Composition of synthesis reaction product of isosorbide-based epoxy compound, paint composition comprising same, and method for preparing isosorbide-based epoxy compound

Abstract

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

Description

Composition of synthetic reaction product of isosorbide-based epoxy compound and paint composition containing same, method for producing isosorbide-based epoxy compound

[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] The present invention relates to a composition resulting from a synthetic reaction of an isosorbide-based epoxy compound having low viscosity and high purity, a paint composition comprising the same, and a method for producing an isosorbide-based epoxy compound with improved yield.

[0003] Typically, 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 derived from biomass resources such as plants.

[0004] In particular, as environmental issues arising from the use of petroleum resources intensify, the sustainability and eco-friendly advantages of biomass resources are increasingly highlighted. From this perspective, the development of biomass-based monomer and polymer production technologies is a critical issue in both academia and industry. In particular, concerns about the potential for increased carbon dioxide emissions and their accumulation, leading to global warming and climate change, are driving the development of polymer resins made from plant-derived monomers that produce extremely low carbon emissions during the manufacturing process.

[0005] Along with the sustainability and environmental friendliness of biomass resources, there is an increasing need for the development of novel polymers with a carbon skeleton structure that can secure mechanical properties equivalent to or superior to those of petroleum-based polymers, as well as low glass transition temperatures.

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

[0007] Methods for producing epoxy resins by reacting isosorbide with epichlorohydrin have been known in various ways and have been described in numerous publications. However, most of the methods described in the literature result in the synthesis of isosorbide diglycidyl ether (n=0) in the form of n=1 or higher, resulting in a higher viscosity. For example, most of the synthesis methods using commercially available caustic soda in the literature have shown viscosities exceeding 10,000 cps at room temperature.

[0008] In addition, when manufacturing isosorbide epoxy resin using most of the manufacturing methods in the literature, it was difficult to additionally recover the epoxy resin remaining in the salt layer, making it difficult to achieve a yield exceeding 90%.

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

[0010] The present invention provides a composition of a synthetic reaction product of an isosorbide-based epoxy compound having the advantages of sustainability of biomass resources and being environmentally friendly, low viscosity and high purity, a paint composition including the same, and a method for producing an isosorbide-based epoxy compound with improved yield, in order to solve the problems of the prior art as described above.

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

[0012] One embodiment of the present invention for achieving the above-described purpose provides a composition as a result of a synthetic reaction of an isosorbide-based epoxy compound, which comprises 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 5,000 ppm.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1,

[0016] R is H or And,

[0017] n is an integer from 0 to 100.

[0018] Another 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 transfer catalyst to obtain a reaction product including a salt and an isosorbide-based epoxy compound; (S30) introducing the reaction product into a candle filter device to filter out the salt and obtain a filtrate; and (S50) removing the organic halide from the filtrate to obtain the isosorbide-based epoxy compound.

[0019] The composition of the synthetic reaction result of an isosorbide-based epoxy compound according to one embodiment of the present invention can provide a composition of the synthetic reaction result of an isosorbide-based epoxy compound having low viscosity and high purity by containing less than 5,000 ppm of hydrolyzable chlorine.

[0020] The method for producing an isosorbide-based epoxy compound according to one embodiment of the present invention can filter out salt using a candle filter device to recover the remaining isosorbide-based epoxy compound, thereby producing a high yield of isosorbide-based epoxy compound.

[0021] A paint composition according to one embodiment of the present invention can provide an environmentally friendly paint composition having excellent paint workability and physical properties by including a composition resulting from a synthetic reaction of the isosorbide-based epoxy compound.

[0022] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0023] In this specification, “A and / or B” means “A and B, or A or B.”

[0024] In this specification, and means a bond that connects to another substituent.

[0025] Hereinafter, the present invention will be described in more detail.

[0026] One embodiment of the present invention provides a composition resulting from a synthetic reaction of an isosorbide-based epoxy compound, which comprises 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 5,000 ppm.

[0027] [Chemical Formula 1]

[0028]

[0029] In the above chemical formula 1,

[0030] R is H or And,

[0031] n is an integer from 0 to 100.

