HIGHLY FUNCTIONAL NATURAL MATERIAL-DERIVED EPOXY RESIN, PREPARATION METHOD THEREFOR, AND EPOXY RESIN CURING COMPOSITION USING SAME

Abstract

Disclosed are a highly functional natural material-derived epoxy resin, a preparation method therefor, and an epoxy resin curing composition using the same. The highly functional natural material-derived epoxy resin represented by chemical formula 1 is obtained by reacting a compound, represented by chemical formula 2, and epichlorohydrin (ECH), which is obtained by using glycerin as a starting material, in the presence of a hydroxide salt.

Claims

1.-3. (canceled)

4. A natural ingredient-derived epoxy resin composition with water debonding property comprising: a natural material-derived epoxy resin represented by the following Formula 1, the natural material-derived epoxy resin being obtained by reacting a compound represented by Formula 2 with epichlorohydrin (ECH) obtained from glycerin as a starting material in the presence of a hydroxide salt; and a polyamide curing agent represented by the following formula 4: ##STR00009## wherein n is a natural number of 0 to 300, ##STR00010## wherein R and R′ are each independently H or CxHy, in which x and y are a natural number of 1 to 30.

5. A natural ingredient-derived epoxy resin composition with anti-fog property comprising: a natural material-derived epoxy resin represented by the following Formula 1, the natural material-derived epoxy resin being obtained by reacting a compound represented by Formula 2 with epichlorohydrin (ECH) obtained from glycerin as a starting material in the presence of a hydroxide salt; and a polyetheramine curing agent represented by the following formula 5: ##STR00011## wherein n is a natural number of 0 to 300, ##STR00012## wherein n is a natural number of 1 to 100.

6. (canceled)

7. A method of preparing the natural material-derived epoxy resin, the method comprising: a first step including mixing 550 to 650 parts by weight of epichlorohydrin (ECH) obtained from glycerin as a starting material with 100 parts by weight of a compound represented by the following Formula 2, dissolving the mixture at an elevated temperature of 60 to 75° C., adding 5 to 11 parts by weight of sodium hydroxide (NaOH) to 100 parts by weight of a compound represented by the following Formula 2 and conducting preliminary reaction for 2 to 4 hours: a second step including conducting main reaction of the reactants of the first step at a temperature of 60 to 75° C. and at a reduced pressure of 180 to 250 torr, the main reaction being carried out for 3 to 6 hours by adding 44 to 60 parts by weight of sodium hydroxide (NaOH) to 100 parts by weight of the compound represented by the following Formula 2; a third step including standing the reaction solution after reaction of the second step, separating the supernatant by reverse aliquoting and filtering the same; and a fourth step including collecting epichlorohydrin from the filtrate. ##STR00013## wherein n is a natural number of 0 to 300, ##STR00014##

8. (canceled)

9. (canceled)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0061] The accompanying drawings are included to provide a further understanding of the present invention, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the present invention and, together with the description, serve to explain principles of the present invention. In the drawings, FIGS. 1 to 5 show GPC patterns of epoxy resins produced in Examples 1 to 4, and Comparative Example 1.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0062] Hereinafter, the present invention will be described with reference to the following Examples, but the present invention is not limited thereto.

Example 1

[0063] 100 g of isosorbide and 633 g of epichlorohydrin were fed to a 1,000 mL round bottom flask with a cooling tube equipped with a decanter, a stirrer and a nitrogen inlet, and dissolved while heating to 63° C. After the solution in the system was thoroughly dissolved, 11 g of a 50% aqueous sodium hydroxide solution was quantitatively injected for 2 hours to conduct preliminary reaction. Then, 109 g of a 50% aqueous sodium hydroxide solution was quantitatively injected at 65° C. and a reduced pressure of 120 torr over 200 minutes to conduct main reaction.

[0064] Water produced during main reaction was continuously removed via the decanter. After completion of main reaction, the reactant was filtered under a reduced pressure with a filter paper and the remaining resin was washed with acetone. The temperature and pressure of the filtered reactant were slowly elevated to 150° C. and 5 torr, and unreacted epichlorohydrin was collected to obtain an epoxy resin of Formula 1 according to the present invention.

[0065] In this case, the produced epoxy resin has an epoxy equivalent weight of 184 g/eq, a viscosity of 16,221 cps at 25° C. and a yield of 98% with respect to the theoretical resin value. The molecular weight distribution (GPC) of the epoxy resin is shown in FIG. 1. An area corresponding to a retention time of 39 minutes is epoxy at n=0 and the content thereof is 32%.

