Synthesis reaction product composition of isosorbide-based epoxy compound, coating composition containing same, and preparation method of isosorbide-based epoxy compound

Abstract

The invention relates to a synthesis reaction product composition of an isosorbide epoxy compound, a coating composition comprising the synthesis reaction product composition, and a preparation method of the isosorbide epoxy compound. The present invention relates to a synthesis reaction product composition of an isosorbide-based epoxy compound having low viscosity and high purity, a coating composition comprising the same, and a method for preparing an isosorbide-based epoxy compound having improved yield.

Description

Technical Field

[0001] This invention claims the benefit of patent application No. 10-2023-0108493 filed with the Korean Intellectual Property Office on August 18, 2023, the entire contents of which are incorporated herein by reference.

[0002] This invention relates to a synthesis reaction product composition of isosorbide-based epoxy compounds with low viscosity and high purity, a coating composition including the same, and a method for preparing isosorbide-based epoxy compounds with improved yield. Background Technology

[0003] Typically, polymer compounds are prepared using raw materials derived from petroleum resources. However, in recent years, the depletion of petroleum resources has raised concerns, creating an urgent need for polymer resins that utilize raw materials obtained from biomass resources such as plants.

[0004] In particular, as environmental problems arising from the use of petroleum resources intensify, the sustainability and environmental advantages of biomass resources become increasingly prominent. Against this backdrop, the development of biomass-based monomer and polymer production technologies has become a crucial issue of common concern to both academia and industry. Especially given the potential for increased carbon dioxide emissions and accumulation to trigger climate change such as global warming, there is a need to develop polymer resins using plant-derived monomers as raw materials, which have extremely low carbon emissions during the preparation process.

[0005] There is an urgent need to develop new structural polymers with novel carbon skeletons that can balance the sustainability and environmental advantages of biomass resources while possessing mechanical and physical properties comparable to or better than those of petroleum-based polymers and ensuring low glass transition temperatures.

[0006] In this respect, isosorbide (1,4:3,6-dianhydrohexitol) differs from existing raw materials based on the petrochemical industry; it is derived from plant resources such as corn and potatoes. When isosorbide is used as a monomer for engineering plastics such as polycarbonate, it exhibits excellent thermal properties due to its robust structure.

[0007] Methods for preparing epoxy resins by reacting isosorbide with epichlorohydrin have been disclosed in various ways and documented in numerous publications. However, when prepared according to most of the methods described in the literature, it is synthesized in the form of isosorbide diglycidyl ether (n=0) rather than in the form of n=1 or more, resulting in higher viscosity. For example, in existing publications using commercially available caustic soda synthesis methods, most exhibit a viscosity of over 10,000 cps at room temperature.

[0008] Furthermore, when isosorbide-based epoxy resins are prepared according to the methods described in most literature, the yield is difficult to exceed 90% because the epoxy resin remaining in the salt layer is difficult to recover further.

[0009] Therefore, it is necessary to develop a novel preparation method for isosorbide diglycidyl ether (n=0) with high content, low viscosity and excellent yield. Summary of the Invention

[0010] Technical issues

[0011] The present invention aims to solve the problems in the prior art as described above, and provides a synthetic reaction product composition of isosorbide-based epoxy compounds with sustainable and environmental advantages of biomass resources, low viscosity and high purity, a coating composition including the isosorbide-based epoxy compounds, and a method for preparing isosorbide-based epoxy compounds with improved yield.

[0012] However, the technical problem to be solved by the present invention is not limited to the technical problems mentioned above. Other technical problems not mentioned can be clearly understood by those skilled in the art from the following description.

[0013] Solution to the problem

[0014] To achieve the above objectives, one embodiment of the present invention provides a synthetic reaction product composition of isosorbide-based epoxy compounds, comprising: an isosorbide-based epoxy compound represented by the following chemical formula 1; and a hydrolyzable chlorine component; wherein the hydrolyzable chlorine component is less than 5000 ppm.

[0015] [Chemical Formula 1]

[0016]

[0017] In the above chemical formula 1,

[0018] R is H or ,

[0019] n is an integer from 0 to 100.

[0020] Another embodiment of the present invention provides a method for preparing isosorbide-based epoxy compounds, comprising: step (S10), reacting isosorbide, an organohalide and a basic compound in the presence of a phase transfer catalyst to obtain a reaction product comprising a salt and an isosorbide-based epoxy compound; step (S30), filtering the salt in a candle filter device to obtain a filtrate; and step (S50), removing the organohalide from the filtrate to obtain the isosorbide-based epoxy compound.

[0021] Invention Effects

[0022] The isosorbide-based epoxy compound synthesis reaction product composition according to an embodiment of the present invention, by including less than 5000 ppm of hydrolyzable chlorine, can provide an isosorbide-based epoxy compound synthesis reaction product composition with low viscosity and high purity.

[0023] According to an embodiment of the present invention, the method for preparing isosorbide-based epoxy compounds utilizes a candle filter device to filter salt, thereby recovering residual isosorbide-based epoxy compounds and thus enabling the preparation of isosorbide-based epoxy compounds in high yield.

