A composition resulting from the synthesis reaction of an isosorbide-based epoxy compound and a paint composition containing the same, and a method for producing an isosorbide-based epoxy compound.

Abstract

The present invention relates to a synthetic reaction product composition of an isosorbide-based epoxy compound and a paint composition containing the same, and a method for producing an isosorbide-based epoxy compound. More specifically, it relates to a synthetic reaction product composition of an isosorbide-based epoxy compound with low viscosity and high purity, a paint composition containing the same, and a method for producing an isosorbide-based epoxy compound with improved yield.

Description

[Technical Field]

[0001] This invention claims the benefits as of the filing date of Patent Application No. 10-2023-0108493, filed with the Korean Intellectual Property Office on August 18, 2023, and all of its contents are included in this invention.

[0002] The present invention relates to a synthesis reaction product composition of an isosorbide-based epoxy compound with low viscosity and high purity, a paint composition containing the same, and a method for producing an isosorbide-based epoxy compound with improved yield. [Background technology]

[0003] Generally, polymer compounds are manufactured using raw materials derived from petroleum resources. However, with recent concerns about the depletion of petroleum resources, there is a growing demand for polymer resins that use raw materials obtained from biomass resources such as plants.

[0004] In particular, as environmental problems arising from the use of petroleum resources become more serious, the sustainability and environmental benefits of biomass resources are becoming even more apparent. From this perspective, the development of biomass-based monomer and polymer production technologies is being treated as an important issue in both academia and industry. Especially given concerns that increased carbon dioxide emissions and accumulation will lead to global warming and climate change, there is a demand for the development of polymer resins made from plant-derived monomers that produce very little carbon during the manufacturing process.

[0005] Along with the sustainability and environmental benefits of biomass resources, there is a growing need for the development of new polymers with novel carbon skeleton structures that can ensure mechanical properties equivalent to or better than petroleum-based polymers, as well as low glass transition temperatures.

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

[0007] Methods for producing epoxy resins by reacting such isosorbide with epichlorohydrin are known in various forms and have been described in numerous publications. However, in most of the methods described in the literature, the resin is synthesized in the form of n=1 or greater rather than isosorbide diglycidyl ether (n=0), resulting in a higher viscosity. For example, commercially applicable synthesis methods using caustic soda, as described in the literature, mostly exhibit a viscosity of 10,000 cps or more at room temperature.

[0008] Furthermore, in most of the manufacturing methods described in the literature for producing isosorbide epoxy resin, it was difficult to recover the epoxy resin remaining in the salt layer, making it challenging to achieve a yield exceeding 90%.

[0009] Therefore, there is a need to develop a novel manufacturing method that has a high content of isosorbide diglycidyl ether (n=0), low viscosity, and excellent yield. [Overview of the project] [Problems that the invention aims to solve]

[0010] To solve the problems of the prior art described above, the present invention provides a synthesis reaction result composition of an isosorbide-based epoxy compound that has the advantages of biomass resource sustainability and environmental consideration, low viscosity and high purity, a paint composition containing the same, and a method for producing an isosorbide-based epoxy compound with improved yield.

[0011] However, the problems to be solved by the present invention are not limited to the above-described problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

Means for Solving the Problems

[0012] One embodiment of the present invention for achieving the above object provides a synthesis reaction product composition of an isosorbide-based epoxy compound containing an isosorbide-based epoxy compound represented by the following Chemical Formula 1; and hydrolyzable chlorine content; wherein the hydrolyzable chlorine content is less than 5,000 ppm.

[0013] [Chemical Formula 1]

[0014]

Chem.

[0015] In the above Chemical Formula 1, R is H or

[0016]

Chem.

[0017] Another embodiment of the present invention provides a method for producing an isosorbide-based epoxy compound, comprising: (S10) reacting isosorbide, an organic halide, and a basic compound in the presence of a phase transfer catalyst to obtain a reaction product containing a salt and an isosorbide-based epoxy compound; (S30) introducing the reaction product into a candle filter device to filter the salt and obtain a filtrate; and (S50) removing the organic halide from the filtrate to obtain an isosorbide-based epoxy compound.

Advantages of the Invention

[0018] The composition of the synthesis reaction product of the isosorbide-based epoxy compound according to one embodiment of the present invention can provide a composition of the synthesis reaction product of a low-viscosity and high-purity isosorbide-based epoxy compound by containing a hydrolyzable chlorine content of less than 5,000 ppm.

[0019] The method for producing an isosorbide-based epoxy compound according to one embodiment of the present invention can recover the remaining isosorbide-based epoxy compound by filtering the salt using a candle filter device, and can produce an isosorbide-based epoxy compound in a high yield.

[0020] The paint composition according to one embodiment of the present invention can provide a paint composition having excellent workability and physical properties for painting and being environmentally friendly by including the composition of the synthesis reaction product of the isosorbide-based epoxy compound.