Example 2

[0066] 100 g of isosorbide and 633 g of epichlorohydrin were fed to a 1,000 mL round bottom flask with a cooling tube equipped with a decanter, a stirrer and a nitrogen inlet, and dissolved while heating to 75° C. After the solution in the system was thoroughly dissolved, 11 g of a 50% aqueous sodium hydroxide solution was quantitatively injected for 4 hours to conduct preliminary reaction. Then, 109 g of a 50% aqueous sodium hydroxide solution was quantitatively injected at 75° C. and a reduced pressure of 220 torr over 200 minutes to conduct main reaction.

[0067] Water produced during main reaction was continuously removed via the decanter. After completion of main reaction, the reactant was filtered under a reduced pressure with a filter paper and the remaining resin was washed with acetone. The temperature and pressure of the filtered reactant were slowly elevated to 150° C. and 5 torr, and unreacted epichlorohydrin was collected to obtain an epoxy resin of Formula 1 according to the present invention.

[0068] In this case, the produced epoxy resin has an epoxy equivalent weight of 182 g/eq, a viscosity of 8,266 cps at 25° C. and a yield of 98% with respect to the theoretical resin value. The molecular weight distribution (GPC) of the epoxy resin is shown in FIG. 2. An area corresponding to a retention time of 39 minutes is epoxy at n=0 and the content thereof is 34%.

Example 3

[0069] 100 g of isosorbide and 633 g of epichlorohydrin were fed to a 1,000 mL round bottom flask with a cooling tube equipped with a decanter, a stirrer and a nitrogen inlet, and dissolved while heating to 75° C. After the solution in the system was thoroughly dissolved, 11 g of a 50% aqueous sodium hydroxide solution was quantitatively injected for 2 hours to conduct preliminary reaction. Then, 120 g of a 50% aqueous sodium hydroxide solution was quantitatively injected at 75° C. and a reduced pressure of 220 torr over 7 hours to conduct main reaction.

[0070] Water produced during main reaction was continuously removed via the decanter. After completion of main reaction, the reactant was filtered under a reduced pressure with a filter paper and the remaining resin was washed with acetone. The temperature and pressure of the filtered reactant were slowly elevated to 150° C. and 5 torr, and unreacted epichlorohydrin was collected to obtain an epoxy resin of Formula 1 according to the present invention.

[0071] In this case, the produced epoxy resin has an epoxy equivalent weight of 168 g/eq, a viscosity of 4,367 cps at 25° C. and a yield of 98% with respect to the theoretical resin value. The molecular weight distribution (GPC) of the epoxy resin is shown in FIG. 3. An area corresponding to a retention time of 39 minutes is epoxy at n=0 and the content thereof is 42%.

Example 4

[0072] 100 g of isosorbide and 633 g of epichlorohydrin were fed to a 1,000 mL round bottom flask with a cooling tube equipped with a decanter, a stirrer and a nitrogen inlet, and dissolved while heating to 75° C. After the solution in the system was thoroughly dissolved, 11 g of a 50% aqueous sodium hydroxide solution was quantitatively injected for 2 hours to conduct preliminary reaction. Then, 108 g of a 50% aqueous sodium hydroxide solution was quantitatively injected at 75° C. and a reduced pressure of 220 torr over 200 minutes to conduct main reaction.

[0073] Water produced during main reaction was continuously removed via the decanter. After completion of main reaction, the reactant was filtered under a reduced pressure with a filter paper and the remaining resin was washed with acetone. The temperature and pressure of the filtered reactant were slowly elevated to 150° C. and 5 torr, and unreacted epichlorohydrin was collected to obtain an epoxy resin of Formula 1 according to the present invention.

[0074] In this case, the produced epoxy resin has an epoxy equivalent weight of 173 g/eq, a viscosity of 3,775 cps at 25° C. and a yield of 98% with respect to the theoretical resin value. The molecular weight distribution (GPC) of the epoxy resin is shown in FIG. 4. An area corresponding to a retention time of 39 minutes is epoxy at n=0 and the content thereof is 39%.