[0024] According to one embodiment of the present invention, the coating composition, through a synthetic reaction product composition comprising the above-mentioned isosorbide-based epoxy compounds, can provide an environmentally friendly coating composition with excellent coating workability and physical properties. Detailed Implementation

[0025] In this specification, when a part is described as "including" a certain constituent element, it does not exclude other constituent elements unless otherwise stated, but rather indicates that other constituent elements may be further included.

[0026] In this specification, "A and / or B" means "A and B, or A, or B".

[0027] In this instruction manual, and This indicates a bond that is linked to other substituents.

[0028] The present invention will now be described in more detail.

[0029] One embodiment of the present invention provides a synthetic reaction product composition of isosorbide-based epoxy compounds, comprising an isosorbide-based epoxy compound represented by the following chemical formula 1 and a hydrolyzable chlorine component, wherein the hydrolyzable chlorine component is less than 5000 ppm.

[0030] [Chemical Formula 1]

[0031]

[0032] In the above chemical formula 1,

[0033] R is H or ,

[0034] n is an integer from 0 to 100.

[0035] The isosorbide-based epoxy compound synthesis reaction product composition according to one embodiment of the present invention is obtained as a composition comprising isosorbide-based epoxy compound and byproducts generated during its synthesis.

[0036] The synthetic reaction product composition of isosorbide-based epoxy compounds according to one embodiment of the present invention includes isosorbide-based epoxy compounds represented by the above-described chemical formula 1. Specifically, by including isosorbide, which has a high biomass carbon content, it can possess the advantages of biomass resource sustainability and environmental protection.

[0037] According to one embodiment of the present invention, the aforementioned isosorbide-based epoxide can be a single isosorbide epoxide of Formula 1, or a mixture of isosorbide epoxides with different substituents R and / or indices n. When multiple types of isosorbide epoxides are present, the substituent R can be applied in various ways as shown in Formula 1. Furthermore, n can be applied in various ways to satisfy a value from 0 to 100. Specifically, n can be a value from 0 to 40.

[0038] The synthetic reaction product composition of isosorbide-based epoxides according to one embodiment of the present invention includes a hydrolyzed chlorine component. Specifically, the hydrolyzed chlorine component (Hy-Cl) refers to hydrolyzable chlorine remaining in the chlorine that has not reacted with the basic compound during the preparation of the isosorbide-based epoxide, and its purity may be related to that of the isosorbide-based epoxide. For example, the hydrolyzed chlorine component may be a haloalcohol ether intermediate, but is not limited thereto, and may also include compounds corresponding to the hydrolyzed chlorine component generated in known synthetic reactions of isosorbide-based epoxides.

[0039] The isosorbide-based epoxy compound synthesis product composition according to one embodiment of the present invention includes less than 5000 ppm of the aforementioned hydrolyzable chlorine component. Specifically, the aforementioned isosorbide-based epoxy compound synthesis product composition may include less than 2000 ppm of the aforementioned hydrolyzable chlorine component. Preferably, it may include 500 ppm to 1650 ppm of the aforementioned hydrolyzable chlorine component. The fact that the hydrolyzable chlorine component in the aforementioned isosorbide-based epoxy compound synthesis product composition is below the aforementioned concentration proves that the isosorbide-based epoxy compound synthesis product composition is prepared with high purity.

[0040] According to one embodiment of the present invention, in the above-described chemical formula 1, the isosorbide-based epoxide compound with n=0 can be from 40% to 70% by weight relative to the total weight of the isosorbide-based epoxide compound. Specifically, in the above-described chemical formula 1, the compound with n=0 can be from 50% to 60% by weight relative to the total weight of the isosorbide-based epoxide compound. By adjusting the proportion of the compound with n=0 in the above-described chemical formula 1 within the above range, the purity of the isosorbide-based epoxide compound can be adjusted.

[0041] According to one embodiment of the present invention, the epoxy equivalent of the above-mentioned isosorbide-based epoxy compound synthesis reaction product composition can be from 120 g / eq to 500 g / eq. Specifically, the epoxy equivalent of the isosorbide-based epoxy compound contained in the isosorbide-based epoxy compound synthesis reaction product composition can be from 120 g / eq to 350 g / eq, 130 g / eq to 300 g / eq, 135 g / eq to 250 g / eq, 140 g / eq to 200 g / eq, or 160 g / eq to 170 g / eq. Here, epoxy equivalent represents the value obtained by dividing the molecular weight by the number of functional groups, and can be measured, for example, by a neutralization titration method.

[0042] According to one embodiment of the present invention, the Brookfield viscosity of the above-mentioned isosorbide-based epoxy compound synthesis reaction product composition, measured at 25°C, can be from 500 cPs to 2000 cPs. Specifically, the viscosity of the above-mentioned isosorbide-based epoxy compound synthesis reaction product composition can be from 800 cPs to 1800 cPs, 900 cPs to 1700 cPs, 1000 cPs to 1600 cPs, 1100 cPs to 1400 cPs, or 1200 cPs to 1300 cPs. Here, Brookfield viscosity represents the fluid resistance value acting on the spindle when measured using a rotational viscometer, and can be measured using a Brookfield viscometer.