Embodiments for Carrying Out the Invention

[0021] In this specification, when a certain part "includes" a certain component, this means that, unless otherwise stated, it does not exclude other components but can further include other components. <http: / / www.google.com / patents / US20110263774A1?cl=en>

[0022] In this specification, "A and / or B" means "A and B, or A or B".

[0023] In this specification,

[0024]

Chemical Formula

[0025]

Chemical Formula

[0026] Hereinafter, the present invention will be described in more detail.

[0027] One embodiment of the present invention provides a synthesis reaction result composition of an isosorbide epoxy compound represented by the following chemical formula 1 and hydrolyzable chlorine, wherein the hydrolyzable chlorine is less than 5,000 ppm.

[0028] [Chemical formula 1]

[0029] [ka]

[0030] In the above chemical formula 1, R is H or

[0031] [ka] And, n is an integer between 0 and 100.

[0032] A composition resulting from the synthesis reaction of an isosorbide-based epoxy compound according to one embodiment of the present invention is obtained as a composition containing the isosorbide-based epoxy compound and by-products generated during its synthesis.

[0033] A composition resulting from the synthesis reaction of an isosorbide-based epoxy compound according to one embodiment of the present invention contains the isosorbide-based epoxy compound represented by the chemical formula 1. Specifically, by including isosorbide with a high biocarbon content, it can offer the benefits of biomass resource sustainability and environmental consideration.

[0034] According to one embodiment of the present invention, the isosorbide epoxy compound may be a single isosorbide epoxide of chemical formula 1, or a mixture of isosorbide epoxides with different substituents R and / or index n. When various types of isosorbide epoxides exist, substituent R is applicable in a variety of ways as explicitly shown in chemical formula 1. Furthermore, n is applicable in a variety of ways, satisfying values ​​from 0 to 100. Specifically, n may be a value satisfying values ​​from 0 to 40.

[0035] A composition resulting from the synthesis reaction of an isosorbide-based epoxy compound according to one embodiment of the present invention contains hydrolyzed chloride. Specifically, the hydrolyzed chloride (Hy-Cl) refers to hydrolyzable chlorine remaining after the production of the isosorbide-based epoxy compound without reacting with the basic compound, and is related to the purity of the isosorbide-based epoxy compound. For example, the hydrolyzed chloride may be, but is not limited to, a halohydrin ether intermediate, and may include compounds equivalent to the hydrolyzed chloride produced in known synthesis reactions of isosorbide-based epoxy compounds.

[0036] The synthesis reaction result composition of an isosorbide-based epoxy compound according to one embodiment of the present invention contains less than 5,000 ppm of hydrolyzable chlorine. Specifically, the synthesis reaction result composition of the isosorbide-based epoxy compound may contain less than 2,000 ppm of hydrolyzable chlorine. Preferably, it may contain 500 ppm to 1,650 ppm of hydrolyzable chlorine. Since the synthesis reaction result composition of the isosorbide-based epoxy compound contains hydrolyzable chlorine at a concentration less than that described above, it can be seen that the synthesis reaction result composition of the isosorbide-based epoxy compound was produced with high purity.

[0037] According to one embodiment of the present invention, the isosorbide-based epoxy compound in which n in chemical formula 1 is 0 may be present in an amount of 40 wt% to 70 wt% relative to the total weight of the isosorbide-based epoxy compound. Specifically, the compound in which n in chemical formula 1 is 0 may be present in an amount of 50 wt% to 60 wt% relative to the total weight of the isosorbide-based epoxy compound. The purity of the isosorbide-based epoxy compound can be adjusted by adjusting the ratio of the compound in which n in chemical formula 1 is 0 within the above range.

[0038] According to one embodiment of the present invention, the synthesis reaction result composition of the isosorbide-based epoxy compound may have an epoxy group equivalent of 120 g / eq to 500 g / eq. Specifically, the epoxy group equivalent of the isosorbide-based epoxy compound contained in the synthesis reaction result composition of the isosorbide-based epoxy compound may be 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, the epoxy group equivalent is the value obtained by dividing the molecular weight by the number of reactive groups, and can be measured, for example, by a neutralization titration method.

[0039] According to one embodiment of the present invention, the synthetic reaction product composition of the isosorbide-based epoxy compound may have a Brookfield viscosity of 500 cPs to 2,000 cPs measured at 25°C. Specifically, the viscosity of the synthetic reaction product composition of the isosorbide-based epoxy compound may be 800 cPs to 1,800 cPs, 900 cPs to 1,700 cPs, 1,000 cPs to 1,600 cPs, 1,100 cPs to 1,400 cPs, or 1,200 cPs to 1,300 cPs. Here, Brookfield viscosity is the resistance value of the fluid applied to the spindle using a rotational viscometer, and can be measured using a Brookfield viscometer.