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

[0033] The composition resulting from the synthesis reaction of an isosorbide-based epoxy compound according to one embodiment of the present invention comprises an isosorbide-based epoxy compound represented by the above chemical formula 1. Specifically, by including isosorbide having a high biocarbon content, it can have the advantages of sustainability of biomass resources and being environmentally friendly.

[0034] According to one embodiment of the present invention, the isosorbide-based epoxy compound may be a single isosorbide epoxide of Chemical Formula 1 or a mixture of isosorbide epoxides having different substituents R and / or indexes n. When multiple types of isosorbide epoxides exist, the substituent R may be applied in various ways as specified in Chemical Formula 1. In addition, n may be applied in various ways as a value satisfying 0 to 100. Specifically, n may be a value satisfying 0 to 40.

[0035] According to one embodiment of the present invention, a composition resulting from a synthetic reaction of an isosorbide-based epoxy compound includes a hydrolyzable chlorine component. Specifically, the hydrolyzable chlorine component (hydrolyzed chloride (Hy-Cl)) refers to chlorine that can be hydrolyzed among the chlorine remaining without reacting with a basic compound during the manufacturing process of the isosorbide-based epoxy compound, and may be related to the purity of the isosorbide-based epoxy compound. For example, the hydrolyzable chlorine component may be a halohydrin ether intermediate, but is not limited thereto, and may include a compound corresponding to a hydrolyzable chlorine component generated in a synthetic reaction of a known isosorbide-based epoxy compound.

[0036] According to one embodiment of the present invention, the composition resulting from the synthesis reaction of an isosorbide-based epoxy compound contains less than 5,000 ppm of the hydrolyzable chlorine. Specifically, the composition resulting from the synthesis reaction of the isosorbide-based epoxy compound may contain less than 2,000 ppm of the hydrolyzable chlorine. Preferably, the composition may contain 500 ppm to 1,650 ppm of the hydrolyzable chlorine. Since the composition resulting from the synthesis reaction of the isosorbide-based epoxy compound contains less than the above-described concentration of the hydrolyzable chlorine, it can be seen that the composition resulting from the synthesis reaction 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 is 0 in the chemical formula 1 may be in an amount of 40 wt% to 70 wt% based on the total weight of the isosorbide-based epoxy compound. Specifically, the compound in which n is 0 in the chemical formula 1 may be in an amount of 50 wt% to 60 wt% based on the total weight of the isosorbide-based epoxy compound. By controlling the ratio of the compound in which n is 0 in the chemical formula 1 within the above-described range, the purity of the isosorbide-based epoxy compound can be controlled.

[0038] According to one embodiment of the present invention, the composition resulting from the synthetic reaction 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 included in the composition resulting from the synthetic reaction 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 represents a value obtained by dividing the molecular weight by the number of reactive groups, and may be measured, for example, by a neutralization titration method.

[0039] According to one embodiment of the present invention, the composition resulting from the synthetic reaction 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 composition resulting from the synthetic reaction 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, the Brookfield viscosity represents the resistance value of a fluid applied to a 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 transfer catalyst to obtain a reaction product including a salt and an isosorbide-based epoxy compound; (S30) introducing the reaction product into a candle filter device 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 composition resulting from the synthesis reaction of the isosorbide-based epoxy compound according to one embodiment of the present invention can be produced as the composition resulting from the synthesis reaction in the method for producing the isosorbide-based epoxy compound.

[0042] Through a method for producing an isosorbide-based epoxy compound according to one embodiment of the present invention, an isosorbide-based epoxy compound having low viscosity, high purity, and significantly improved yield can be produced.

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

[0044] The candle filter may be, specifically, a candle-shaped cylindrical filter composed of a porous, permeable material. By pressurizing and filtering a fluid using the candle filter, desired solid particles having a predetermined size or larger can be filtered out and separated from the liquid. For example, in the method for producing the isosorbide-based epoxy compound, the reaction product can be pressurized and filtered using the candle filter, thereby preventing the solid salt from passing through the porous, permeable material within the candle filter and separating it from the filtrate.