[0043] An embodiment of the present invention provides a method for preparing isosorbide-based epoxy compounds, comprising: step (S10), reacting isosorbide, an organohalide, and a basic compound in the presence of a phase transfer catalyst to obtain a reaction product comprising a salt and an isosorbide-based epoxy compound; step (S30), filtering the salt in a candle filter device to obtain a filtrate; and step (S50), removing the organohalide from the filtrate to obtain the isosorbide-based epoxy compound.

[0044] The synthetic reaction product composition of the isosorbide-based epoxy compound according to an embodiment of the present invention can be prepared as the synthetic reaction product composition in the preparation method of the isosorbide-based epoxy compound.

[0045] The isosorbide-based epoxy compounds with low viscosity, high purity, and significantly improved yield can be prepared by the preparation method of isosorbide-based epoxy compounds according to an embodiment of the present invention.

[0046] According to one embodiment of the present invention, the steps for obtaining the above-mentioned reaction product may include: step (S11), mixing the above-mentioned isosorbide with the above-mentioned organohalide in the presence of the above-mentioned phase transfer catalyst, and carrying out a ring-opening reaction at a temperature of 40°C to 100°C; step (S12), adding the above-mentioned basic compound to the product of the above-mentioned ring-opening reaction, and carrying out an epoxy substitution reaction at a temperature of 40°C to 100°C; and step (S13), carrying out a ring-closing reaction of the product of the above-mentioned substitution reaction at a temperature of 40°C to 100°C and under reduced pressure by an azeotropic distillation reaction.

[0047] Specifically, the aforementioned candle filter can be a cylindrical filter shaped like a candle and can be made of a porous, permeable material. By pressurizing and filtering a fluid using the aforementioned candle filter, target solid particles of a predetermined size or larger can be filtered and separated from the liquid. For example, in the aforementioned method for preparing isosorbide-based epoxy compounds, by pressurizing and filtering the reaction product using the aforementioned candle filter, solid salts cannot pass through the porous, permeable material within the candle filter, thereby enabling separation from the filtrate.

[0048] According to one embodiment of the present invention, in the method for preparing isosorbide-based epoxy compounds, the candle filter device described above can filter salts with a particle size of 2.7 μm or more. Preferably, the candle filter device can filter salts with a particle size of 3.0 μm or more. By using the candle filter device to filter salts that exist in solid form in the reaction product fluid while recovering isosorbide-based epoxy compounds remaining in the filtered salts, the yield can be improved.

[0049] According to one embodiment of the present invention, in the method for preparing isosorbide-based epoxy compounds, the step of obtaining the above-mentioned filtrate can be a step of filtering under conditions maintained at a temperature of 20°C to 100°C. By maintaining the above-mentioned temperature conditions, the efficiency of the step of obtaining the above-mentioned filtrate can be improved.

[0050] According to one embodiment of the present invention, in the method for preparing isosorbide-based epoxy compounds, the isosorbide-based epoxy compounds may be compounds represented by the following chemical formula 1.

[0051] [Chemical Formula 1]

[0052]

[0053] In the above chemical formula 1,

[0054] R is H or ,

[0055] n is an integer from 0 to 100.

[0056] Specifically, the aforementioned isosorbide-based epoxides are, as described above, bio-derived compounds different from existing petroleum-based compounds, characterized in that their bio-carbon content, based on 100% of the total carbon atoms, is 100%. Here, the aforementioned bio-carbon content can be measured by calculating the proportion of bio-derived carbon in all organic carbon. For example, the bio-carbon content of the aforementioned isosorbide-based epoxides can be determined based on the proportion of radioactive isotopes in the total organic carbon content (…). 14 C) The percentage (%) is calculated and measured, specifically according to ASTM D 6866. Here, the biocarbon content can be expressed as a percentage of the number of carbon atoms.

[0057] Furthermore, the aforementioned isosorbide-based epoxides can be a single isosorbide epoxide of Formula 1, or a mixture of isosorbide epoxides with different substituents R and / or indices n. When multiple types of isosorbide epoxides are present, the substituent R can be used in various ways as shown in Formula 1. Furthermore, n can be used in various ways to satisfy values ​​from 0 to 100. Specifically, n can be used to satisfy values ​​from 0 to 40.

[0058] According to one embodiment of the present invention, in the method for preparing isosorbide-based epoxides, the yield of the isosorbide-based epoxide obtained in the step of obtaining the aforementioned isosorbide-based epoxide can be 90% or more. Specifically, the yield of the isosorbide-based epoxide in the filtrate obtained by the aforementioned candle filter apparatus can be 90% or more and less than 100%, 95% or more and less than 100%, 96% or more and less than 100%, 97% or more and less than 100%, or 98% or more and less than 100%. As described above, by feeding the reaction product into the aforementioned candle filter apparatus to filter the salt and recover the isosorbide-based epoxide remaining in the salt, the yield of the isosorbide-based epoxide in the aforementioned synthetic reaction product can be improved.

[0059] One embodiment of the present invention provides a coating composition comprising the synthetic reaction product composition of the above-mentioned isosorbide-based epoxy compounds.

