Manufacturing method of cashew nut shell oil (CNSL) based precursor

Abstract

The present invention relates to a manufacturing method of a precursor based on cashew nut shell oil (CNSL) and, more specifically, to a manufacturing method of the precursor using hydrogenated cardanol in which an unsaturated aromatic ring has been modified.

Description

Method for producing a precursor based on cashew nut shell oil (CNSL)

[0001] The present invention relates to a method for producing a precursor using cardanol obtained from cashew nut shell oil (CNSL).

[0002] Cardanol, an aromatic oil derived from further refining cashew nut shell oil (CNSL), is a natural biomass raw material with chemical and corrosion resistance, high adhesiveness, insulating properties, water resistance, and flexibility. The market for cardanol is steadily expanding, driven by the global trend toward low-carbon and eco-friendly products. Furthermore, because the material is non-edible, its applications in paint and coating markets are increasing. Major known uses include epoxy coatings, as a non-reactive diluent for flooring materials, as an isocyanate blocker, and as a raw material for chemical material synthesis.

[0003] Meanwhile, CNSL can be processed to produce high-purity, brightly colored cardanol grades. Cardanol is a unique and versatile material that can be used as is (e.g., as a diluent or NCO blocker) or as a starting monomer for various polymers. As seen in the average structure of cardanol, the long aliphatic chains provide excellent water and moisture resistance, flexibility, and excellent surface wetting properties, while the aromatic rings impart excellent chemical, heat, and flame resistance. The phenolic hydroxyls provide excellent adhesion, slight polarity (surfactant properties), and accelerate the epoxy-amine reaction.

[0004] Cardanol is a versatile, biorenewable monomer with numerous performance advantages. However, while incorporating cardanol into formulations offers numerous performance benefits, the unsaturation of its side chains and aromatic rings makes it susceptible to oxidation and, through side reactions, adversely affects the mechanical and chemical properties of resins when manufactured.

[0005] Therefore, the present invention aims to solve the above problems by using hydrogenated cardanol produced by hydrogenating an unsaturated side chain instead of conventional cardanol.

[0006] The present invention has been devised to solve the above problems, and the purpose of the present invention is to provide a method for producing a cardanol-based precursor that can solve problems that occur when using existing cardanol derivatives by using hydrogenated cardanol in which an unsaturated aromatic ring is modified.

[0007] The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0008] In order to achieve the above object, the present invention comprises: (A) a step of mixing cardanol, potassium hydroxide, methyl iodide and dimethyl sulfoxide represented by the following chemical formula 1 and stirring at room temperature to synthesize a compound represented by the following chemical formula 2; (B) a step of mixing the compound represented by the following chemical formula 2 prepared in step (A), N-bromosuccinimide, hydrogen chloride and acetone and stirring at room temperature to synthesize a compound represented by the following chemical formula 3; (C) a step of mixing mequinol, potassium hydroxide, dimethylacetamide and toluene and stirring to synthesize a first product; (D) a step of mixing the compound represented by the following chemical formula 3 prepared in step (B), the first product, copper and dimethylacetimide and stirring to synthesize a compound represented by the following chemical formula 4; And (E) a step of mixing and stirring the compound represented by the following chemical formula 4 manufactured in step (D), acetic acid and hydrobromic acid to synthesize a compound represented by the following chemical formula 5 is provided.

[0009]

[0010] [Chemical Formula 1]

[0011]

[0012] [Chemical Formula 2]

[0013]

[0014] [Chemical Formula 3]

[0015]

[0016] [Chemical Formula 4]

[0017]

[0018] [Chemical Formula 5]

[0019]

[0020] In the above chemical formulas 1 to 5, R is as follows:

[0021]

[0022]

[0023] In the above step (A), a molar ratio of 2 to 5 of the potassium hydroxide and a molar ratio of 3 to 15 of the dimethyl sulfoxide can be mixed with respect to a molar ratio of 1 of the cardanol.

[0024] The step (B) above may include a step of mixing the compound represented by the chemical formula 2 prepared in the step (A), N-bromosuccinimide, hydrogen chloride, and acetone, and stirring at room temperature to perform a synthesis reaction; and a step of vacuum concentrating the mixture in which the synthesis reaction has been performed to remove acetone, and then removing unreacted substances through a flash chromatography column tube.

[0025] In the above step (C), a molar ratio of 2 to 15 of the dimethylacetamide and a molar ratio of 1 to 5 of the toluene can be mixed with respect to a molar ratio of 1 of the mequinol.

[0026] The above step (D) can be stirred at 170 to 210°C for 7 to 10 hours.