[0040] One embodiment of the present invention provides a method for producing an isosorbide-based epoxy compound, comprising the steps of (S10) reacting isosorbide, an organic halide, and a basic compound in the presence of a phase transition catalyst to obtain a reaction product containing a salt and an isosorbide-based epoxy compound; (S30) introducing the reaction product into a candle filter apparatus to filter out the salt and obtain a filtrate; and (S50) removing the organic halide from the filtrate to obtain an isosorbide-based epoxy compound.

[0041] The synthesis reaction result composition of the isosorbide-based epoxy compound according to one embodiment of the present invention can be produced as the synthesis reaction result composition in the method for producing the isosorbide-based epoxy compound.

[0042] A method for producing isosorbide-based epoxy compounds according to one embodiment of the present invention makes it possible to produce isosorbide-based epoxy compounds with low viscosity, high purity, and significantly improved yield.

[0043] According to one embodiment of the present invention, the step of obtaining the reaction result may include (S11) mixing the isosorbide and the organic halide in the presence of the phase transition catalyst and carrying out a ring-opening reaction under temperature conditions of 40°C to 100°C; (S12) adding the basic compound to the result of the ring-opening reaction and carrying out an epoxy substitution reaction under temperature conditions of 40°C to 100°C; and (S13) carrying out a ring-closing reaction of the result of the substitution reaction by azeotropic distillation under reduced pressure at a temperature of 40°C to 100°C.

[0044] The candle filter is specifically a cylindrical filter in the shape of a candle, and may be made of a porous, permeable material. By pressurizing and filtering a fluid using the candle filter, target solid particles of a certain size or larger can be filtered out and separated from the liquid. For example, in the method for producing the isosorbide epoxy compound, by pressurizing and filtering the reaction product using the candle filter, the solid salt can be prevented from passing through the porous, permeable material in the candle filter and separated from the filtrate.

[0045] According to one embodiment of the present invention, in a method for producing an isosorbide-based epoxy compound, the candle filter device can filter salts with a particle size of 2.7 μm or larger. Preferably, the candle filter device can filter salts with a particle size of 3.0 μm or larger. The candle filter device can improve the yield by filtering out salts present in a solid state within the reaction result material while recovering the isosorbide-based epoxy compound remaining in the filtered salt.

[0046] According to one embodiment of the present invention, in a method for producing an isosorbide-based epoxy compound, the step of obtaining the filtrate may be a step of filtration while maintaining a temperature condition of 20°C to 100°C. By maintaining the above temperature conditions, the efficiency of the step of obtaining the filtrate can be improved.

[0047] According to one embodiment of the present invention, in a method for producing an isosorbide-based epoxy compound, the isosorbide-based epoxy compound may be represented by the following chemical formula 1.

[0048] [Chemical formula 1]

[0049] [ka]

[0050] In the above chemical formula 1, R is H or

[0051] [ka] And, n is an integer between 0 and 100.

[0052] Specifically, the isosorbide-based epoxy compound is, as described above, a bio-derived compound that is not an existing petroleum-based compound, and is characterized by having a biocarbon content of 100% based on 100% of the total number of carbon atoms. Here, the biocarbon content can be measured by calculating the ratio of bio-derived carbon to total organic carbon. For example, the biocarbon content of the isosorbide-based epoxy compound is calculated by the ratio of radioisotopes to the total number of organic carbon atoms ( 14 It can be estimated and measured by analogy using the ratio (%) of the number of C) elements, and specifically, it can be measured using ASTM D 6866 of the American Society for Testing and Materials as a standard. Here, the biocarbon content can be expressed as the number of carbon elements in percentage.

[0053] Furthermore, the isosorbide epoxy compound may be a single isosorbide epoxide of chemical formula 1, or a mixture of isosorbide epoxides with different substituents R and / or index n. When various types of isosorbide epoxides exist, substituent R can be applied in a variety of ways as explicitly shown in chemical formula 1. Also, n can be applied in a variety of ways, satisfying values ​​from 0 to 100. Specifically, n may be a value satisfying values ​​from 0 to 40.

[0054] According to one embodiment of the present invention, in a method for producing an isosorbide-based epoxy compound, the yield of the isosorbide-based epoxy compound obtained in the step of obtaining the isosorbide-based epoxy compound may be 90% or more. Specifically, the yield of the isosorbide-based epoxy compound in the filtrate obtained by the candle filter device may be 90% or more but less than 100%, 95% or more but less than 100%, 96% or more but less than 100%, 97% or more but less than 100%, or 98% or more but less than 100%. As described above, the yield of the isosorbide-based epoxy compound in the synthesis reaction result can be improved by introducing it into a candle filter device and recovering the isosorbide-based epoxy compound remaining in the salt while filtering out the salt.

[0055] One embodiment of the present invention provides a paint composition comprising a synthetic reaction product composition of the isosorbide-based epoxy compound.