Comparative Example 1

[0075] 100 g of isosorbide and 1,266 of epichlorohydrin were fed to a 1,000 mL round bottom flask with a cooling tube equipped with a decanter, a stirrer and a nitrogen inlet, and dissolved while heating to 115° C. After the solution in the system was thoroughly dissolved, 120 g of a 50% aqueous sodium hydroxide solution was quantitatively injected for 12 hours to conduct preliminary reaction.

[0076] In this case, the produced epoxy resin has an epoxy equivalent weight of 306 g/eq, a viscosity of 13,365 cps at 50° C. and a yield of 98% with respect to the theoretical resin value. The molecular weight distribution (GPC) of the epoxy resin is shown in FIG. 5. An area corresponding to a retention time of 39 minutes is epoxy at n=0 and the content thereof is 34%.

Application Example 1 (Molding for Heavy Electric Equipment)

[0077] An isosorbide epoxy resin produced in Example 4 as an epoxy resin, hexahydrophthalic anhydride (hereinafter, referred to as “HHPA”), which is an acid anhydride curing agent, as a curing agent, and benzyldimethylamine (hereinafter, referred to as “BDMA”) as a curing accelerator were mixed to prepare an epoxy resin composition (A) of the present invention and the epoxy resin composition (A) was cured at 130° C. for 14 hours.

Comparative Example 2 (Preparation of General Bisphenol A-Type Epoxy Resin Composition and Cured Substance Thereof)

[0078] A cured epoxy resin was prepared in the same manner as in Application Example 1, except that YD-128 (available from Kukdo chemical Co., Ltd.) was used as an epoxy resin.

[0079] Ingredients of epoxy resin compositions of Application Example 1 and Comparative Example 2, and contents thereof are summarized in Table 1.

TABLE-US-00001 TABLE 1 Application Comparative Example 1 Example 2 (content g) (content g) Epoxy resin Example 4 epoxy YD-128 (100) (100) Curing agent 85 76 (HHPA) Curing accelerator 1 1 (BDMA)

[0080] The heat resistance, absorbance, tensile strength and tensile modulus, flexural strength and flexural modulus of the cured epoxy resin shown in Table 1 were measured and shown in the following Table 2.

TABLE-US-00002 TABLE 2 Application Comparative Example 1 Example 2 Curing agent HHPA Curing accelerator BDMA Tg (DSC,° C.) 108.4 134.5 Flexural strength (MPa) 114.2 134.7 Flexural modulus (MPa) 2811.9 2833.9 Tensile strength (MPa) 80.3 38.1 Tensile modulus (MPa) 3146.3 3866.3 Elongation (%) 5.3 1.5 Absorbance (%) 0.55 0.21 Measurement of heat resistance: Tg (glass transition temperature) was measured by DSC analysis. Measurement of absorbance: Variation in weight after storing in 25° C. distilled water for 72 hours was measured. Measurement of tensile strength and tensile modulus: specimen was prepared in accordance with ASEM 638, the width and thickness of the specimen were measured with a micrometer and tensile strength and tensile modulus were measured using a U.T.M tester. Measurement of flexural strength and flexural modulus: a specimen was prepared, the width and thickness of the specimen were measured with a micrometer, and flexural strength and flexural modulus were measured using a U.T.M tester.

[0081] As can be seen from Table 2, when the epoxy resin according to the present invention is used, moldings that exhibit similar flexural strength, but 3 times or higher elongation, as compared to petroleum-derived bisphenol A-type epoxy can be produced.

Application Example 2 (Adhesives Debonded in Water)

[0082] The isosorbide epoxy resin produced in Example 4 as an epoxy resin was mixed with G-5022X70 (available from Kukdo chemical Co., Ltd.), which is a polyamide curing agent, as a curing agent, to form a thin film with a thickness of 150 μm on an iron substrate, thereby producing an epoxy resin composition (B) of the present invention. The epoxy resin composition (B) was cured at room temperature for 24 hours and at 80° C. for 2 hours.

Comparative Example 3 (Preparation of General Bisphenol A-Type Epoxy Resin Composition and Cured Substance Thereof)

[0083] A cured epoxy resin was prepared in the same manner as in Application Example 2, except that YD-128 (available from Kukdo chemical Co., Ltd.) was used as an epoxy resin.

[0084] Ingredients of epoxy resin compositions of Application Example 2 and Comparative Example 3, and contents thereof are summarized in Table 3.