[0045] According to one embodiment of the present invention, in the method for producing an isosorbide-based epoxy compound, the candle filter device can filter a salt having a particle size of 2.7 μm or more. Preferably, the candle filter device can filter a salt having a particle size of 3.0 μm or more. The candle filter device can filter a salt existing in a solid state in the reaction product fluid, and thereby recover the isosorbide-based epoxy compound remaining in the filtered salt, thereby improving the yield.

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

[0050] In the above chemical formula 1,

[0051] R is H or And,

[0052] n is an integer from 0 to 100.

[0053] Specifically, the isosorbide-based epoxy compound is a bio-derived compound rather than a conventional petroleum-based compound as described above, and is characterized by a biocarbon content of 100% based on 100% of the total carbon number. Here, the biocarbon content can be measured by calculating the ratio of bio-derived carbon to the total organic carbon. For example, the biocarbon content of the isosorbide-based epoxy compound is a radioisotope ( 14 C) It can be measured by inferring the number ratio (%), and specifically, it can be measured according to the American Society for Testing and Materials ASTM D 6866 standard. Here, the biocarbon content can be said to be expressed as a number % according to the carbon number ratio.

[0054] In addition, the isosorbide-based epoxy compound may be a single isosorbide epoxide of Chemical Formula 1 or a mixture of isosorbide epoxides having different substituents R and / or indexes n. When multiple types of isosorbide epoxides exist, the substituent R may be applied in various ways as specified in Chemical Formula 1. In addition, n may be applied in various ways as a value satisfying 0 to 100. Specifically, n may be a value satisfying 0 to 40.

[0055] According to one embodiment of the present invention, in the 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 through the candle filter device may 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 filtering the salt by putting it into the candle filter device and recovering the isosorbide-based epoxy compound remaining in the salt, the yield of the isosorbide-based epoxy compound in the resultant of the synthesis reaction can be improved.

[0056] One embodiment of the present invention provides a paint composition comprising a composition resulting from a synthetic reaction of the isosorbide-based epoxy compound.

[0057] A paint composition according to one embodiment of the present invention comprises a composition resulting from a synthetic reaction of the isosorbide-based epoxy compound, thereby maintaining environmental friendliness and excellent paint workability and appearance while securing properties required for paint, such as adhesion, moisture resistance, light resistance, and moisture resistance.

[0058] Hereinafter, the manufacturing method of the above-described isosorbide-based epoxy compound is explained step by step as follows.

[0059]

[0060] (S10) Step for obtaining reaction results

[0061] Step (S10) is a step of reacting isosorbide with an organic halide and a basic compound in the presence of a phase transfer catalyst to obtain a reaction product including a salt and an isosorbide-based epoxy compound.

[0062] The method for producing an isosorbide-based epoxy compound according to the present invention is characterized by performing a process of mixing isosorbide and an organic halide in the presence of a phase transfer catalyst in step (S10) to perform a ring-opening reaction, and then reacting a basic compound to perform a substitution reaction and a ring-closing reaction to obtain a reaction product including a salt and an isosorbide-based epoxy compound.

[0063] The reaction product obtained according to step (S10) may include an isosorbide-based epoxy compound, a phase transfer catalyst, an organic halide, a hydrolyzable chlorine component, and a salt.

[0064]

[0065] <(S11) Opening reaction>

[0066] This is a step of performing a ring-opening reaction under atmospheric pressure conditions rather than the conventional reduced pressure conditions in a mild atmosphere of 40°C to 100°C by mixing isosorbide and organic halides in the presence of a phase transfer catalyst.

[0067] Specifically, the ring opening reaction pressure may be performed at 752 mmHg to 768 mmHg, or 755 mmHg to 765 mmHg, or 758 mmHg to 762 mmHg. For example, the ring opening reaction may be performed under a pressure condition of about 760 mmHg.

[0068] In addition, the ring-opening reaction temperature may 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. For example, the ring-opening reaction may be performed under a temperature condition of 48°C to 55°C.