[0056] A paint composition according to one embodiment of the present invention, by including the synthesis reaction product composition of the isosorbide-based epoxy compound, can ensure the physical properties required of paints, such as adhesion, moisture resistance, light resistance, and humidity resistance, while maintaining environmental friendliness, excellent paintability, and appearance.

[0057] The method for producing the isosorbide-based epoxy compounds described above will be explained below, broken down by each step of the process.

[0058] (S10) Step to obtain the reaction product

[0059] Step (S10) is a step in which isosorbide is reacted with an organic halide and a basic compound in the presence of a phase transition catalyst to obtain a reaction product containing a salt and an isosorbide-based epoxy compound.

[0060] The present invention provides a method for producing an isosorbide-based epoxy compound, characterized in that, in step (S10), isosorbide and an organic halide are mixed in the presence of a phase transition catalyst to carry out a ring-opening reaction, and thereafter a basic compound is reacted to carry out a substitution reaction and a ring-closing reaction to obtain a reaction product containing a salt and an isosorbide-based epoxy compound.

[0061] The reaction product obtained in step (S10) may include an isosorbide epoxy compound, a phase transition catalyst, an organic halide, hydrolyzable chlorine, and a salt.

[0062] <(S11) Ring-opening reaction>

[0063] This step involves mixing isosorbide and an organic halide in the presence of a phase transition catalyst, and carrying out the ring-opening reaction under atmospheric pressure conditions, rather than the existing reduced-pressure conditions, in a mild atmosphere at a temperature of 40°C to 100°C.

[0064] Specifically, the ring-opening reaction pressure can be carried out at 752 mmHg to 768 mmHg, or 755 mmHg to 765 mmHg, or 758 mmHg to 762 mmHg. As an example, the ring-opening reaction can be carried out under a pressure condition of about 760 mmHg.

[0065] In addition, the ring-opening reaction temperature can be 45 °C or higher, or 48 °C or higher, or 50 °C or higher and 90 °C or lower, or 80 °C or lower, or 70 °C or lower, or 65 °C or lower, or 60 °C or lower. As an example, the ring-opening reaction can be carried out under a temperature condition of 48 °C to 55 °C.

[0066] The ring-opening reaction can be carried out for 0.1 hour to 6 hours. Specifically, it can be carried out for 0.12 hour to 5 hours, 0.14 hour to 3 hours, or 0.16 hour to 2 hours.

[0067] In the method for producing an isosorbide-based epoxy according to the present invention, a compound represented by the following chemical formula 2 can be used as the phase transfer catalyst.

[0068] [Chemical formula 2]

[0069] Ar a R 2 4-a N + (X 1 b ) -

[0070] In the chemical formula 2, Ars are the same as or different from each other, and each independently is a substituted or unsubstituted C 6-20 aryl, or a C 6-20 alkyl substituted with a substituted or unsubstituted C 1-3 aryl, Rs are the same as or different from each other, and each independently is a C 2 alkyl, 1-20 and X 1These are either identical or distinct from one another, and each is independently chloro(Cl), bromo(Br), iod(I), or fluoro(F). a is an integer between 1 and 4. b is an integer between 1 and 3.

[0071] On the other hand, unless otherwise specified, the following terms may be defined as follows:

[0072] The halogen may be fluoro(F), chloro(Cl), bromo(Br), or iodine(I).

[0073] Said C 1-20 The alkyl group, that is, the alkyl group having 1 to 20 carbon atoms, may be linear, branched, or cyclic alkyl group. Specifically, the alkyl group having 1 to 20 carbon atoms may be a linear alkyl group having 1 to 20 carbon atoms; a linear alkyl group having 1 to 15 carbon atoms; a linear 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 alkyl group having 1 to 20 carbon atoms (C 1-20 Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0074] In particular, C 1-3 The alkyl group, i.e., the alkyl group having 1 to 3 carbon atoms, may be a linear or branched alkyl group. Specifically, examples of alkyl groups having 1 to 3 carbon atoms include methyl, ethyl, propyl, and isopropyl, but are not limited to these.

[0075] Said C 6-20The aryl group, i.e., the aryl group having 6 to 20 carbon atoms, may be monocyclic, bicyclic, or tricyclic aromatic hydrocarbons. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, anthracenyl, phenantrenyl, and fluorenyl.

[0076] The substituents described above may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl groups; halogens; alkyl or alkenyl, aryl, or alkoxy groups; alkyl or alkenyl, aryl, or alkoxy groups containing one or more heteroatoms from groups 14 to 16; silyl groups; alkylsilyl or alkoxysilyl groups; phosphine groups; phosphine groups; sulfonate groups; and sulfone groups, within the range that exhibits the same or similar effects as the desired effect.

[0077] As an example, the phase transition catalyst represented by chemical formula 2 may be one or more 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 transition catalyst represented by chemical formula 2 may be one or more of benzyltrimethylammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), or benzyltributylammonium chloride (BTBAC). More preferably, the phase transition catalyst represented by chemical formula 2 may be benzyltriethylammonium chloride (BTEAC).