[0027] In the above step (D), the dimethylacetamide can be divided into 5 to 10 parts and additionally added every 1 to 3 hours during the synthetic reaction.

[0028] In the above step (E), 40 to 110 molar ratios of the acetic acid and 8 to 33 molar ratios of the hydrobromic acid can be mixed with respect to 1 molar ratio of the compound represented by the above chemical formula 4.

[0029] By means of solving the above problem, the present invention can provide a method for producing a precursor based on cashew nut shell oil (CNSL) having excellent stability, excellent polymer reactivity and polymerizability, and excellent yield by using hydrogenated cardanol having a modified unsaturated aromatic ring.

[0030] In addition, the cashew oil-based precursor according to the present invention can secure expanded uses and excellent physical properties.

[0031] The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

[0032] Figure 1 shows the NMR analysis results of a compound manufactured in STEP 1 of one embodiment of the present invention.

[0033] Figure 2 shows the NMR analysis results of a compound manufactured in STEP 2 of one embodiment of the present invention.

[0034] Figure 3 shows the NMR analysis results of a compound manufactured in STEP 3 of one embodiment of the present invention.

[0035] Figure 4 shows the NMR analysis results of a compound manufactured in STEP 4 of one embodiment of the present invention.

[0036] The terms used in this invention have been selected from widely used, current terms, taking into account the functions of the invention. However, these terms may vary depending on the intentions of those skilled in the art, precedents, the emergence of new technologies, etc. Furthermore, in certain cases, terms may be arbitrarily selected by the applicant, in which case their meanings will be described in detail in the relevant description of the invention. Therefore, the terms used in this invention should not be defined simply as names, but rather based on their inherent meanings and the overall content of the invention.

[0037] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and will not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0038] When a part of a specification is said to “include” a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise stated.

[0039] Below, with reference to the attached drawings, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0040]

[0041] Hereinafter, the present invention will be described in detail.

[0042]

[0043] The present invention comprises: (A) a step of mixing cardanol, potassium hydroxide, methyl iodide, and dimethyl sulfoxide represented by the following chemical formula 1 and stirring at room temperature to synthesize a compound represented by the following chemical formula 2; (B) a step of mixing the compound represented by the following chemical formula 2 prepared in step (A), N-bromosuccinimide, hydrogen chloride, and acetone, and stirring at room temperature to synthesize a compound represented by the following chemical formula 3; (C) a step of mixing mequinol, potassium hydroxide, dimethyl acetate, and toluene, and stirring to prepare a first product; (D) a step of mixing the compound represented by the following chemical formula 3 prepared in step (B), the first product, copper, and dimethyl acetamide, and stirring to prepare a compound represented by the following chemical formula 4; And (E) a step of mixing and stirring the compound represented by the following chemical formula 4 manufactured in step (D), acetic acid and hydrobromic acid to manufacture a compound represented by the following chemical formula 5 is provided.

[0044] [Chemical Formula 1]

[0045]

[0046] [Chemical Formula 2]

[0047]

[0048] [Chemical Formula 3]

[0049]

[0050] [Chemical Formula 4]

[0051]

[0052] [Chemical Formula 5]

[0053]

[0054] In the above chemical formulas 1 to 5, R is as follows:

[0055]

[0056]

[0057] In this regard, the cardanol used in the present invention is hydrogenated cardanol prepared by hydrogenating an unsaturated side chain, and is modified by completely hydrogenating the unsaturated aromatic ring in the side chain portion (R) of the cardanol. At this time, the side chain portion (R) is characterized in that the (a) structure accounts for 90 to 95 wt%, and the remainder contains 5 to 10 wt% of the (b) to (d) structures and impurities.

[0058] In this regard, conventional general cardanol has a high proportion of structures (b) to (d) with aromatic rings in the side chain portion compared to hydrogenated cardanol. In this case, the aromatic rings in the side chain portion are prone to unsaturated oxidation and cause side reactions. Therefore, there is a problem of adversely affecting the mechanical and chemical performance when manufacturing a resin.

[0059] The hydrogenated cardanol used in the present invention provides brighter colors than conventional cardanol and, furthermore, has superior UV resistance. Furthermore, unlike conventional liquid cardanol, hydrogenated cardanol has the distinct characteristic of a waxy form.

[0060] Meanwhile, in the above step (A), the methyl iodide can be used to substitute the hydroxy group functional group of the cardanol with a methyl group, and the potassium hydroxide can be used as a base catalyst to speed up the reaction.

