KR101833446B1 - Bisfuran derivative compound, composition comprising the same, and method for preparing the same - Google Patents

Abstract

The present invention relates to a bis-furan derivative compound, a composition comprising the same, and a manufacturing method thereof, and more particularly, to a bis-furan derivative compound having two or more acrylate groups at the terminal thereof, and to a manufacturing method thereof. The bis-furan derivative compound of the present invention has a furan-based compound as a basic skeleton and substitutes an acrylate group at the terminal thereof, so that damage due to contact of moisture is minimized to improve mechanical strength, and hardening shrinkage and water absorption are reduced.

Description

TECHNICAL FIELD The present invention relates to a bisfuran derivative compound, a composition containing the bisfuran derivative compound, and a process for producing the same. BACKGROUND ART [0002]

More particularly, the present invention relates to a curing type bisfuran derivative compound having two or more acrylate groups at the terminal thereof, and a process for producing the same.

Curable materials such as adhesives, adhesives, sealants, coatings and paints are currently being used in various industrial fields such as packaging, bookbinding, automotive, electronics, precision, optical products, woodworking, plywood, It is widely used for home use, and its use has become widespread, and recently it has also been applied to concrete. Such adhesives and the like are manufactured in the form of a mixture of chemical materials based on a synthetic resin. Since the volatile organic compounds (VOC) are added due to the organic solvent (solvent) used in the manufacturing process and various volatile additives added to improve the physical properties, , Dioxins, and environmental hormones. In recent years, environmental regulations under international agreements have strictly restricted the production and use of these harmful substances. Furthermore, the EU has used such regulations as a means of new trade sanctions. In keeping with this trend, conventional solvent type adhesives have been replaced by water-soluble, solvent-free, hot-melt type and the like. Furthermore, not only these adhesive materials, but most of the fine chemical materials we currently use are petrochemical products derived from the Oil Refinery Process. However, international oil prices are steadily rising due to a decrease in reserves and a surge in demand centering on BRICs. As international conventions that strictly regulate greenhouse gas emissions become effective, future use of irreversible fossil resources such as oil will lead to enormous environmental costs .

Therefore, many efforts have been made to obtain existing petroleum-derived fine chemical products from new resources, and the most representative example is to use carbohydrate-based biomass as a supply source. The natural world produces about 170 billion tons of carbohydrates every year through photosynthesis. Human beings use only about 3% of them as food, paper, furniture, and building materials. Thus, fine chemicals manufactured from renewable and sustainable carbohydrate biomass are expected to replace petrochemicals. Accordingly, in order to replace conventional light source curing adhesive materials derived from petroleum resources, development of a technology for synthesizing compounds having predetermined adhesion or adhesion properties using such environmentally friendly carbohydrate-based biomass is required. As representative carbohydrate-based biomass, there are furan compound derivatives.

However, in general, a curable, particularly a photo-curable adhesive material having a functional group such as an acrylate or isocyanate group has a rapid curing property at room temperature through radical polymerization, but the shrinkage phenomenon is very large due to such a rapid curing speed It has a problem. Due to this excessive shrinkage phenomenon, introduction of a material having a small shrinkage ratio after curing is required in an industrial field using adhesive materials, particularly in fields requiring precise dimensional stability such as electronic materials

However, in the case of a dental filler derived from a conventional biomass, the mechanical strength is weakened due to the property of absorbing moisture, and the aesthetics of the dental filler are lowered due to shrinkage of the material itself.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-described problems, and it is an object of the present invention to provide a furan-based compound having a basic skeleton and substituting an acrylate group at the terminal thereof, A composition containing the bisfuran derivative, and a process for producing the same.

According to one aspect of the present invention, a bisfuran derivative compound represented by the following structural formula 1 is provided.

 [Structural formula 1]

In formula 1,

R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected.

R ¹ , R ² and R ³ may be the same or different from each other, and each independently may be a hydrogen atom or a methyl group.

The compound represented by Formula 1 may be a compound represented by Formula 1 below.

[Chemical Formula 1]

The bisfuran derivative compound can be used as a dental material.

