selected from the following C-1, C-2, D-1, D-2 material:

An acrylic derivative compound formed from the chemical formula of claim 1 and represented by the following general formula (4):
[Chemical Formula 4]

Wherein X and Y are each O or S, n is 1 to 4, and R represents H or CH ₃ .
The method of claim 3,
The compound is an acrylic derivative compound, characterized in that one selected from the following G-1, G-2, G-3, G-4 material:

Wherein n is 1 or 2.
A method for producing a polyurethane compound, which is obtained by reacting at least one compound selected from formulas (2) and (4) of claim 1 or 2 with an isocyanate or derivative thereof.
The method of claim 5,
The isocyanate compounds include toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), 1,6-hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI), and isoprene diisocyanate (IPDI). Method for producing a polyurethane compound, characterized in that at least one selected from the group consisting of.
The method of claim 5,
Method for producing a polyurethane compound, characterized in that hydrogen or all of hydrogen bonded to nitrogen (N) in the polyurethane compound is substituted with deuterium (D).
A method for producing a polyurethane film, which is obtained by mixing a material obtained by reacting an isocyanate compound with a methacrylate compound and a compound represented by the following formula (4), adding a polymerization initiator, and then polymerizing it.
[Chemical Formula 4]

Wherein X and Y are each O or S, n is 1 to 4, and R represents H or CH ₃ .
9. The method of claim 8,
The isocyanate compound is a toluene diisocyanate or isoprene diisocyanate material, the methacrylate-based compound is a method of producing a polyurethane film, characterized in that 2-hydroxyl methacrylate (HEMA).
9. The method of claim 8,
A method for producing a polyurethane film, wherein hydrogen is substituted with deuterium (D) in a material obtained by reacting the isocyanate compound with a methacrylate compound.

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