US20170253692A1 - Highly functional natural material-derived epoxy resin, preparation method therefor, and epoxy resin curing composition using same - Google Patents

Highly functional natural material-derived epoxy resin, preparation method therefor, and epoxy resin curing composition using same Download PDF

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US20170253692A1
US20170253692A1 US15/316,804 US201515316804A US2017253692A1 US 20170253692 A1 US20170253692 A1 US 20170253692A1 US 201515316804 A US201515316804 A US 201515316804A US 2017253692 A1 US2017253692 A1 US 2017253692A1
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epoxy resin
weight
derived
epichlorohydrin
natural
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Hye Seung Lee
Jae Il Kim
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Kukdo Chemical Co Ltd
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Kukdo Chemical Co Ltd
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Assigned to KUKDO CHEMICAL CO., LTD. reassignment KUKDO CHEMICAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIM, JAE IL, LEE, HYE SEUNG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen

Definitions

  • the present invention relates to a highly functional natural material-derived epoxy resin, a method of preparing the same and an epoxy resin curing composition containing the same. More specifically, the present invention relates to a highly functional natural material-derived epoxy resin prepared by reaction of isosorbide derived from sugar (carbohydrate) with epichlorohydrin (ECH) derived from glycerin, a method of preparing the same and an epoxy resin curing composition containing the same.
  • ECH epichlorohydrin
  • bisphenol-based epoxy resins are widely used in a variety of fields including coating, adhesive agents, electrical and electronic engineering, and civil engineering and construction, due to advantages of excellent adhesive strength, mechanical properties and chemical resistance, and less shrinkage deformation during curing.
  • Chemical materials containing the bisphenol-based epoxy resin as a main ingredient are derived from petroleum and produce chemicals harmful to human such as endocrine disruptors during the production and use.
  • This research is conducted by reaction at 115° C. for 12 hours using ECH derived from propylene, which is a petroleum resource, thus having problems of low economic efficiency and industrial inapplicability.
  • the inventors of the present invention suggested a method of preparing a 100% biomass-derived epoxy resin by reacting carbohydrate-derived isosorbide with glycerin-derived ECH under optimum reaction conditions.
  • n is an integer of 0 to 300.
  • the compound represented by Formula 1 according to the present invention is a natural material-derived isosorbide epoxy compound having a molecular structure in which two epoxy groups are linked to an isosorbide skeleton.
  • the natural material-derived isosorbide used for the method of the present invention has a structure represented by the following Formula 2:
  • carbohydrate natural material-derived isosorbide (Formula 2) is used as a basic skeleton so that it is utilized in eco-friendly application fields, food and human-contact application fields, instead of bisphenol A, which is derived from a petroleum resource and issued as an endocrine disruptor.
  • the method of preparing Formula 1 according to the present invention may include the following steps: (Reaction Scheme 2)
  • the compound represented by Formula 2 may be derived from a carbohydrate polymer. Specifically, the compound represented by Formula 2 may be prepared from the carbohydrate polymer, as depicted by the following Reaction Scheme 3.
  • a carbohydrate polymer such as cellulose present in an amount of about 30 to about 40% in a terrestrial plant is extracted and subjected to hydrolysis or saccharification including treatment with an enzyme to obtain a hexose compound, an aldehyde group of the hexose compound is reduced by hydrogenation or the like to prepare hexane-1,2,3,4,5,6-hexol having six hydroxyl groups, and the compound is subjected to cyclization using dehydrogenation under the condition of an acidic catalyst to obtain a compound represented by Formula 2 as a bicyclic compound in which two five-numbered rings are fused.
  • the first step is carried out by reacting isosorbide (Formula 2) with epichlorohydrin in the presence of a hydroxide salt, which provides reaction conditions for producing chlorohydrins by reacting isosorbide (Formula 2) with epichlorohydrin.
  • the hydroxide salt is composed of an alkali metal and a hydroxyl group and, specifically, for example includes one or more selected from LiOH, NaOH, KOH and the like, but the present invention is not limited thereto.
  • epichlorohydrin is preferably present in an amount of 200 to 1,300 parts by weight, more preferably 550 to 650 parts by weight, with respect to 100 parts by weight of the compound represented by Formula 2.
  • sodium hydroxide is preferably present in an amount of 4 to 13 parts by weight, more preferably 5 to 11 parts by weight, with respect to 100 parts by weight of the compound represented by Formula 2.
  • hydroxide salt is present in an amount of less than 4 parts by weight or higher than 13 parts by weight, with respect to 100 parts by weight of the compound represented by Formula 2, there is a drawback of high side reactant content.
  • a reaction time of the first step is preferably 0.5 to 6 hours, more preferably 2 to 4 hours.