According to another aspect of the present invention, there is provided a process for preparing a compound 3 by reacting Compound 1 with Compound 2, as shown in Reaction Scheme 1 below (Step a); Reacting compound 3 to produce compound 4 (step b); Reacting compound 4 to prepare compound 5 (step c); And compound 5 to prepare compound 6 (step d); ≪ / RTI > is provided.

[Reaction Scheme 1]

In the above Reaction Scheme 1,

R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected.

R ¹ , R ² and R ³ may be the same or different from each other, and each independently may be a hydrogen atom or a methyl group.

The above step d is as shown in the following Reaction Scheme 2, and the reaction of Reaction Scheme 2 can be carried out by reacting Compound 5 with Compound 7.

[Reaction Scheme 2]

R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected.

According to another aspect of the present invention, there is provided a bisfuran derivative compound represented by the structural formula 1; Initiator; And fillers; ≪ / RTI > is provided.

Wherein the bisfuran derivative composition comprises 100 parts by weight of the bisfuran derivative compound of formula 1; 0.1 to 5 parts by weight of the initiator; And 50 to 500 parts by weight of the filler.

The initiator may be a photopolymerization initiator.

Wherein the initiator is selected from the group consisting of camphoquinone, ethyl-4-dimethylamino benzoate, tertiary amine initiator, diphenyl iodonium chloride, diphenyl iodonium hexafluorophosphate, diphenyl Iodonium tetrafluoroborate, tolylcumyl iodonium tetrakis (pentafluorophenyl) borate, acyl, bisacylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis 2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2- 2-methyl-1-phenylpropan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy- Ethyl 2,4,6-trimethylbenzyl phenylphosphinate, and the like.

Wherein the filler is selected from the group consisting of barium glass fillers, barium aluminosilicates, synthetic amorphous silicas, crystalline silicas, barium silicates, barium borosilicates, barium fluoroaluminosilicates, But are not limited to, barium fluoroaluminoborosilicate, barium aluminoborosilicate, strontium silicate, strontium borosilicate, strontium aluminoborosilicate, calcium silicate, May be at least one selected from alumino silicate, silicon nitrides, titanium dioxide, calcium hydroxyapatite, zirconia, and bioactive glass. have.

The bisfuran derivative composition may be used as a dental filler.

In another aspect of the present invention, there is provided a dental filler prepared by curing the bisfuran derivative composition.

The bisfuran derivative compound prepared according to the present invention has a basic skeleton of a furan compound and substitutes an acrylate group at the terminal to minimize damage caused by contact with water to improve mechanical strength, .

FIG. 1 shows nuclear magnetic resonance (NMR) analysis results of the compound prepared according to Example 1. FIG.
2 is a graph showing an analysis result of the curing behavior according to Test Example 1. Fig.
Fig. 3 is a SEM (scanning electron microscope) image of the fracture surface of the dental composition according to Test Example 2. Fig.
4 is a graph showing the results of analysis of flexural strength and compressive strength according to Test Example 3. Fig.
5 is a graph showing the results of analysis of resin shrinkage percentage according to Test Example 4. Fig.
6 is a graph showing the results of analysis of water absorption according to Test Example 5. Fig.

The invention is capable of various modifications and may have various embodiments, and particular embodiments are exemplified and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Furthermore, terms including an ordinal number such as first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

Also, when an element is referred to as being "formed" or "laminated" on another element, it may be directly attached or laminated to the front surface or one surface of the other element, It will be appreciated that other components may be present in the < / RTI >

The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, the bisfuran derivative compound of the present invention will be described.

The bisfuran derivative compound of the present invention may be a compound represented by the following structural formula (1).

[Structural formula 1]

In formula 1,

R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected.

Preferably, R ¹ , R ^2, and R ³ are the same or different from each other and each independently may be a hydrogen atom or a methyl group, and more preferably R ¹ , R ^2, and R ³ may be a methyl group.

The compound represented by Formula 1 may be a compound represented by Formula 1 below.

[Chemical Formula 1]

The structural formula 1 may be prepared by following the procedure of Scheme 1 below.

The bisfuran derivative compound may be for use as a dental material.