[0060] According to one embodiment of the present invention, the coating composition, through a synthetic reaction product composition comprising the above-mentioned isosorbide-based epoxy compounds, can ensure the physical properties required for a coating, namely adhesion, lightfastness, and moisture resistance, while maintaining environmental friendliness, excellent coating workability and appearance.

[0061] The preparation methods of the above-mentioned isosorbide-based epoxy compounds are described below according to each process step.

[0062] (S10) Step to obtain the reaction product

[0063] Step (S10) is a step in which isosorbide, an organohalide and a basic compound are reacted in the presence of a phase transfer catalyst to obtain a reaction product including a salt and an isosorbide-based epoxy compound.

[0064] The method for preparing isosorbide-based epoxy compounds according to the present invention is characterized in that, in step (S10), isosorbide is mixed with an organic halide in the presence of a phase transfer catalyst to carry out a ring-opening reaction, and then a basic compound is reacted to carry out a substitution reaction and a ring-closing reaction, thereby performing a process to obtain a reaction product including a salt and isosorbide-based epoxy compounds.

[0065] The reaction products obtained according to step (S10) may include isosorbide-based epoxy compounds, phase transfer catalysts, organohalides, hydrolyzable chlorine components, and salts.

[0066] <(S11) Ring-opening reaction>

[0067] This step involves mixing isosorbide with an organohalide in the presence of a phase transfer catalyst and carrying out a ring-opening reaction under ambient pressure rather than reduced pressure conditions in a mild atmosphere at temperatures ranging from 40°C to 100°C.

[0068] Specifically, the pressure for the above-mentioned ring-opening reaction can be from 752 mmHg to 768 mmHg, or from 755 mmHg to 765 mmHg, or from 758 mmHg to 762 mmHg. As an example, the above-mentioned ring-opening reaction can be carried out under a pressure of approximately 760 mmHg.

[0069] Furthermore, the temperature for the above-mentioned ring-opening reaction can be above 45°C, above 48°C, or above 50°C, and can be below 90°C, below 80°C, below 70°C, below 65°C, or below 60°C. As an example, the above-mentioned ring-opening reaction can be carried out at a temperature between 48°C and 55°C.

[0070] The above ring-opening reaction can proceed for 0.1 hours to 6 hours, specifically 0.12 hours to 5 hours, 0.14 hours to 3 hours, or 0.16 hours to 2 hours.

[0071] The method for preparing isosorbide-based epoxy compounds according to the present invention can use a compound represented by the following chemical formula 2 as a phase transfer catalyst.

[0072] [Chemical Formula 2]

[0073] Ar a R 2 4-a N + (X 1b ) -

[0074] In the above chemical formula 2,

[0075] Ar are either the same as or different from each other, and each is independently either substituted or unsubstituted C. 6-20 aryl, or substituted or unsubstituted C 6-20 aryl-substituted C 1-3 alkyl,

[0076] R 2 They are the same or different from each other, and each is independently C. 1-20 alkyl,

[0077] X 1 They may be the same as or different from each other, and each is independently chlorine (Cl), bromine (Br), iodine (I), or fluorine (F).

[0078] a is an integer from 1 to 4.

[0079] b is an integer from 1 to 3.

[0080] In addition, unless otherwise specified, the following terms may be defined as follows in this specification.

[0081] Halogens can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0082] The above C 1-20 The alkyl group, i.e., the alkyl group having 1 to 20 carbon atoms, can be straight-chain, branched, or cyclic alkyl. Specifically, the alkyl group having 1 to 20 carbon atoms can be a straight-chain alkyl group having 1 to 20 carbon atoms; a straight-chain alkyl group having 1 to 15 carbon atoms; a straight-chain alkyl group having 1 to 5 carbon atoms; a branched or cyclic alkyl group having 3 to 20 carbon atoms; a branched or cyclic alkyl group having 3 to 15 carbon atoms; or a branched or cyclic alkyl group having 3 to 10 carbon atoms. As an example, the above-mentioned alkyl groups having 1 to 20 carbon atoms (C 1-20 The alkyl group of () may include, but is not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0083] In particular, the aforementioned C 1-3 Alkyl groups, that is, alkyl groups having 1 to 3 carbon atoms, can be straight-chain or branched alkyl groups. Specifically, alkyl groups having 1 to 3 carbon atoms can include, but are not limited to, methyl, ethyl, propyl, isopropyl, etc.

[0084] The above C 6-20The aryl group, that is, an aryl group with 6 to 20 carbon atoms, can be a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon. As an example, the aforementioned aryl group can include phenyl, biphenyl, naphthyl, anthracene, phenanthryl, fluorene, etc., but is not limited to these.

[0085] The substituents described above may be substituted with at least one substituent selected from the group consisting of hydroxyl; halogen; alkyl or alkenyl, aryl, alkoxy; alkyl or alkenyl, aryl, alkoxy containing at least one heteroatom from groups 14 to 16; silyl; alkylsilyl or alkoxysilyl; phosphin; phosphoro; sulfonate; and sulfonyl.