TABLE-US-00003 TABLE 3 Application Comparative Example 2 Example 3 (content g) (content g) Epoxy resin Example 4 YD-128 epoxy (100) (100) Curing agent 144.5 134.4 (G-5022X70)

[0085] The heat resistance, absorbance, adhesive strength and water debonding test of cured epoxy resins shown in Table 3 were measured and shown in the following Table 4.

TABLE-US-00004 TABLE 4 Application Comparative Example 2 Example 3 Curing agent G-5022X70 Tg (DSC,° C.) 64.5 66.7 Absorbance (%) 33 1 Adhesion (cross cut) 100/100 100/100 Water debonding test 30 sec or less 7 days or longer (70° C.) Measurement of heat resistance: Tg (glass transition temperature) was measured by DSC analysis. Measurement of absorbance: Variation in weight after storing in 25° C. distilled water for 72 hours was measured. Measurement of adhesive strength: a line was drawn with a cutter on a coated substrate to prepare a 100-square grid, and immediately after a sharp tape was attached to the line, the tape was peeled off and then the number of squares remaining on the substrate was recorded (ASTM D3359) Water debonding test: after x-cut was made on a coated substrate and immersed in 70° C. water, a time by during which a coating film was peeled off was measured.

[0086] As can be seen from Table 4, in a case in which the epoxy resin according to the present invention was used, as compared to petroleum-derived and based bisphenol A-type epoxy, the epoxy resin exhibited similar adhesive strength, but exhibited rapid deterioration in adhesive strength when immersed in hot water. Accordingly, based on this property, the epoxy resin was applicable as an adhesive agent for debonding an article due to rapidly deteriorated adhesive strength in wet environments while requiring excellent adhesive strength in dry environments.

Application Example 3 (Anti-Fog Absorbance Coating)

[0087] The isosorbide epoxy resin produced in Example 4 as an epoxy resin was mixed with polyoxyalkylene triamine (JEFFAMINE T-403, available from Huntsman Specialty Chemicals Corp.) as a curing agent, to form a thin film with a thickness of 150 μm on a glass substrate, thereby producing an epoxy resin composition (C) of the present invention. The epoxy resin composition (C) was cured at room temperature for 24 hours and at 80° C. for 2 hours.

Comparative Example 4 (Preparation of General Aliphatic Polyglycidyl Ether Composition and Cured Substance Thereof)

[0088] A cured epoxy resin was prepared in the same manner as in Comparative Example 3, except that 57 g of an aliphatic polyglycidyl ether compound (DE-211, available from Hajin chemtech Co., Ltd.) was used as an epoxy resin.

[0089] Absorbance and fog resistance test was conducted by standing a specimen at 20° C. and at a relative humidity of 50% for one hour and then placing the specimen above 40° C. warm water and measuring a time by which penetration distortion by a water film was considered to occur. Commonly, a soda lime glass with no anti-fogging treatment was fogged within 2 to 5 seconds. An anti-fog property of 50 seconds or longer was practically required to prevent fogging. Preferably, an anti-fog property was 70 seconds or longer, more preferably 100 seconds or longer.

[0090] Ingredients of epoxy resin compositions of Application Example 3 and Comparative Example 4, and contents and anti-fog property thereof are summarized in Table 5.

TABLE-US-00005 TABLE 5 Application Comparative Example 3 Example 4 (content g) (content g) Epoxy resin Example 4 DE-211 epoxy (100) (100) Curing agent 42.3 57 (G-5022X70) Absorbance anti- 600 sec 180 sec fog property or more (second)

[0091] As can be seen from Table 5, the epoxy resin according to the present invention exhibited 3 times or more superior properties in absorbance anti-fog property test, as compared to conventional aliphatic polyglycidyl ether compounds, thus being applicable to anti-fog films.

[0092] The natural material-derived isosorbide epoxy represented by Formula 1 according to the present invention can replace a bisphenol A-based epoxy substance, and uses glycerin-derived epichlorohydrin and is thus derived from 100% natural ingredients, rather than petroleum resources, thus advantageously responding to a high-price oil age and reducing generation of irreversible carbon dioxide and thus advantageously being eco-friendly.

[0093] In addition, the present invention has advantages in that natural material-derived epoxy with low viscosity can be produced under optimum process conditions, thereby advantageously realizing equivalent or superior physical properties of cured epoxy to conventional petroleum resource-derived epoxies, despite using natural ingredients as ingredients.