[Reaction Scheme 1]

In the above Reaction Scheme 1,

R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected.

Preferably, R ¹ , R ^2, and R ³ are the same or different from each other and each independently may be a hydrogen atom or a methyl group, and more preferably a methyl group.

First, compound 1 is reacted with compound 2 to prepare compound 3 (step a).

The reaction may be carried out at 40 to 80 캜, preferably 45 to 75 캜, more preferably 50 to 70 캜.

The reaction may be carried out for 3 to 48 hours, preferably 4 to 36 hours, more preferably 5 to 30 hours. However, the time at which the reaction is carried out may vary depending on the reaction temperature of step a.

Next, Compound 3 is reacted to prepare Compound 4 (Step b).

This step is a reaction for reducing an ester to a primary alcohol, and lithium aluminum hydride (LiAlH ₄ ) can be used as a reducing agent.

Compound 4 is then reacted to produce compound 5 (step c) .

In this step, epichlorohydrin is added as a substance for introducing an epoxide functional group into the furan compound represented by the formula (4).

Preferably, the mixture containing the compound 4 and epichlorohydrin is reacted with a phase transfer catalyst (PTC) as a catalyst in a bi-phasic solvent system to which an aqueous solution of sodium hydroxide (NaOH) is added .

The phase transfer catalyst is a catalyst which facilitates transfer of a chemical species from a liquid phase to a liquid phase. The reaction between the reactants present in the adjacent liquid phase separately, however, is carried out by transferring one reactant across the interface Can accelerate.

Wherein the phase transfer catalyst is selected from the group consisting of tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium chloride, tetrabutylammoniumhydrogen sulfate, methyltrioctylammonium chloride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyl Benzyltrimethylammonium hydroxide, triethylammonium chloride, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltributylammonium chloride, benzyltributylammonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tributylhexadecylphosphonium Bromide, butyltriphenylphosphonium chloride, ethyltrioctylphosphonium bromide, and tetraphenylphosphonium bromide. In addition to these, a phase transition catalyst Is not particularly limited.

Finally, compound 5 is reacted to prepare compound 6 (step d).

Step d is as shown in Reaction Scheme 2, and Compound 5 can be reacted with Compound 7 to prepare Compound 6.

[Reaction Scheme 2]

R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected.

The solvent used in step (d) may be toluene, trimethylamine (TEA), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) Is not limited thereto.

In the above reaction, the methacrylate group may be substituted at the terminal by reacting the epoxide group contained in the terminal of the compound 5 with methacrylic acid.

A bisfuran derivative compound represented by the structural formula 1; Initiator; And fillers; ≪ / RTI > is provided.

The initiator may be a photopolymerization initiator and is preferably selected from the group consisting of camphoquinone, ethyl-4-dimethylamino benzoate, tertiary amine initiator, diphenyl iodonium chloride, (Pentafluorophenyl) borate, an acyl, a bisacylphosphine oxide, bis (2,4,6-trimethylbenzoyl) amide, bis ) Bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, bis (2,6- dimethoxybenzoyl) -2,4,4-trimethyl 2-methyl-1-phenylpropan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy- Phenylpropan-1-one, and ethyl 2,4,6-trimethylbenzyl phenylphosphinate.

The filler may be selected from the group consisting of barium glass filler, barium aluminosilicate, synthetic amorphous silica, crystalline silica, barium silicate, barium borosilicate, barium fluoroaluminosilicate, But are not limited to, barium fluoroaluminoborosilicate, barium aluminoborosilicate, strontium silicate, strontium borosilicate, strontium aluminoborosilicate, calcium silicate, Alumino silicate, silicon nitrides, titanium dioxide, calcium hydroxyapatite, zirconia, and bioactive glass may be used. Preferably, a barium glass filler is used There. However, the scope of the present invention is not limited thereto.