[0069] The above ring opening reaction can be carried out for 0.1 to 6 hours, specifically for 0.12 to 5 hours, for 0.14 to 3 hours, or for 0.16 to 2 hours.

[0070]

[0071] The method for producing an isosorbide-based epoxy 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 1 b ) -

[0074] In the above chemical formula 2,

[0075] Ar are identical or different and each independently represents a substituted or unsubstituted C 6-20 Aryl, or substituted or unsubstituted C 6-20 C substituted with aryl 1-3 is alkyl,

[0076] R 2 are identical or different from each other, and each is independently C 1-20 It is alkyl,

[0077] X 1 are the same or different from each other, and each independently represents chloro (Cl), bromo (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]

[0081] Meanwhile, in this specification, unless otherwise specifically limited, the following terms may be defined as follows:

[0082] The halogen can be fluorine (F), chloro (Cl), bromo (Br), or iodine (I).

[0083] C above 1-20 The alkyl, i.e., alkyl having 1 to 20 carbon atoms, may be straight-chain, branched-chain or cyclic alkyl. Specifically, the alkyl having 1 to 20 carbon atoms may be straight-chain alkyl having 1 to 20 carbon atoms; straight-chain alkyl having 1 to 15 carbon atoms; straight-chain alkyl having 1 to 5 carbon atoms; branched-chain or cyclic alkyl having 3 to 20 carbon atoms; branched-chain or cyclic alkyl having 3 to 15 carbon atoms; or branched-chain or cyclic alkyl having 3 to 10 carbon atoms. For example, the alkyl having 1 to 20 carbon atoms (C 1-20 ) 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.

[0084] In particular, the above C 1-3 The alkyl, i.e., alkyl having 1 to 3 carbon atoms, may be straight-chain or branched-chain alkyl. Specifically, alkyl having 1 to 3 carbon atoms includes, but is not limited to, methyl, ethyl, propyl, isopropyl, etc.

[0085] C above 6-20 The aryl, i.e., aryl having 6 to 20 carbon atoms, may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Examples of the aryl include, but are not limited to, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, and the like.

[0086] The above-described substituents may be optionally substituted with one or more substituents selected from the group consisting of a hydroxy group; a halogen; an alkyl or alkenyl, an aryl, an alkoxy; an alkyl or alkenyl, an aryl, an alkoxy containing one or more heteroatoms of groups 14 to 16; a silyl; an alkylsilyl or alkoxysilyl; a phosphine group; a phosphide group; a sulfonate group; and a sulfone group, within a range that exhibits the same or similar effect as the desired effect.

[0087] For example, the phase transfer catalyst represented by the above chemical formula 2 may 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 may be at least one selected from the group consisting of benzyltrimethylammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), and benzyltributylammonium chloride (BTBAC). More preferably, the phase transfer catalyst represented by the above chemical formula 2 may be benzyltriethylammonium chloride (BTEAC).

[0088] In step (S10), the phase transfer catalyst may be added in an amount of 0.1 wt% to 6 wt% based on the weight of the isosorbide. Specifically, the phase transfer catalyst may be added in an amount 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%.

[0089] In step (S10), the organic halide may be at least one selected from the group consisting of epibromohydrin, epifluorohydrin, epiiodohydrin, and epichlorohydrin. Preferably, the organic halide may be epichlorohydrin.

[0090] In step (S10), the organic halide may be introduced in an amount of 1.0 mol to 20.0 mol relative to the isosorbide hydroxyl group. For example, the organic halide may be introduced in an amount 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.

[0091]

[0092] <(S12) Substitution reaction>

[0093] After performing the ring opening reaction, this is a step of adding a basic compound and performing an epoxy substitution reaction under normal pressure conditions rather than the existing reduced pressure conditions in a mild atmosphere of 40°C to 100°C.

[0094] Specifically, the substitution reaction pressure may be performed at 752 mmHg to 768 mmHg, 755 mmHg to 765 mmHg, or 758 mmHg to 762 mmHg. For example, the substitution reaction may be performed under a pressure condition of about 760 mmHg.