  • the reaction time is shorter than 0.5 hours, there is a drawback of high polymer content and when the reaction time is longer than 6 hours, there is a drawback of bad color of final products.
  • the reaction time of the first step is preferably 30 to 100° C., more preferably 60 to 90° C.
  • the reaction temperature is lower than 60° C., there is a drawback in which polymerization proceeds and molecular weight increases, and when the reaction temperature is higher than 90° C., there is a drawback of increased by-products.
  • This step includes reacting chlorohydrin with epichlorohydrin at a reduced pressure in the presence of a hydroxide salt, which provides reaction conditions enabling cyclization of epichlorohydrin to produce an epoxy group.
  • the hydroxide salt is preferably present in an amount of 40 to 70 parts by weight, more preferably 44 to 60 parts by weight, with respect to 100 parts by weight of the compound represented by Formula 2.
  • the hydroxide salt is present in an amount lower than 40 parts by weight, with respect to 100 parts by weight of the compound represented by Formula 2, there is a drawback in that by-products increase and, when the hydroxide salt is present in an amount higher than 70 parts, a part of the hydroxide salt remains unreacted in the resin, disadvantageously increasing a pH of the resin.
  • a reaction time of the second step is preferably 2 to 12 hours, more preferably 3 to 6 hours.
  • the reaction time is shorter than 2 hours, there is a drawback of high polymer content and when the reaction time is longer than 12 hours, there is a drawback of increased by-products.
  • the reaction time of the second step is preferably 30 to 100° C., more preferably 60 to 90° C.
  • the reaction temperature is lower than 60° C., there is a drawback in that polymerization proceeds and molecular weight increases, and when the reaction temperature is higher than 90° C., there is a drawback of increased by-products.
  • the reduced pressure of the second step is preferably 300 to 100 torr, more preferably 180 to 250 torr.
  • excess water remains in the system, thus disadvantageously interrupting reaction and, when the reduced pressure is higher than 100 torr, reflux increases, thus disadvantageously causing increased polymer content.
  • the third step includes stopping stirring and standing for a predetermined time, and then collecting the supernatant using a pump and filtering the same to remove by-products remaining in the resin.
  • the fourth step includes collecting epichlorohydrin remaining unreacted with the compound represented by Formula 2.
  • collection is preferably carried out at 160° C. and 5 to 20 torr.
  • the present invention provides epoxy resin curing compositions (A, B and C) which include the compound represented by Formula 1 and a curing agent.
  • the curing agent for the epoxy resin curing composition A may be an acid anhydride curing agent represented by the following Formula 3.
  • the curing agent may include hexahydrophthalic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, anhydrous methyl nadic acid(methyl nadic anhydride), dodecenyl anhydride succinic acid, maleic anhydride, pyromellitic anhydride and anhydrous chlorendic acid and the like.
  • R and R′ are each independently H or CxHy (in which x and y are a natural number of 1 to 30).
  • polycarboxylic acid anhydride having no aromatic nucleus may be, for example, succinic acid anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methyl hexahydrophthalic anhydride or the like.
  • the acid anhydride curing agent that can be used in the present invention may be used alone or in combination of two or more thereof.
  • the curing agent for the epoxy resin curing compositions B and C may include a compound having two or more reactive groups reacting with an epoxy group, such as polyamine, polycarboxylic acid anhydride, polyamide and polythiol, or a curing catalyst such as tertiary amine, imidazole, a Lewis acid, an onium salt, dicyandiamide, organic acid dihydrazide or porphine.
  • an epoxy group such as polyamine, polycarboxylic acid anhydride, polyamide and polythiol
  • a curing catalyst such as tertiary amine, imidazole, a Lewis acid, an onium salt, dicyandiamide, organic acid dihydrazide or porphine.
  • the compound having two or more reactive groups is preferably polyamine having no aromatic nucleus or polycarboxylic acid anhydride
  • the curing catalyst is preferably tertiary amine, imidazole, porphine or an allyl sulfonium salt.
  • the polyamine is preferably polyamine having two to four amino groups
  • the polycarboxylic acid anhydride is preferably dicarboxylic acid anhydride, tricarboxylic acid anhydride and tetra carboxylic acid anhydride.
  • the polyamine having no aromatic nucleus is preferably an aliphatic polyamine compound or an alicyclic polyamine compound.
  • the polyamine may specifically include ethylenediamine, trimethylene tetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylene polyamine, isophorone diamine, benzenediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro (5.5) undecane or the like.
  • the polyoxyalkylene polyamine is a polyamine having a structure in which a hydroxyl group of polyoxyalkylene polyol is replaced by an amino group and for example includes a compound having two to four amino groups.
  • the polyamide curing agent used in the present invention may be a compound represented by the following Formula 4.
  • R and R′ are each independently H or CxHy (in which x and y are a natural number of 1 to 30) and n is a natural number of 1 to 100.
  • the epoxy resin of the present invention may include a polyether amine curing agent represented by the following Formula 5.