Wherein the bisfuran derivative composition comprises 100 parts by weight of the compound of Formula 1; 0.1 to 5 parts by weight of the initiator; 50 to 500 parts by weight of the filler; . ≪ / RTI >

[Example]

Example  One: Bisfuran  A derivative compound Bisfuran GMA  Synthesis method

(Step a)

After adding 80 mL of H ₂ SO ₄ to the cooled flask, 10 g of methyl furan-2-carboxylate and 11.64 mL of acetone were slowly added dropwise. After increasing the reaction temperature by 50 ° C, 5.82 mL of acetone was added and reacted for 24 hours. After the reaction, the reaction product was cooled, and the product was extracted with ethyl acetate to obtain an extract. Water in the extract obtained with magnesium sulfate (MgSO ₄ ) was removed to obtain a product. Thereafter, ethyl acetate contained in the product was removed using a rotary evaporator, and compound a was obtained through column purification.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.14-7.06 (d, 1H), 6.24-6.16 (d, 1H), 3.86 (s, 3H), 1.74 (s, 3H).

[Reaction Scheme 3]

(Step b)

In a cooled flask, 2.5 g of lithium aluminum hydride (LiAlH ₄ ) was dissolved in 150 mL of tetrahydrofuran (THF) to obtain a solution. In another flask, compound a was dissolved in 200 mL of tetrahydrofuran, and then the resulting solution was administered. Thereafter, the reaction was allowed to proceed with stirring at room temperature for 24 hours. When the reaction was completed, excess lithium aluminum hydride (LiAlH ₄ ) was removed with sodium sulfate (Na ₂ SO ₄ ) solution to obtain a product. The obtained product was extracted with dichloromethane, followed by column purification to obtain compound b.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 6.18 (d, 2H), 5.98 (d, 2H), 4.54 (s, 4H), 2.40 (s, 2H) 1.65 (s, 6H).

[Reaction Scheme 4]

(Step c)

An aqueous solution of 50% sodium hydroxide (NaOH) and 1.365 g of tertbutylamino bromide were mixed at room temperature, and 34.266 g of epichlorohydrin was slowly added dropwise to prepare a mixture. A solution prepared by dissolving 10 g of the compound b obtained in the above step b in 170 mL of THF was slowly added dropwise to the mixture and reacted at room temperature for 4 hours to obtain a reaction product. The obtained reaction product was extracted with dichloromethane, and water was removed by adding MgSO ₄ . Thereafter, the solvent was removed by a rotary evaporator, and the final product compound c was obtained through column refining.

_{1H NMR (300MHz, CDCl 3)} : δ 6.28-6.20 (m, 2H), 6.00-5.92 (m, 2H), 4.52-4.40 (m, 4H), 3.75-3.65 (m, 2H), 3.48-3.38 ( m, 2H), 3.18-3.06 (m, 2H), 2.82-2.74 (m, 2H), 2.64-2.56 (m, 2H), 1.63 (s, 6H).

[Reaction Scheme 5]

(Step d)

10 g of the compound c obtained in the above step c, 1.12 g of triphenyl phosphine, 0.045 g of hydroquinone and 150 mL of toluene were placed in a flask, and 12.36 g of methacrylic acid was added thereto To prepare a mixture. The reaction temperature of the mixture was increased to 100 < 0 > C and allowed to react for 24 hours. After the reaction was completed, the product was extracted with dichloromethane, the water was removed with MgSO ₄ solution, and the solvent was removed using a rotary evaporator. Thereafter, the product was subjected to column purification to obtain the final product compound d (Bisfuran GMA).

[Reaction Scheme 6]

¹ H NMR and ¹³ C NMR analyzes of the prepared compound d (Bisfuran GMA) are shown in FIG. 1, and the data of ¹ H NMR (a) and ¹³ C NMR (b)

_{(a) 1H NMR (CDCl 3} 300MHZ): δ 6.23-6.30 (d, 2H), 6.12-6.19 (s, 2H), 5.96-6.04 (d, 2H), 5.55-5.63 (s, 2H), 4.42- 2H), 3.40-3.60 (m, 4H), 2.65-2.85 (s, 2H), 1.93-1.98 (s, 6H ), 1.63-1.70 (s, 6H).

(b) ¹³ C NMR (CDCl ₃ 300 MHz):? 167 (2C), 160 (2C), 150 (2C), 136 (2C), 126 (2C), 110 2C), 69 (2C), 66 (2C), 65 (2C), 38 (1C), 27 (2C), 19 (2C).