[0078] In step (S10), the phase transition catalyst can be added in an amount of 0.1% to 6% by weight based on the weight of the isosorbide. Specifically, the phase transition catalyst can be added in amounts of 0.3% to 5.5% by weight, 0.5% to 5% by weight, 0.7% to 4.5% by weight, 0.9% to 4% by weight, 1.1% to 3.5% by weight, 1.3% to 3% by weight, or 1.5% to 2.5% by weight.

[0079] In step (S10), the organic halogen may be one or more selected from the group consisting of epibromohydrin, epifluorohydrin, epiiodohydrin, and epichlorohydrin. Preferably, the organic halogen may be epichlorohydrin.

[0080] In step (S10), the organic halide can be added in an amount of 1.0 mole to 20.0 moles relative to the isosorbide hydroxyl groups. For example, the organic halide can be added in amounts of 1.5 mole to 18.0 moles, 2.0 mole to 15.0 moles, 2.5 mole to 10.0 moles, 3.0 mole to 8.0 moles, and 3.2 mole to 6.0 moles relative to the isosorbide hydroxyl groups.

[0081] <(S12) Substitution reaction>

[0082] This step involves performing a ring-opening reaction, then adding a basic compound, and carrying out an epoxy substitution reaction under atmospheric pressure conditions (not the existing reduced-pressure conditions) in a mild atmosphere at 40°C to 100°C.

[0083] Specifically, the substitution reaction pressure can be 752 mmHg to 768 mmHg, 755 mmHg to 765 mmHg, or 758 mmHg to 762 mmHg. As an example, the substitution reaction can be carried out under pressure conditions of approximately 760 mmHg.

[0084] Furthermore, the substitution reaction temperature can be 45°C or higher, or 48°C or higher, or 50°C or higher and 90°C or lower, or 80°C or lower, or 70°C or lower, or 60°C or lower, or 55°C or lower. For example, the substitution reaction can be carried out under temperature conditions of 50°C to 55°C.

[0085] The substitution reaction can be carried out for 0.1 to 6 hours, specifically for 0.5 to 5 hours, 1.0 to 4 hours, or 1.5 to 3 hours.

[0086] In the substitution reaction, the basic compound may be one or more alkali metal hydroxides. Specifically, the basic compound may be one or more selected from the group consisting of lithium hydroxide, potassium hydroxide, calcium hydroxide, and sodium hydroxide (NaOH). Preferably, the basic compound may be sodium hydroxide (NaOH).

[0087] In the substitution reaction described above, the basic compound can be added in an amount of 0.05 to 2.5 moles relative to the isosorbide hydroxyl groups. For example, the basic compound can be added in amounts of 0.05 to 2.0 moles, 0.06 to 1.5 moles, 0.06 to 1.0 moles, 0.06 to 0.8 moles, 0.07 to 0.5 moles, 0.08 to 0.4 moles, or 0.1 to 0.3 moles relative to the isosorbide hydroxyl groups.

[0088] On the other hand, the pressure difference (△mmHg) between the ring-opening reaction and the substitution reaction described above is close to 0, meaning that the reactions can be carried out under substantially the same pressure conditions.

[0089] <(S13) Ring-closing reaction>

[0090] The process involves a substitution reaction followed by a ring-closing reaction by azeotropic distillation under reduced pressure at a temperature of 40°C to 100°C to obtain a reaction product containing an isosorbide-based epoxy compound and a salt.

[0091] Specifically, the azeotropic distillation reaction pressure can be carried out under pressure conditions of 70 mmHg to 500 mmHg. More specifically, the azeotropic distillation reaction pressure may be 75 mmHg or higher, or 80 mmHg or higher, or 85 mmHg or higher, 90 mmHg or higher, or 95 mmHg or higher, or 100 mmHg or higher, or 110 mmHg or higher, or 120 mmHg or higher, or 130 mmHg or higher, or 140 mmHg or higher, and 480 mmHg or lower, or 450 mmHg or lower, or 420 mmHg or lower, or 400 mmHg or lower, or 380 mmHg or lower, or 350 mmHg or lower, or 320 mmHg or lower, or 300 mmHg or lower, or 280 mmHg or lower, or 250 mmHg or lower, or 220 mmHg or lower, or 200 mmHg or lower. For example, the azeotropic distillation reaction can be carried out under pressure conditions of 140-160 mmHg.

[0092] Furthermore, the azeotropic distillation reaction temperature may be between 40°C and 100°C. Specifically, the azeotropic distillation reaction temperature can be 45°C or higher, or 48°C or higher, or 50°C or higher, or 52°C or higher, or 55°C or higher and 90°C or lower, or 85°C or lower, or 80°C or lower, or 78°C or lower, or 75°C or lower, or 72°C or lower. As an example, the azeotropic distillation reaction can be carried out under temperature conditions of 60°C to 70°C.