  • R and R′ are each independently H or CxHy (in which x and y are a natural number of 1 to 30) and n is a natural number of 1 to 100.
  • the polyether amine may for example include ⁇ -(2-aminoethylmethyl) ⁇ -(2-aminomethylethoxy) (JEFFAMINE® D-230, D-400), triethyleneglycoldiamine and an oligomer thereof (JEFFAMINE® XTJ-504, JEFFAMINE® XTJ-512), poly(oxy(methyl-1,2-ethanediyl)), ⁇ , ⁇ ′-(oxydi-2,1-ethanediyl)bis ( ⁇ -(isaaminomethylethoxy)) (JEFFAMINE® XTJ-511), bis(3-aminopropyl)polytetrahydrofuran 350, bis(3-aminopropyl)polytetrahydrofuran 750, poly(oxy(methyl-1,2-ethanediyl)), ⁇ -hydro- ⁇ -(2-aminomethylethoxy) ether and 2-ethyl-2-(hydroxymethyl)-1,
  • the epoxy resin curing compositions (A, B and C) of the present invention may include a curing accelerator.
  • the curing accelerator may be any tertiary amine and may more preferably include one or more selected from the group consisting of dimethylaminomethyl phenol, tris(dimethylaminomethyl)phenol, and benzyldimethylamine. In this case, it is possible to maximize curing rate and curing properties.
  • the epoxy resin curing compositions (A, B and C) of the present invention may further include an inorganic filler. It is effective that the inorganic filler includes at least one of silica, alumina and talc.
  • the epoxy resin curing compositions (A, B and C) of the present invention may further include a variety of additives including a release agent such as a silane coupling agent, stearic acid, palmitic acid, zinc stearate and calcium stearate, and a pigment.
  • a release agent such as a silane coupling agent, stearic acid, palmitic acid, zinc stearate and calcium stearate, and a pigment.
  • the epoxy resin curing compositions (A, B and C) of the present invention can be produced by thoroughly mixing the mixture in an extruder, a kneader or a roll and then homogenizing the same.
  • a mix ratio between polyepoxide and the curing agent is preferably an equivalent ratio of the reactive group of the curing agent with respect to epoxy, of about 0.8 to about 1.2. At this ratio, physical properties of the cured substance product may be readily deteriorated.
  • An epoxy-based resin including a combination of the polyepoxy group and a curing agent may be blended with a reactive additive or a non-reactive additive.
  • the reactive additive may include a compound having one reactive group reacted with epoxy such as alkyl monoamine, a coupling agent having an epoxy group or an amino group, or the like.
  • epoxy-based resin including the polyepoxy, the curing agent and the additive polyepoxide is preferably present in an amount of 4 to 80 wt % with respect to the epoxy-based resin.
  • the natural material-derived isosorbide epoxy represented by Formula 1 can replace a conventional harmful 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.
  • 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-derived epoxy substances, despite using natural ingredients as ingredients.
  • FIGS. 1 to 5 show GPC patterns of epoxy resins produced in Examples 1 to 4, and Comparative Example 1.
  • 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 .
  • 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 .
  • 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 .
  • 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 .
  • 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 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.
  • HHPA hexahydrophthalic anhydride
  • BDMA benzyldimethylamine
  • 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.
  • 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.
  • 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 ⁇ m 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.
  • 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.
  • 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.
  • the epoxy resin according to the present invention 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.
  • 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 ⁇ m 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.
  • 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.
  • DE-211 an aliphatic polyglycidyl ether compound
  • 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.
  • 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.
  • an anti-fog property was 70 seconds or longer, more preferably 100 seconds or longer.
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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KR1020140091096A KR101660237B1 (ko) 2014-07-18 2014-07-18 고기능성 천연원료 유래 에폭시 수지 및 그의 제조방법과 이를 이용한 에폭시수지 경화 조성물.
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PCT/KR2015/005742 WO2016010261A1 (ko) 2014-07-18 2015-06-09 고기능성 천연원료 유래 에폭시 수지 및 그의 제조방법과 이를 이용한 에폭시수지 경화 조성물

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CN109851761A (zh) * 2019-01-09 2019-06-07 中国林业科学研究院林产化学工业研究所 蓖麻油基可双重交联活性树脂单体及其制备方法
US20200123308A1 (en) * 2015-08-13 2020-04-23 Roquette Freres Use of a composition of low-viscosity bis-anhydrohexitol ethers as a reactive diluent for crosslinkable resin, adhesive, coating and matrix compositions for composites
FR3111895A1 (fr) 2020-06-30 2021-12-31 Roquette Freres Procédé d’obtention de polyépoxydes biosourcés aux propriétés améliorées
US11958253B2 (en) 2017-12-21 2024-04-16 Elantas Europe S.R.L. Use of isosorbide

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US20180230261A1 (en) 2018-08-16
JP2017526752A (ja) 2017-09-14
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CN107075084B (zh) 2019-06-21
KR101660237B1 (ko) 2016-09-27

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