Example  2: Bisfuran  Method for preparing derivative composition

1 wt% initiator composed of camphoquinone / ethyl-4-dimethylamino benzoate (1: 2) was added to 5.0 g of the compound prepared according to Example 1 (Bisfuran GMA), 7.5 g of barium glass filler Based on 60wt%) and then mixed using a planetary vacuum mixer at 2000 rpm for 3 minutes to prepare a bisfuran derivative composition.

Comparative Example  One: BisGMA / TEGDMA  Preparation of mixture

(BisGMA: TEGDMA = 6: 4 weight ratio (wt%)) 3 g of the compound represented by the following formula 2 (BisGMA) and 2 g of the compound represented by the following formula 3 (TEGDMA) The mixture was prepared three times for three minutes.

(2)

(3)

Comparative Example  2: BisGMA / TEGDMA  Composition

To the mixture of Comparative Example 1, 7.5 g of barium aluminosilicate as a filler (60 wt% based on the total amount) was added and 1 wt% of an initiator composed of camphoquinone / ethyl-4-dimethylamino benzoate (1: 2) And mixed three times for 3 minutes at 2000 rpm using a planetary vacuum mixer to prepare a BisGMa / TEGDMA composition of Comparative Example 2. [

Comparative Example  3: IsoGMA  Compound manufacturing

(Step 1)

Isosorbide (1.0 g, 6.8 mmol) and KOH (2.8 g, 42 mmol) were placed in a 50 mL round-bottomed flask and covered with a rubber stopper, followed by dry DMSO (5 mL) under N ₂ atmosphere. 40 bases were immersed in a round bottom flask containing the reaction solution and thermally equilibrated. When thermal equilibrium was established inside the flask, epibromohydrin (3.84g, 28mmol) was slowly added dropwise via syringe. At this time, it was observed that the color of the suspension inside the flask gradually changed to dark brown depending on the drop amount. After dropwise addition, the mixture was reacted by stirring at 40 for 2 hours. Thereafter, the reaction solution was filtered through a syringe filter to remove salts from the residue, the filtrate was diluted with an appropriate amount of methylene chloride, and then transferred to a separating funnel. The mixture was washed with distilled water and brine in this order, and the organic layer was washed with water (MgSO ₄ ), filtered, concentrated under reduced pressure, and purified by flash chromatography (hexane: ethyl acetate = 1: 1) to give an isospoid The resulting compound (1-2) was obtained (1.1 g, 4.3 mmole, 63%).

The reaction of Step 1 is shown in Scheme 7 as shown below.

[Reaction Scheme 7]

(Step 2)

(1 g, 3.8 mmol), diphenyl picrylhydrazyl (10 mg, 0.6 mmol), and methacrylic acid (1 g) were added to a 100 mL round bottom flask under a nitrogen atmosphere. methacrylic acid (7 mL, 78 mmol) were added and stirred. Then, 3 drops of tetraethylamine (TEA) was added dropwise and the mixture was stirred at 100 for 4 hours. After completion of the reaction, a dark brown reaction solution was obtained. The reaction solution was transferred to a separatory funnel, washed 5 times with 20 wt% NaHCO ₃ aqueous solution and treated with water / ethyl acetate (water / EA). The organic layer of the treated product was distilled to remove the solvent, and a viscous colorless compound (IsoGMA) was prepared by flash chromatography of hexane: ethyl acetate (1: 2, v / v) (1.23 g, 2.9 mmole, 75%).

The reaction of Step 2 is shown in Scheme 8 as shown below.

[Reaction Scheme 8]

Comparative Example  4: IsoGMA  Composition manufacturing

A barium aluminosilicate (60 wt% based on the total amount), which is a filler, was added to the IsoGMA compound prepared according to Comparative Example 3. Thereafter, 1 wt% of an initiator composed of camphoquinone / ethyl-4-dimethylamino benzoate (1: 2) was added and mixed three times for 3 minutes at 2000 rpm using a planetary vacuum mixer to prepare a composition of Comparative Example 2.