[0095] In addition, the substitution reaction temperature may 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 may be performed under a temperature condition of 50°C to 55°C.

[0096] The above 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.

[0097] In the above 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).

[0098] In the above substitution reaction, the basic compound may be introduced in an amount of 0.05 mol to 2.5 mol relative to the isosorbide hydroxyl group. For example, the basic compound may be introduced 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.

[0099] Meanwhile, in the above-described ring opening reaction and the substitution reaction, the pressure difference (△mmHg) of the substitution reaction is close to 0, and can be performed under substantially the same pressure conditions.

[0100]

[0101] <(S13) Ring closure reaction>

[0102] After performing the substitution reaction, this is a step of performing a ring closure reaction by an azeotropic distillation reaction under reduced pressure conditions at a temperature of 40°C to 100°C to obtain a reaction product including an isosorbide-based epoxy compound and a salt.

[0103] Specifically, the azeotropic distillation reaction pressure can be performed under pressure conditions of 70 mmHg to 500 mmHg. More specifically, the azeotropic distillation reaction pressure may be 75 mmHg or more, or 80 mmHg or more, or 85 mmHg or more, or 90 mmHg or more, or 95 mmHg or more, or 100 mmHg or more, or 110 mmHg or more, or 120 mmHg or more, or 130 mmHg or more, or 140 mmHg or more, and 480 mmHg or less, or 450 mmHg or less, or 420 mmHg or less, or 400 mmHg or less, or 380 mmHg or less, or 350 mmHg or less, or 320 mmHg or less, or 300 mmHg or less, or 280 mmHg or less, or 250 mmHg or less, or 220 mmHg or less, or 200 mmHg or less. For example, the azeotropic distillation reaction can be performed under pressure conditions of 140 to 160 mmHg.

[0104] In addition, the azeotropic distillation reaction temperature may be 40° C. to 100° C. Specifically, the azeotropic distillation reaction temperature may 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. For example, the azeotropic distillation reaction may be performed under a temperature condition of 60° C. to 70° C.

[0105] In the above ring-closing reaction, a basic compound may be additionally added and the azeotropic distillation reaction may be performed. 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).

[0106] In the above ring-closing reaction, the basic compound may be introduced in an amount of 0.05 mol to 2.5 mol relative to the isosorbide hydroxyl group. For example, the basic compound may be introduced in an amount 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.

[0107] Specifically, in the above-described ring-closure reaction, the amount of the basic compound input may be about 2 to about 15 times, about 3.5 to about 12.5 times, or about 4 to about 9 times, based on weight, the amount of the basic compound input in the above-described substitution reaction, while the basic compound is input in the molar ratio as described above. Preferably, the amount may be about 4 times.

[0108] The above 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.

[0109] Meanwhile, the pressure difference (β) of the ring opening reaction and the azeotropic distillation reaction described above may be 250 mmHg or more or 250 mmHg to 698 mmHg, and specifically, 270 mmHg or more or 270 mmHg to 610 mmHg. In particular, in the present invention, the ring opening reaction is performed under pressure conditions close to atmospheric pressure, whereas the azeotropic distillation reaction is performed under pressure conditions with a relatively large degree of reduced pressure.

[0110] In addition, the pressure difference (β) of the above-described substitution reaction and the azeotropic distillation reaction may be 250 mmHg or more or 250 mmHg to 698 mmHg, and specifically, 270 mmHg or more or 270 mmHg to 610 mmHg. In particular, in the present invention, the substitution reaction is performed under pressure conditions close to atmospheric pressure, whereas the azeotropic distillation reaction is performed under pressure conditions with a relatively large degree of reduced pressure.

[0111]

[0112] (S30) Step for separating salt and obtaining filtrate

[0113] Step (S30) is a step of filtering the salt by passing the reaction product obtained through step (S10) through a candle filter device under temperature conditions of 20°C to 100°C and obtaining a filtrate.

[0114] Specifically, the reaction product fluid generated through step (S10) is sent to a candle filter by a pump, and as it passes through the candle filter, it is separated into a liquid filtrate that passes through the candle filter and a solid salt that is filtered out by the candle filter. The liquid filtrate that passes through the candle filter can be sent back to the fluid inlet to perform step (S30) again or stored to perform step (S50) described below.