[0093] The azeotropic distillation reaction can be carried out by adding a basic compound in the ring-closing reaction, and the basic compound may be one or more alkali metal hydroxides. Specifically, the basic compound may be one or more selected from the group consisting of lithium hydroxide, potassium hydroxide, calcium hydroxide, and sodium hydroxide (NaOH). Preferably, the basic compound may be sodium hydroxide (NaOH).

[0094] In the ring-closing reaction, the basic compound can be added in an amount of 0.05 to 2.5 moles relative to the isosorbide hydroxyl groups. For example, the basic compound can be added in amounts of 0.08 to 2.0 moles, 0.1 to 1.8 moles, 0.2 to 1.6 moles, 0.3 to 1.5 moles, 0.4 to 1.35 moles, 0.5 to 1.2 moles, or 0.7 to 1.1 moles relative to the isosorbide hydroxyl groups.

[0095] Specifically, in the ring-closing reaction, the amount of basic compound added can be approximately 2 to 15 times, 3.5 to 12.5 times, or 4 to 9 times the amount of basic compound added in the ring-closing reaction, based on weight, compared to the amount of basic compound added in the substitution reaction. Preferably, it can be added at approximately 4 times the amount.

[0096] The azeotropic distillation reaction can be carried out for 0.5 to 10 hours, specifically for 1 to 9 hours, 2 to 8 hours, or 3 to 7 hours.

[0097] On the other hand, the pressure difference (β) between the ring-opening reaction and the azeotropic distillation reaction described above may be 250 mmHg or more, or 250 mmHg to 698 mmHg, and more specifically, 270 mmHg or more, or 270 mmHg to 610 mmHg. In particular, in the present invention, the ring-opening reaction is carried out under pressure conditions close to atmospheric pressure, while the azeotropic distillation reaction is carried out under pressure conditions with a relatively large degree of reduced pressure.

[0098] Furthermore, the pressure difference (β) between the substitution reaction and the azeotropic distillation reaction may be 250 mmHg or more, or 250 mmHg to 698 mmHg, and more specifically, 270 mmHg or more, or 270 mmHg to 610 mmHg. In particular, in the present invention, the substitution reaction is carried out under pressure conditions close to atmospheric pressure, while the azeotropic distillation reaction is carried out under pressure conditions with a relatively large degree of reduced pressure.

[0099] (S30) Step to separate the salt and obtain the filtrate.

[0100] Step (S30) involves passing the reaction product obtained in step (S10) through a candle filter under a temperature of 20°C to 100°C to filter out the salt and obtain a filtrate.

[0101] Specifically, the reaction result fluid generated in step (S10) is sent to a candle filter by a pump, where it is separated into a liquid filtrate that permeates the candle filter and a solid salt that is filtered out by the candle filter. The liquid filtrate that has passed through the candle filter may be sent back to the fluid inlet to repeat step (S30) or stored for step (S50) described later.

[0102] By passing the salt through the aforementioned candle filter to obtain a filtrate, the salt present in a solid state is filtered out while recovering the isosorbide-based epoxy compound remaining in the filtered salt, thereby maximizing the yield of the isosorbide-based epoxy compound.

[0103] The filtrate obtained by filtering the salt in step (S30) may contain isosorbide-based epoxy compounds, organic halides, hydrolyzable chlorine, and phase transition catalysts.

[0104] The salt filtered in step (S30) may have a particle size of 2.7 μm or larger, or 3.0 μm or larger.

[0105] The salt filtered in step (S30) may be sodium chloride (NaCl). Specifically, when the salt layer filtered through the candle filter reaches a certain thickness, the rate at which the reaction result material passes through the salt decreases, the filtration efficiency decreases, and the pressure in the filter increases. This allows for the sufficient recovery of the isosorbide-based epoxy compound remaining in the salt, and then the salt layer that has reached the specific thickness can be separated.

[0106] Furthermore, the temperature at which step (S30) is performed may be between 20°C and 100°C. Specifically, step (S30) can be performed at a temperature of 25°C or higher, or 28°C or higher, or 30°C or higher, or 32°C or higher, or 35°C or higher and 90°C or lower, or 80°C or lower, or 70°C or lower, or 60°C or lower, or 50°C or lower, or 40°C or lower. As an example, step (S30) can be performed under temperature conditions of 35°C to 40°C. Preferably, the temperature at which step (S30) is performed may be 35°C.

[0107] (S50) Step to obtain an isosorbide epoxy compound.

[0108] Step (S50) is a step in which organic halides are removed from the filtrate obtained in step (S30) to obtain an isosorbide-based epoxy compound.

[0109] The synthetic reaction result composition obtained in step (S50) may contain an isosorbide-based epoxy compound and hydrolyzable chlorine, and an isosorbide-based epoxy compound can be obtained from the synthetic reaction result composition.