[0086] As an example, the phase transfer catalyst represented by the above chemical formula 2 can be at least one selected from the group consisting of benzyltrimethylammonium chloride (BTMAC), benzyltrimethylammonium bromide, benzyltriethylammonium chloride (BTEAC), benzyltriethylammonium bromide, benzyltributylammonium chloride (BTBAC), benzyltributylammonium bromide, benzyltrimethylammonium dichloroiodate, benzyltriphenylammonium chloride, and methyltriphenylammonium chloride. Preferably, the phase transfer catalyst represented by the above chemical formula 2 can be at least one selected from the group consisting of benzyltrimethylammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), or benzyltributylammonium chloride (BTBAC). More preferably, the phase transfer catalyst represented by the above chemical formula 2 can be benzyltriethylammonium chloride (BTEAC).

[0087] In step (S10), the phase transfer catalyst may be added in an amount of 0.1 wt% to 6 wt% relative to the weight of isosorbide. Specifically, the phase transfer catalyst may be added in amounts of 0.3 wt% to 5.5 wt%, 0.5 wt% to 5 wt%, 0.7 wt% to 4.5 wt%, 0.9 wt% to 4 wt%, 1.1 wt% to 3.5 wt%, 1.3 wt% to 3 wt%, or 1.5 wt% to 2.5 wt%.

[0088] In step (S10), the organohalide may be at least one selected from the group consisting of epibromopropane, epifluoropropane, epiiodopropane, and epichlorohydrin. Preferably, the organohalide may be epichlorohydrin.

[0089] In step (S10), the organohalide may be added in an amount of 1.0 mol to 20.0 mol relative to the isosorbide hydroxyl group. As an example, the organohalide may be added in amounts of 1.5 mol to 18.0 mol, 2.0 mol to 15.0 mol, 2.5 mol to 10.0 mol, 3.0 mol to 8.0 mol, or 3.2 mol to 6.0 mol relative to the isosorbide hydroxyl group.

[0090] <(S12) Substitution Reaction>

[0091] This is the step of adding a basic compound after the ring-opening reaction, and carrying out the epoxide substitution reaction under normal pressure conditions instead of the existing reduced pressure conditions, in a mild atmosphere at a temperature of 40°C to 100°C.

[0092] Specifically, the pressure for the above substitution reaction can be 752 mmHg to 768 mmHg, 755 mmHg to 765 mmHg, or 758 mmHg to 762 mmHg. As an example, the above substitution reaction can be carried out under a pressure of about 760 mmHg.

[0093] Furthermore, the temperature of the above substitution reaction can be above 45°C, above 48°C, or above 50°C, and can be below 90°C, below 80°C, below 70°C, below 60°C, or below 55°C. As an example, the above substitution reaction can be carried out at a temperature of 50°C to 55°C.

[0094] The above substitution reaction can proceed for 0.1 hours to 6 hours, specifically 0.5 hours to 5 hours, 1.0 hours to 4 hours, or 1.5 hours to 3 hours.

[0095] In the above substitution reaction, the basic compound can be at least one alkali metal hydroxide. Specifically, the basic compound can be at least one selected from the group consisting of lithium hydroxide, potassium hydroxide, calcium hydroxide, and sodium hydroxide (NaOH). Preferably, the basic compound can be sodium hydroxide (NaOH).

[0096] In the above substitution reaction, the basic compound may be added in an amount of 0.05 mol to 2.5 mol relative to the isosorbide hydroxyl group. As an example, the basic compound may be added in an amount of 0.05 mol to 2.0 mol, 0.06 mol to 1.5 mol, 0.06 mol to 1.0 mol, 0.06 mol to 0.8 mol, 0.07 mol to 0.5 mol, 0.08 mol to 0.4 mol, or 0.1 mol to 0.3 mol relative to the isosorbide hydroxyl group.

[0097] On the other hand, in the above-mentioned ring-opening reaction and the above-mentioned substitution reaction, the pressure difference (ΔmmHg) of the above-mentioned substitution reaction is close to 0, and they can be carried out under substantially the same pressure conditions.

[0098] <(S13) Closed-loop reaction>

[0099] The step involves performing a ring-closing reaction via azeotropic distillation at temperatures ranging from 40°C to 100°C under reduced pressure to obtain a reaction product comprising isosorbide-based epoxides and salts.

[0100] Specifically, the pressure of the above-mentioned azeotropic distillation reaction can be carried out under pressure conditions ranging from 70 mmHg to 500 mmHg. More specifically, the pressure of the above-mentioned azeotropic distillation reaction can be above 75 mmHg, or above 80 mmHg, or above 85 mmHg, or above 90 mmHg, or above 95 mmHg, or above 100 mmHg, or above 110 mmHg, or above 120 mmHg, or above 130 mmHg, or above 140 mmHg, and can be below 480 mmHg, or below 450 mmHg, or below 420 mmHg, or below 400 mmHg, or below 380 mmHg, or below 350 mmHg, or below 320 mmHg, or below 300 mmHg, or below 280 mmHg, or below 250 mmHg, or below 220 mmHg, or below 200 mmHg. As an example, the above-mentioned azeotropic distillation reaction can be carried out under pressure conditions of 140 mmHg to 160 mmHg.