[0115] By filtering the salt and obtaining a filtrate by passing it through the candle filter, the yield of the isosorbide-based epoxy compound can be maximized by filtering the salt existing in a solid state and recovering the isosorbide-based epoxy compound remaining in the filtered salt.

[0116] In step (S30), the salt is filtered and the obtained filtrate may include an isosorbide-based epoxy compound, an organic halide, a hydrolyzable chlorine component, and a phase transfer catalyst.

[0117] The salt filtered in step (S30) may have a particle size of 2.7 ㎛ or more or 3.0 ㎛ or more.

[0118] The salt filtered in step (S30) may be sodium chloride (NaCl). Specifically, when the salt layer filtered through the candle filter reaches a specific 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 sufficiently recovering the isosorbide-based epoxy compound remaining in the salt, the salt layer that has reached the specific thickness can be separated.

[0119] In addition, the temperature at which step (S30) is performed may be 20°C to 100°C. Specifically, the temperature at which step (S30) is performed may be 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. For example, the temperature at which step (S30) is performed may be performed under a temperature condition of 35°C to 40°C. Preferably, the temperature at which step (S30) is performed may be 35°C.

[0120]

[0121] (S50) Step for obtaining an isosorbide-based epoxy compound

[0122] Step (S50) is a step of removing organic halides from the filtrate obtained through step (S30) to obtain an isosorbide-based epoxy compound.

[0123] The composition resulting from the synthetic reaction obtained in step (S50) may include an isosorbide-based epoxy compound and a hydrolyzable chlorine component, and an isosorbide-based epoxy compound may be obtained from the composition resulting from the synthetic reaction.

[0124] Specifically, the unreacted organic halides remaining from the filtrate obtained in (S30) can be removed to obtain a composition resulting from the synthetic reaction including the isosorbide-based epoxy compound. When removing the unreacted organic halides remaining, the organic halides can be removed by volatilization at a high temperature, but may not be completely removed. Preferably, the temperature can be increased to 160°C and the pressure reduced to a maximum of 5 Torr to remove the unreacted organic halides remaining.

[0125] Hereinafter, preferred examples are presented to aid in understanding the present invention. However, the following examples are provided solely to facilitate a better understanding of the present invention and are not intended to limit the scope of the present invention.

[0126]

[0127] <Example>

[0128] Example 1

[0129] In a 1,000 mL round-bottomed flask equipped with a decanter, a condenser, a stirrer, and a nitrogen inlet, 100 g of isosorbide (ISB) and 510 g of epichlorohydrin were added and dissolved while heating to 60°C. Here, epichlorohydrin (ECH) was added in an amount of 4 moles relative to the hydroxyl groups (OH) of isosorbide. When the solution in the system was completely dissolved, 2 g of benzyltriethylammonium chloride (BTEAC) was added and the ring-opening reaction was performed for 10 minutes under the conditions of 50°C and atmospheric pressure (760 mmHg). Here, benzyltriethylammonium chloride (BTEAC), a phase transfer catalyst, was added in an amount of 2 wt% based on 100 wt% of the weight of isosorbide. And, after the ring-opening reaction, 22 g of 50% caustic soda (NaOH) aqueous solution was added twice every hour, and the epoxy substitution reaction was performed for 2 hours under the conditions of 50 ℃ and atmospheric pressure (760 mmHg). Here, the molar ratio of caustic soda was added so that it was 0.2 moles with respect to the hydroxyl group (OH) of isosorbide. Afterwards, the temperature was raised to 65 ℃, and under the pressure condition of 150 mmHg, 88 g of 50% caustic soda (NaOH) aqueous solution was quantitatively injected for 3 hours while continuously removing the reaction water through reflux reaction, and the epoxy ring-closure reaction was performed by azeotropic distillation under reduced pressure, thereby obtaining a reaction product containing a salt and an isosorbide-based epoxy compound. Here, the molar ratio of caustic soda was added so that it was 0.8 moles with respect to the hydroxyl group (OH) of isosorbide. The total amount of caustic soda added in the above substitution reaction and ring closure reaction was 1 mole relative to the hydroxyl group (OH) of isosorbide.