[0110] Specifically, the unreacted organic halides remaining from the filtrate obtained in (S30) can be removed to obtain a synthetic reaction result composition containing the isosorbide-based epoxy compound. When removing the unreacted organic halides, they can be removed by volatilizing them at high temperatures, but they may not be completely removed. Preferably, the unreacted organic halides can be removed after raising the temperature to 160°C and reducing the pressure to a maximum of 5 Torr.

[0111] The following are preferred embodiments for understanding the present invention. However, these embodiments are provided only to facilitate understanding the present invention and do not limit its scope.

[0112] <Examples>

[0113] Example 1

[0114] 100 g of isosorbide (ISB) and 510 g of epichlorohydrin were added to a 1,000 mL round-bottom flask equipped with a condenser with a decanter, a stirrer, and a nitrogen inlet, and dissolved while heating to 60°C. Here, epichlorohydrin (ECH) was added at a ratio of 4 moles (OH) to the hydroxyl groups (OH) of isosorbide. Once the solution in the system was completely dissolved, 2 g of benzyltriethylammonium chloride (BTEAC) was added, and the ring-opening reaction was carried out for 10 minutes under conditions of 50°C and atmospheric pressure (760 mmHg). Here, the benzyltriethylammonium chloride (BTEAC), which is the phase transition catalyst, was added at a ratio of 2% by weight relative to 100% by weight of isosorbide. Following the ring-opening reaction, 22 g of a 50% sodium hydroxide (NaOH) aqueous solution was added in two separate additions at 1-hour intervals, and the epoxy substitution reaction was carried out for 2 hours under conditions of 50°C and atmospheric pressure (760 mmHg). Here, the molar ratio of sodium hydroxide was 0.2 moles relative to the hydroxyl groups (OH) of isosorbide. Subsequently, the temperature was raised to 65°C and under a pressure of 150 mmHg, 88 g of a 50% sodium hydroxide (NaOH) aqueous solution was added quantitatively over 3 hours while continuously removing the reaction water by reflux, and the epoxy ring-closing reaction was carried out by azeotropic distillation under reduced pressure to obtain a reaction product containing a salt and an isosorbide-based epoxy compound. Here, the molar ratio of sodium hydroxide was 0.8 moles relative to the hydroxyl groups (OH) of isosorbide. The total amount of caustic soda added in the substitution and ring-closing reactions was such that it amounted to 1 mole relative to the isosorbide hydroxyl group (OH).

[0115] After the ring-closing reaction described above was completed, the resulting reaction product was placed in a candle filter apparatus, and the salt (NaCl) was filtered out to obtain a salt layer, from which a separate filtrate was obtained. This filtration could be performed at 35°C.

[0116] Epichlorohydrin (ECH) was then heated to 160°C, reduced to a maximum of 5 Torr, and removed to obtain a synthetic reaction composition of an isosorbide-based epoxy compound.

[0117] <Comparative Example>

[0118] Comparative Example 1

[0119] In Example 1, after the ring-closing reaction was completed, 2.2 times the amount of water equivalent to the theoretical salt (NaCl) was added to the obtained first reaction product, stirred, and then transferred to a funnel to remove the aqueous layer at the bottom and remove the salt (NaCl). Except for this, a synthesis reaction product composition of an isosorbide-based epoxy compound was obtained in the same manner as in Example 1.

[0120] The reaction yields in the production process of the isosorbide-based epoxy compound synthesis reaction results compositions according to Example 1 and Comparative Example 1 are shown in Table 1 below.

[0121] [Table 1]

[0122] In Table 1 above, the reaction yield is the total weight of the isosorbide-based epoxy compound in the synthetic reaction result composition produced in step (S50) as a percentage (%) of the total weight of isosorbide added in step (S10).

[0123] <Example Test>

[0124] The synthetic reaction product compositions of isosorbide-based epoxy compounds obtained in Example 1 and Comparative Example 1 were subjected to the following physical property evaluations, and the measured values ​​are shown in Table 2 below.

[0125] a) Content of the compound n=0 in the synthesis reaction result composition of isosorbide epoxy compounds

[0126] The synthesis reaction results compositions of the isosorbide epoxy compounds obtained in Example 1 and Comparative Example 1 were dissolved in THF at a concentration of 2.5 wt% and analyzed by gel permeation chromatography (GPC, Gel Permeation Chromatography systems; Shimazu, Shodex, KF-801, 802, 803, 805 Columns). The analysis temperature was 40°C, and the mobile phase was Tetrahydrofuran (HPLC grade) flowed at 1 mL / min. The GPC data obtained in this way confirmed the content (GPC, %) of the isosorbide diglycidyl ether (n=0) compound in the total content of the composition.

[0127] b) Epoxy group equivalent

[0128] The epoxy group equivalents of the isosorbide-based epoxy compounds obtained in Example 1 and Comparative Example 1 were measured by neutralization titration. Specifically, the isosorbide-based epoxy compound synthesis reaction result compositions were dissolved in 1,4-Dioxane, reacted with a 0.2N-HCl solution, and then titrated with a 0.1N-NaOH-Methanol solution to measure the epoxy group equivalents (EEW, g / eq). Here, the epoxy group equivalents (EEW, g / eq) represent the molecular weight divided by the number of reactive groups, and can be measured, for example, by neutralization titration.