[0101] Furthermore, the temperature of the aforementioned azeotropic distillation reaction can range from 40°C to 100°C. Specifically, the temperature of the aforementioned azeotropic distillation reaction can be above 45°C, or above 48°C, or above 50°C, or above 52°C, or above 55°C, and can be below 90°C, or below 85°C, or below 80°C, or below 78°C, or below 75°C, or below 72°C. As an example, the aforementioned azeotropic distillation reaction can be carried out at a temperature of 60°C to 70°C.

[0102] In the above-described closed-loop reaction, an alkaline compound may be added and the above-described azeotropic distillation reaction may be performed. The alkaline compound may be at least one alkali metal hydroxide. Specifically, the alkaline compound may be at least one selected from the group consisting of lithium hydroxide, potassium hydroxide, calcium hydroxide, and sodium hydroxide (NaOH). Preferably, the alkaline compound may be sodium hydroxide (NaOH).

[0103] In the above-described ring-closing reaction, the basic compound may be added in an amount of 0.05 mol to 2.5 mol relative to the isosorbide hydroxyl group. As an example, the basic compound may be added in amounts of 0.08 mol to 2.0 mol, 0.1 mol to 1.8 mol, 0.2 mol to 1.6 mol, 0.3 mol to 1.5 mol, 0.4 mol to 1.35 mol, 0.5 mol to 1.2 mol, or 0.7 mol to 1.1 mol relative to the isosorbide hydroxyl group.

[0104] Specifically, in the aforementioned ring-closing reaction, the amount of the basic compound added can be approximately 2 to 15 times, approximately 3.5 to 12.5 times, or approximately 4 to 9 times by weight relative to the amount of the basic compound added in the aforementioned substitution reaction. Preferably, it can be approximately 4 times.

[0105] The above-mentioned azeotropic distillation reaction can be carried out for 0.5 hours to 10 hours, specifically, for 1 hour to 9 hours, 2 hours to 8 hours, or 3 hours to 7 hours.

[0106] On the other hand, the pressure difference (ΔmmHg) between the aforementioned ring-opening reaction and the aforementioned azeotropic distillation reaction can be 250 mmHg or more, or 250 mmHg to 698 mmHg; specifically, it can be 270 mmHg or more, or 270 mmHg to 610 mmHg. In particular, in this invention, the aforementioned ring-opening reaction is carried out under pressure conditions close to atmospheric pressure, while the aforementioned azeotropic distillation reaction is carried out under pressure conditions with a relatively large decompression.

[0107] Furthermore, the pressure difference (ΔmmHg) between the aforementioned substitution reaction and the aforementioned azeotropic distillation reaction can be 250 mmHg or more, or 250 mmHg to 698 mmHg; specifically, it can be 270 mmHg or more, or 270 mmHg to 610 mmHg. In particular, in this invention, the aforementioned substitution reaction is carried out under pressure conditions close to atmospheric pressure, while the aforementioned azeotropic distillation reaction is carried out under pressure conditions with a relatively large degree of decompression.

[0108] (S30) Step of separating salt and obtaining filtrate

[0109] Step (S30) is a step in which the reaction product obtained in step (S10) is filtered through a candle filter device to obtain a filtrate at a temperature of 20°C to 100°C.

[0110] Specifically, the reaction product fluid generated in step (S10) is pumped to a candle filter, where it is separated into a liquid filtrate that has passed through the candle filter and a solid salt that has been filtered out by the candle filter. The liquid filtrate that has passed through the candle filter can be returned to the fluid inlet to repeat step (S30), or it can be stored for performing step (S50) as described later.

[0111] By filtering the salt through the aforementioned candle filter to obtain the filtrate, the isosorbide-based epoxides remaining in the filtered salt can be recovered while filtering the salt in its solid state, thereby maximizing the yield of the isosorbide-based epoxides.

[0112] The filtrate obtained by filtering the salt in step (S30) may include isosorbide-based epoxy compounds, organic halides and hydrolyzable chlorine components, as well as a phase transfer catalyst.

[0113] The salt filtered in step (S30) may have a particle size of 2.7 μm or more or 3.0 μm or more.

[0114] The salt filtered in step (S30) can be sodium chloride (NaCl). Specifically, when the salt layer filtered by the candle filter reaches a certain thickness, the rate at which the reaction product fluid passes through the salt decreases, the filtration efficiency decreases, and the filter pressure increases. Therefore, after fully recovering the isosorbide-based epoxy compounds remaining in the salt, the salt layer reaching the aforementioned specific thickness can be separated.

[0115] Furthermore, the temperature for performing step (S30) can be between 20°C and 100°C. Specifically, the temperature for performing step (S30) can be above 25°C, or above 28°C, or above 30°C, or above 32°C, or above 35°C, and below 90°C, or below 80°C, or below 70°C, or below 60°C, or below 50°C, or below 40°C. As an example, the temperature for performing step (S30) can be between 35°C and 40°C. Preferably, the temperature for performing the above step (S30) can be 35°C.