[0130] After the above-described ring-closure reaction is completed, the resulting reaction product fluid is injected into a candle filter device to filter out the salt (NaCl) to obtain a salt layer, and a filtrate is obtained separately. At this time, the filtration was performed at 35°C.

[0131] From this, epichlorohydrin (ECH) was heated to 160°C, depressurized to a maximum of 5 Torr, and then removed to obtain a composition resulting from the synthetic reaction of an isosorbide-based epoxy compound.

[0132]

[0133] <Comparative Example>

[0134] Comparative Example 1

[0135] After the ring closure reaction in Example 1 was completed, 2.2 times the theoretical salt (NaCl) amount of water was added to the first reaction product obtained, stirred, and transferred to a funnel to remove the lower water layer to remove the salt (NaCl), and a composition resulting from the synthesis reaction of an isosorbide-based epoxy compound was obtained in the same manner as in Example 1, except that the salt (NaCl) was removed.

[0136]

[0137] The reaction yield in the manufacturing process of the composition resulting from the synthetic reaction of the isosorbide-based epoxy compound according to Example 1 and Comparative Example 1 is as shown in Table 1 below.

[0138]

[0139] Example 1 Comparative Example 1 Yield (%) 98.155.4

[0140] In the above Table 1, the reaction yield is a value expressed as a percentage (%) of the total weight of the isosorbide-based epoxy compound in the synthetic reaction result composition produced by step (S50) relative to the total weight of isosorbide introduced in step (S10).

[0141]

[0142] <Example of an exam>

[0143] The composition of the synthetic reaction result of the isosorbide-based epoxy compound obtained according to Example 1 and Comparative Example 1 was evaluated for physical properties as follows, and the measured values ​​are shown in Table 2 below.

[0144]

[0145] a) Content of the compound with n=0 in the composition resulting from the synthetic reaction of isosorbide epoxy compound

[0146] The composition resulting from the synthetic reaction of the isosorbide epoxy compound obtained according to Example 1 and Comparative Example 1 was dissolved in THF at a concentration of 2.5 wt% and subjected to gel permeation chromatography (GPC, Gel Permeation Chromatography systems; Shimazu, Shodex, KF-801, 802, 803, 805 Columns) analysis. At this time, the analysis temperature was 40°C, and Tetrahydrofuran (HPLC grade) was flowed as the mobile phase at 1 mL / min. The content (GPC, %) of the isosorbide diglycidyl ether (n=0) compound among the total content of the composition was confirmed through the GPC data measured in this way.

[0147]

[0148] b) Epoxy group equivalent

[0149] The epoxy group equivalent was measured for the composition resulting from the synthetic reaction of the isosorbide-based epoxy compound obtained according to Example 1 and Comparative Example 1 by a neutralization titration method. Specifically, the composition resulting from the synthetic reaction of the isosorbide-based epoxy compound was dissolved in 1,4-Dioxane, and then a 0.2 N-HCl solution was added to react, and then the epoxy group equivalent (EEW, g / eq) was measured by titrating with a 0.1 N-NaOH methanol solution. Here, the epoxy group equivalent (EEW, g / eq) represents 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.

[0150]

[0151] c) viscosity

[0152] For the compositions resulting from the synthetic reaction of the isosorbide-based epoxy compound obtained according to Example 1 and Comparative Example 1, the viscosity (cPs) was measured at 25°C using a rotational viscometer, a Brookfield viscometer. At this time, the Brookfield viscosity represents the resistance value of the fluid applied to the spindle using a rotational viscometer.