[0129] c) Viscosity

[0130] The viscosity (cPs) of the isosorbide-based epoxy compound synthesis reaction compositions obtained in Example 1 and Comparative Example 1 was measured at 25°C using a rotational viscometer and a Brookfield viscometer. Brookfield viscosity represents the fluid resistance value applied to the spindle using a rotational viscometer.

[0131] d) Concentration of hydrolyzable chlorine (Hy-Cl)

[0132] The hydrolyzable chlorine content in the synthesis reaction results compositions of isosorbide-based epoxy compounds obtained in Example 1 and Comparative Example 1 was measured by a neutralization titration method. Specifically, the synthesis reaction results compositions of the isosorbide-based epoxy compounds were dissolved in 1,4-Dioxane, a 0.1N KOH-methanol solution was added, a condenser was attached, and the mixture was heated at 70°C to react. After that, glacial acetic acid was added, and the concentration of hydrolyzable chlorine was measured by titration with an aqueous AgNO3 solution.

[0133] [Table 2]

[0134] As shown in Table 2 above, in Example 1, in which the reaction result logistics obtained by performing step (S10) according to the present invention was put into a candle filter apparatus and the salt was filtered out to remove epichlorohydrin, the epoxy group equivalent and viscosity were higher compared to Comparative Example 1, which used a method in which water was added and transferred to a funnel before removing the salt. In particular, the concentration of hydrolyzable chlorine (Hy-Cl), a by-product, was significantly reduced, and it was confirmed that the production yield of isosorbide-based epoxy compounds was significantly improved.

Claims

1. Isosorbide epoxy compounds represented by the following chemical formula 1; and Contains hydrolyzable chlorine; The hydrolyzable chlorine content is less than 5,000 ppm. Composition resulting from the synthesis reaction of isosorbide-based epoxy compounds: [Chemical formula 1] 【Chemistry 1】 In the aforementioned chemical formula 1, R is H or 【Chemistry 2】 And, n is an integer between 0 and 100.

2. The compound in which n in the chemical formula 1 is 0 is present in an amount of 40 wt% to 70 wt% of the total weight of the isosorbide-based epoxy compound. A composition resulting from the synthesis reaction of an isosorbide-based epoxy compound as described in claim 1.

3. The epoxy group equivalent is 120 g / eq to 500 g / eq. A composition resulting from the synthesis reaction of an isosorbide-based epoxy compound as described in claim 1.

4. The Brookfield viscosity measured at 25°C is between 500 cPs and 2,000 cPs. A composition resulting from the synthesis reaction of an isosorbide-based epoxy compound as described in claim 1.

5. (S10) A step of reacting isosorbide, an organic halide, and a basic compound in the presence of a phase transition catalyst to obtain a reaction product containing a salt and an isosorbide-based epoxy compound, (S30) The reaction product is put into a candle filter device to filter out the salt and obtain a filtrate, (S50) The step of removing organic halides from the filtrate to obtain an isosorbide-based epoxy compound, A method for producing isosorbide-based epoxy compounds.

6. The step of obtaining the reaction result is: (S11) A step of mixing the isosorbide and the organic halide in the presence of the phase transition catalyst and carrying out a ring-opening reaction under temperature conditions of 40°C to 100°C, (S12) The basic compound is added to the product of the ring-opening reaction, and an epoxy substitution reaction is carried out under temperature conditions of 40°C to 100°C. (S13) The process includes the step of carrying out a ring-closing reaction of the product of the substitution reaction by azeotropic distillation under reduced pressure at a temperature of 40°C to 100°C, A method for producing an isosorbide-based epoxy compound according to claim 5.

7. The aforementioned candle filter device is Filter out salts with a particle size of 2.7 μm or larger. A method for producing an isosorbide-based epoxy compound according to claim 5.

8. The step of obtaining the aforementioned filtrate is, This step involves filtration while maintaining a temperature of 20°C to 100°C. A method for producing an isosorbide-based epoxy compound according to claim 5.

9. The isosorbide epoxy compound is Represented by the following chemical formula 1, A method for producing the isosorbide-based epoxy compound according to claim 5: [Chemical formula 1] 【Transformation 3】 In the aforementioned chemical formula 1, R is H or 【Chemistry 4】 And, n is an integer between 0 and 100.

10. The yield of the isosorbide-based epoxy compound obtained in the step of obtaining the isosorbide-based epoxy compound is 90% or more. A method for producing an isosorbide-based epoxy compound according to claim 5.

11. A paint composition comprising a synthetic reaction product composition of an isosorbide-based epoxy compound according to any one of claims 1 to 4.

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