[0116] (S50) Step to obtain isosorbide-based epoxides

[0117] Step (S50) is a step of removing organic halides from the filtrate obtained in step (S30) to obtain isosorbide-based epoxy compounds.

[0118] The synthetic reaction product composition obtained in step (S50) may include isosorbide-based epoxy compounds and hydrolyzable chlorine components, and isosorbide-based epoxy compounds can be obtained from the above synthetic reaction product composition.

[0119] Specifically, unreacted residual organohalides can be removed from the filtrate obtained in step (S30) to obtain a synthetic reaction product composition comprising the aforementioned isosorbide-based epoxides. In removing the unreacted residual organohalides, removal can be achieved by volatilizing them at high temperatures, but complete removal may not be possible. Preferably, the temperature can be increased to 160°C and the pressure reduced to a maximum of 5 Torr to remove the unreacted residual organohalides.

[0120] Embodiments for implementing the present invention

[0121] Preferred embodiments are presented below to aid in understanding the present invention. However, these embodiments are provided for the purpose of understanding the present invention only and are not intended to limit the scope of the invention.

[0122] <Example>

[0123] Example 1

[0124] In a 1000 mL round-bottom flask equipped with a water separator, condenser, stirrer, and nitrogen inlet, 100 g of isosorbide (ISB) and 510 g of epichlorohydrin were added and dissolved while the temperature was raised to 60 °C. Epichlorohydrin (ECH) was added at a rate of 4 moles relative to the hydroxyl group (OH) of isosorbide. After the solution was completely dissolved, 2 g of benzyltriethylammonium chloride (BTEAC) was added, and a ring-opening reaction was carried out at 50 °C and 760 mmHg for 10 minutes. Benzyltriethylammonium chloride (BTEAC), as a phase transfer catalyst, was added at a rate of 2 wt% based on a 100% weight percentage of isosorbide. Subsequently, after the ring-opening reaction, 22 g of a 50% sodium hydroxide (NaOH) aqueous solution was added in two portions, one hour apart, and an epoxy substitution reaction was carried out at 50 °C and 760 mmHg for 2 hours. In this process, caustic soda was added at a molar ratio of 0.2 moles relative to the isosorbide hydroxyl (OH) group. Subsequently, the temperature was raised to 65°C, and 88 g of a 50% caustic soda (NaOH) aqueous solution was quantitatively injected over 3 hours under a pressure of 150 mmHg. While continuously removing reaction water through reflux, an azeotropic distillation reaction under reduced pressure was carried out to achieve an epoxy ring-closure reaction, thereby obtaining the reaction product comprising salt and isosorbide-based epoxy compounds. In this process, caustic soda was added at a molar ratio of 0.8 moles relative to the isosorbide hydroxyl (OH) group. The total amount of caustic soda added in the above substitution and ring-closure reactions was 1 mole relative to the isosorbide hydroxyl (OH) group.

[0125] After the closed-loop reaction is completed, the obtained reactants, i.e., the reaction product fluid, are fed into a candle filter device to filter the salt (NaCl) to obtain a salt layer, and a filtrate is also obtained. At this time, filtration can be carried out at 35°C.

[0126] Therefore, epichlorohydrin (ECH) is heated to 160°C and depressurized to a maximum of 5 Torr before removal, thereby obtaining the synthetic reaction product composition of isosorbide-based epoxy compounds.

[0127] <Comparative Example>

[0128] Comparative Example 1

[0129] In Example 1, after the ring-closing reaction was completed, water equivalent to 2.2 times the amount of theoretical salt (NaCl) was added to the obtained first reaction product, stirred, and transferred to a separatory funnel to remove the lower aqueous phase to remove the salt (NaCl). Otherwise, the synthesis reaction product composition of isosorbide-based epoxy compounds was obtained by the same method as in Example 1 above.

[0130] The reaction yields of the isosorbide-based epoxy compound synthesis reaction product compositions according to the above-described Examples 1 and Comparative Example 1 are shown in Table 1 below.

[0131]

[0132] In Table 1 above, the reaction yield refers to the percentage (%) of the total weight of isosorbide-based epoxy compounds in the synthetic reaction product composition generated by step (S50) compared to the total weight of isosorbide added to step (S10).

[0133] <Experimental Example>

[0134] The physical properties of the isosorbide-based epoxy compound synthesis product compositions obtained according to Example 1 and Comparative Example 1 were evaluated as follows, and the measured values ​​are shown in Table 2 below.

[0135] a) Content of the compound with n=0 in the synthesis product composition of isosorbide epoxide

[0136] The synthesis product composition of the isosorbide epoxide obtained according to Example 1 and Comparative Example 1 was dissolved in THF at a concentration of 2.5% by weight and analyzed by gel permeation chromatography (GPC, Gel Permeation Chromatography systems; Shimadzu, Shodex, KF-801, 802, 803, 805 columns). The analysis temperature was 40°C, the mobile phase was tetrahydrofuran (HPLC grade), and the flow rate was 1 mL / min. The GPC data obtained in this manner confirmed the content (GPC, %) of isosorbide diglycidyl ether (n=0) in the total composition.