[0153]

[0154] d) Concentration of hydrolyzable chlorine (Hy-Cl)

[0155] The composition resulting from the synthetic reaction of the isosorbide-based epoxy compound obtained according to Example 1 and Comparative Example 1 was measured for the hydrolyzable chlorine content in the composition by a neutralization titration method. Specifically, the composition resulting from the synthetic reaction of the isosorbide-based epoxy compound was dissolved in 1,4-Dioxane, 0.1 N KOH-methanol solution was added, a cooling tube was attached, the mixture was heated at 70° C. for reaction, glacial acetic acid was added, and titration was performed with an aqueous solution of AgNO3 to measure the concentration of hydrolyzable chlorine content.

[0156]

[0157] Example 1 Comparative Example 1 n=0 Content (GPC, %) 55.6 55.5 EEW (g / eq) 161.5 159.3 25 ℃ Viscosity (cPs·s) 122 1893 Hy-Cl Concentration (ppm) 162 0.4 50 4 5.5 Yield (%) 98.1 55.4

[0158] As shown in Table 2 above, Example 1, in which the reaction product fluid obtained by performing step (S10) according to the present invention was injected into a candle filter device to filter out salts and remove epichlorohydrin therefrom, showed higher epoxy group equivalents and viscosity than Comparative Example 1, in which water was injected, transferred to a funnel, and then salts were removed, and in particular, the concentration of hydrolyzable chlorine (Hy-Cl), which is a by-product, was significantly reduced, and it was confirmed that the production yield of the isosorbide-based epoxy compound was significantly improved.

Claims

1. An isosorbide-based epoxy compound represented by the following chemical formula 1; and Contains hydrolyzable chlorine; The above hydrolyzable chlorine content is less than 5,000 ppm. Composition of the synthetic reaction product of isosorbide-based epoxy compound: [Chemical Formula 1] In the above chemical formula 1, R is H or And, n is an integer from 0 to 100.

2. In paragraph 1, In the above chemical formula 1, the compound in which n is 0 is 40 wt% to 70 wt% of the total weight of the isosorbide-based epoxy compound. A composition resulting from the synthetic reaction of an isosorbide-based epoxy compound.

3. In paragraph 1, The epoxy group equivalent weight is 120 g / eq to 500 g / eq. A composition resulting from the synthetic reaction of an isosorbide-based epoxy compound.

4. In paragraph 1, Brookfield viscosity measured at 25°C is 500 cPs to 2,000 cPs. A composition resulting from the synthetic reaction of an isosorbide-based epoxy compound. 5.(S10) A step of reacting isosorbide, an organic halide, and a basic compound in the presence of a phase transfer catalyst to obtain a reaction product including a salt and an isosorbide-based epoxy compound; (S30) A step of putting the above reaction result into a candle filter device to filter the salt and obtain a filtrate; and (S50) A step of removing organic halides from the filtrate to obtain an isosorbide-based epoxy compound; Method for producing an isosorbide-based epoxy compound.

6. In paragraph 5, The steps for obtaining the above reaction results are: (S11) A step of performing a ring-opening reaction by mixing the isosorbide and the organic halide in the presence of the above-mentioned phase transfer catalyst under a temperature condition of 40°C to 100°C; (S12) A step of adding the basic compound to the result of the ring opening reaction and performing an epoxy substitution reaction under temperature conditions of 40°C to 100°C; and (S13) A step of performing a ring closure reaction by azeotropic distillation under reduced pressure conditions at a temperature of 40°C to 100°C on the result of the above substitution reaction; Method for producing an isosorbide-based epoxy compound.

7. In paragraph 5, The above candle filter device, Filtering salt with particle size of 2.7 ㎛ or more Method for producing an isosorbide-based epoxy compound.

8. In paragraph 5, The step of obtaining the above filtrate is: A filtering step that maintains temperature conditions of 20℃ to 100℃. Method for producing an isosorbide-based epoxy compound.

9. In paragraph 5, The above isosorbide-based epoxy compound is, Represented by the following chemical formula 1 Method for preparing isosorbide-based epoxy compounds: [Chemical Formula 1] In the above chemical formula 1, R is H or And, n is an integer from 0 to 100.

10. In paragraph 5, The yield of the isosorbide-based epoxy compound obtained in the step of obtaining the above isosorbide-based epoxy compound is 90% or more. Method for producing an isosorbide-based epoxy compound.

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

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