[Chemical Formula 5]

[Test Example]

Test Example 1: Measurement of photocuring behavior

Figure 2 shows the results of Photo-DSC to analyze photo-curing behavior. To measure Photo-DSC, 1 wt% of Darocur TPO (Ciba) photoinitiator was added to each of the resins of Example 1, Comparative Example 1 and Comparative Example 3 to prepare a resin mixture. Then, 1 mg of the resin mixture was taken in a DSC cell And the photo-DSC (DSC Q200, TA instruments) was measured by irradiating UV intensity 10 mW / cm ² at room temperature.

As a result of Photo-DSC analysis, as shown in Fig. 2, in the case of the compound of Example 1, the photo-curing reaction progressed somewhat later at the beginning, but gradually increased to be similar to that of Comparative Example 1, It can be seen that the conversion rate is relatively high because the final calorific value is high.

Test Example  2: Surface morphology analysis of dental composition SEM for (scanning electron microscope) image analysis

FIG. 3 shows SEM image analysis results of fracture profiles of the compositions prepared according to Example 2, Comparative Example 2, and Comparative Example 4. FIG.

According to FIG. 3 (c), it was confirmed that the composition prepared according to Example 2 had barium glass filler uniformly dispersed in the composition.

Thus, the difference in the interfacial energy between the filler and the resin affects the wettability of the resin, so that air or voids are formed at the interface. However, in Example 2, no significant difference is shown between Comparative Example 2 and Comparative Example 4 , And there is no problem in using the existing filler.

Therefore, it is judged that the dental filler resin has appropriate physical properties such as viscosity and surface energy.

Test Example  3: Compressive Strength and Flexural Strength Analysis

4 shows measurement results of compressive strength and flexural strength of the compositions of Example 2, Comparative Example 2, and Comparative Example 4. Fig.

The specimens for measuring the compressive strength were prepared by filling a cylindrical (Φ x L = 4 x 6 mm) SUS mold with the prepared resin mixture and using a 3M ESPE Elipar ^TM The specimen was irradiated with visible light for 40 seconds on the front and back sides using a S10 spot cure apparatus. For the flexural strength measurement, specimens were filled in a rectangular parallelepiped (H x W x L = 2 x 2 x 25 mm) SUS mold and irradiated with visible light for 20 seconds, The opposite side was also prepared by the same method. The compressive strength of the specimens was measured at Lord Sell 5000N, crosshead speed 1mm / min using a universal testing machine UTM (Universal Testing Machine) Shimadzu AGS-X. The strength was measured. Measurement was carried out according to the international standard test (compression strength: ISO9917, flexural strength: ISO4049).

According to Fig. 4, the dental composition of Example 2 showed an excellent compressive strength as compared with the composition of Comparative Example 4, and the flexural strength was found to be similar.

Test Example 4: Analysis of Shrinkage Resin Comparison

Fig. 5 shows the results of resin shrinkage analysis of the compositions prepared according to Example 2, Comparative Example 2 and Comparative Example 4. Fig. In order to measure the shrinkage rate, 1 mL of the composition was dropped onto a slide glass, covered with a stainless steel plate, and then irradiated with light under a slide glass to microscopically move the sample in the irradiated direction. Using a linear variable differential transducer (LVDT) Were measured.

5, it was confirmed that the composition prepared according to Example 2 had a lower shrinkage rate than the compositions of Comparative Examples 2 and 4.

Therefore, the composition of Example 2 has a relatively low hardening shrinkage ratio as compared with the compositions of Comparative Examples 2 and 4, and it is analyzed that the dimensional stability is high, and the peeling problem upon bonding can be improved.

Test Example 5: Analysis of Water Sorption (Water Sorption)

FIG. 6 shows the results of moisture absorption analysis of the compositions prepared according to Example 2, Comparative Examples 2 and 4.