[0137] b) Epoxy equivalent

[0138] For the isosorbide-based epoxy compound synthesis product compositions obtained according to Example 1 and Comparative Example 1, the epoxy equivalent was determined by neutralization titration. Specifically, the above-mentioned isosorbide-based epoxy compound synthesis product compositions were dissolved in 1,4-dioxane, reacted with 0.2N-HCl solution, and then titrated with 0.1N-NaOH methanol solution to determine the epoxy equivalent (EEW, g / eq). Here, epoxy equivalent (EEW, g / eq) represents the value obtained by dividing the molecular weight by the number of functional groups, and can be determined, for example, by neutralization titration.

[0139] c) Viscosity

[0140] For the synthesis reaction product compositions of isosorbide-based epoxy compounds obtained according to Example 1 and Comparative Example 1, the viscosity (cPs) was measured at 25°C using a rotational viscometer and a Brinell viscometer. Here, Brinell viscosity refers to the fluid resistance value applied to the rotor as expressed using a rotational viscometer.

[0141] d) Concentration of hydrolyzable chlorine component (Hy-Cl)

[0142] For the isosorbide-based epoxy compound synthesis reaction product compositions obtained according to Example 1 and Comparative Example 1, the hydrolyzable chlorine content in the compositions was determined by neutralization titration. Specifically, the above-mentioned isosorbide-based epoxy compound synthesis reaction product compositions were dissolved in 1,4-dioxane, 0.1N KOH-methanol solution was added, a condenser was installed, and the mixture was heated at 70°C to allow the reaction to proceed. Subsequently, glacial acetic acid was added, and titration was performed with an aqueous solution of AgNO3 to determine and express the concentration of the hydrolyzable chlorine content.

[0143]

[0144] As shown in Table 2 above, according to the present invention, Example 1, which removes epichlorohydrin by feeding the reaction product fluid obtained by performing step (S10) into a candle filter device to filter salt, exhibits a higher epoxy equivalent and higher viscosity compared to Comparative Example 1, which removes salt by feeding water and transferring it to a separatory funnel. In particular, the concentration of hydrolyzable chlorine component (Hy-Cl) as a byproduct is significantly reduced, and it can be confirmed that the preparation yield of isosorbide-based epoxy compounds is significantly improved.

Claims

1. A composition of synthetic reaction products of isosorbide-based epoxides, characterized in that, include: Isosorbide-based epoxy compounds represented by the following chemical formula 1; as well as Hydrolyzable chlorine components; The hydrolyzable chlorine content is less than 5000 ppm. [Chemical Formula 1] In the above chemical formula 1, R is H or , n is an integer from 0 to 100.

2. The synthetic reaction product composition of isosorbide-based epoxides according to claim 1, characterized in that, In the above chemical formula 1, the content of the compound with n=0 is 40% to 70% by weight relative to the total weight of the above isosorbide-based epoxy compounds.

3. The synthetic reaction product composition of isosorbide-based epoxides according to claim 1, characterized in that, The epoxy group equivalent ranges from 120 g / eq to 500 g / eq.

4. The synthetic reaction product composition of isosorbide-based epoxides according to claim 1, characterized in that, The Brinell viscosity measured at 25°C ranged from 500 cPs to 2000 cPs.

5. A method for preparing isosorbide-based epoxide compounds, characterized in that, include: Step (S10): In the presence of a phase transfer catalyst, isosorbide, organohalides and basic compounds are reacted to obtain reaction products including salts and isosorbide-based epoxy compounds. Step (S30): The above reaction product is fed into a candle filter device to filter the salt and obtain the filtrate; and Step (S50): Remove organic halides from the above filtrate to obtain isosorbide-based epoxy compounds.

6. The method for preparing isosorbide-based epoxides according to claim 5, characterized in that, The steps to obtain the above reaction products include: Step (S11): In the presence of the phase transfer catalyst, isosorbide is mixed with the organic halide and the ring-opening reaction is carried out at a temperature of 40°C to 100°C. Step (S12): The basic compound is added to the product of the above ring-opening reaction, and an epoxide substitution reaction is carried out at a temperature of 40°C to 100°C; and Step (S13) involves subjecting the product of the above substitution reaction to a ring-closing reaction via azeotropic distillation at a temperature of 40°C to 100°C under reduced pressure.

7. The method for preparing isosorbide-based epoxides according to claim 5, characterized in that, The above-mentioned candle filter device filters salt with a particle size of 2.7 μm or larger.

8. The method for preparing isosorbide-based epoxides according to claim 5, characterized in that, The step of obtaining the above filtrate is to perform filtration while maintaining a temperature of 20°C to 100°C.

9. The method for preparing isosorbide-based epoxides according to claim 5, characterized in that, The above-mentioned isosorbide-based epoxides are isosorbide-based epoxides represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R is H or , n is an integer from 0 to 100.

10. The method for preparing isosorbide-based epoxides according to claim 5, characterized in that, The yield of isosorbide-based epoxy compounds obtained in the above-mentioned steps is over 90%.

11. A coating composition, characterized in that, Compositions comprising the synthetic reaction products of isosorbide-based epoxides according to any one of claims 1 to 4.

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