Measurement specimens for measuring water absorption were prepared by filling a prepared resin mixture with a cylindrical SUS mold (Φ x L = 15 × 1 mm) and using a 3M ESPE Elipar ^™ S10 spot cure apparatus was used to irradiate visible light for 8 seconds around the center and center for 20 seconds, respectively. The water absorption measurement was carried out in accordance with the International Standard Test (ISO4049) as follows. The weight of the prepared specimens was measured, and the specimens were dried until the specimens were uniformly weighed. The weight of M ₀ and was wiped with a specimen of phosphate buffer solution (Phosphate buffer solution, PBS, pH = 7.41) was taken out after 10ml put in a containing vial was allowed to stand for 7 days 37 ℃ oven smooth the sample surface absorptive good paper. Then, it was put in a desiccator for 1 hour, dried and then weighed. At this time, the specimen was dried until the weight of the specimen was constant. This weight is called M ₇ . The water absorption was calculated by the following equation.

WS (/ / mm ³ ) = M ₇ - M ₀ / V

Where V is the initial volume of the sample.

According to Fig. 6, the composition of Example 2 showed lower water absorption than the compositions of Comparative Examples 2 and 4, and the physical properties were improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is possible.

Claims (14)

A bisfuran derivative compound represented by the following structural formula (1).
[Structural formula 1]

In formula 1,
R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected. The method according to claim 1,
R ¹ , R ² and R ³ are the same or different from each other, and each independently represents a hydrogen atom or a methyl group. The method according to claim 1,
Wherein the compound represented by the structural formula (1) is a compound represented by the following formula (1).
[Chemical Formula 1]

The method according to claim 1,
Wherein said bisfuran derivative compound is used as a dental material. As shown in Reaction Scheme 1 below,
Reacting compound 1 with compound 2 to produce compound 3 (step a);
Reacting compound 3 to produce compound 4 (step b);
Reacting compound 4 to prepare compound 5 (step c); And
Reacting compound 5 to prepare compound 6 (step d); To
≪ / RTI >
[Reaction Scheme 1]

In the above Reaction Scheme 1,
R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected,
R ⁴ is a methyl group. 6. The method of claim 5,
Wherein R ¹ , R ² and R ³ are the same or different and are each independently a hydrogen atom or a methyl group. 6. The method of claim 5,
Step d is as in Scheme 2,
Wherein the reaction of Reaction Scheme 2 is carried out by reacting Compound 5 with Compound 7 to prepare Compound 6.
[Reaction Scheme 2]

R ¹ , R ² and R ³ are the same or different from each other and each independently represents a hydrogen atom, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, a C 2 to C 6 alkynyl group, a C 5 to C 6 cycloalkyl group, and a C 6 to C 10 aryl group Any one selected. A bisfuran derivative compound of claim 1;
Initiator; And
A filler;
A bisfuran derivative composition for use as a dental filler. 9. The method of claim 8,
100 parts by weight of the compound of claim 1;
0.1 to 5 parts by weight of the initiator; And
50 to 500 parts by weight of the filler;
≪ RTI ID = 0.0 > bisfuran < / RTI > derivative composition. 9. The method of claim 8,
Wherein the initiator is a photopolymerization initiator. 9. The method of claim 8,
Wherein the initiator is selected from the group consisting of camphoquinone, ethyl-4-dimethylamino benzoate, tertiary amine initiator, diphenyl iodonium chloride, diphenyl iodonium hexafluorophosphate, diphenyl Iodonium tetrafluoroborate, tolylcumyl iodonium tetrakis (pentafluorophenyl) borate, acyl, bisacylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis 2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2- 2-methyl-1-phenylpropan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy- Ethyl 2,4,6-trimethylbenzyl phenylphosphinate, and mixtures thereof. 9. The method of claim 8,
Wherein the filler is selected from the group consisting of barium glass fillers, barium aluminosilicates, synthetic amorphous silicas, crystalline silicas, barium silicates, barium borosilicates, barium fluoroaluminosilicates, But are not limited to, barium fluoroaluminoborosilicate, barium aluminoborosilicate, strontium silicate, strontium borosilicate, strontium aluminoborosilicate, calcium silicate, At least one selected from alumino silicate, silicon nitrides, titanium dioxide, calcium hydroxyapatite, zirconia, and bioactive glass may be used. Characterized in that the bisfuran derivative group Honesty. delete A dental filler prepared by curing the bisfuran derivative composition of claim 8.

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