[0061] In the above step (A), 2 to 5 molar ratios of potassium hydroxide, 1 to 2 molar ratios of methyl iodide, and 3 to 15 molar ratios of dimethyl sulfoxide may be mixed with respect to 1 molar ratio of the cardanol. Preferably, 2 to 4 molar ratios of potassium hydroxide, 1 to 1.5 molar ratios of methyl iodide, and 3 to 12 molar ratios of dimethyl sulfoxide may be mixed with respect to 1 molar ratio of the cardanol, but is not limited thereto. According to one embodiment of the present invention, when potassium hydroxide, methyl iodide, and dimethyl sulfoxide are mixed in the above ranges, the yield may be 95% or more.

[0062] The compound synthesized in the above step (A) may further include a step of extracting the compound using ethyl acetate and distilled water after the synthesis reaction is completed, separating only the ethyl acetate layer, then separately adding sodium sulfate to filter the resulting solid, and then vacuum concentrating only the solution. Next, the concentrated solution may be passed through a chromatography column tube using a hexane developing solution to remove unreacted substances, thereby isolating only the compound represented by the above chemical formula 2.

[0063] The above N-bromosuccinimide can be used as a bromine radical source by selectively brominating allyl and benzyl positions during a bromine substitution reaction in the compound synthesized in step (A), and the above hydrogen chloride can be used as an acid catalyst to accelerate the reaction rate.

[0064] In the above step (B), the N-bromosuccinimide may be mixed in a molar ratio of 1 to 5 and the hydrogen chloride in a molar ratio of 0.01 to 1 with respect to the compound represented by the above chemical formula 2. Preferably, the N-bromosuccinimide may be mixed in a molar ratio of 1 to 4 and the hydrogen chloride in a molar ratio of 0.01 to 0.5 with respect to the compound represented by the above chemical formula 2, but is not limited thereto.

[0065] The step (B) may include a step of mixing the compound represented by the chemical formula 2 prepared in the step (A), N-bromosuccinimide, hydrogen chloride, and acetone, and stirring at room temperature to perform a synthesis reaction; and a step of vacuum concentrating the mixture in which the synthesis reaction has been performed to remove acetone and removing unreacted substances through a flash chromatography column tube using a hexane developing solution. The application of the flash chromatography column tube not only allows for the application of a smaller amount of silica gel by lowering the silica gel layer compared to the application of a general chromatography column, but also allows for the column time to be shortened by increasing the flow rate through pressurization.

[0066] The above mequinol is a raw material used for the coupling reaction, and the bromine functional group of the compound synthesized in step (B) can be substituted with the mequinol to produce a coupling compound. The dimethylacetamide can be used as a solvent to dissolve the mequinol and potassium hydroxide and mix the reactants, and fluidity can be controlled according to the amount introduced. The toluene forms an azeotrope with the water produced in step (C), and can be separated separately in a distillation trap.

[0067] In the above step (C), the dimethylacetamide may be mixed in a molar ratio of 2 to 15 and the toluene may be mixed in a molar ratio of 1 to 5 with respect to the mequinol. Preferably, the dimethylacetamide may be mixed in a molar ratio of 4 to 11 and the toluene may be mixed in a molar ratio of 2 to 5 with respect to the mequinol, but is not limited thereto. If the dimethylacetamide and the toluene are mixed in a range below the above, the yield may be reduced.

[0068] The above step (C) can be stirred at 110 to 150°C for 5 to 9 hours. Preferably, it can be stirred at 130°C for 7 hours, but is not limited thereto.

[0069] The above copper can be used as a metal catalyst to speed up the reaction.

[0070] The above step (D) can be stirred at 170 to 210°C for 7 to 10 hours. Preferably, it can be stirred at 190°C for 8 hours, but is not limited thereto.

[0071] In the above step (D), the dimethylacetamide may be divided into 5 to 10 portions and additionally added every 1 to 3 hours during the synthetic reaction. Preferably, the dimethylacetamide may be divided into 5 to 6 portions and additionally added every 2 hours, but is not limited thereto. If the dimethylacetamide is not additionally added, the reaction time may increase rapidly as the conversion rate decreases due to a decrease in fluidity, and the resultant yield may decrease somewhat.

[0072] The above acetic acid can be used as a catalyst to speed up the reaction rate, and at the same time can be used as a solvent to improve the fluidity of the reactants.

[0073] The above hydrobromic acid can be used to substitute the methyl group of the compound synthesized in the above step (D) with a hydroxy group under a strong acid atmosphere, and at the same time can be used as a solvent to improve the fluidity of the reactants.

[0074] In the above step (E), 40 to 110 molar ratios of the acetic acid and 8 to 33 molar ratios of the hydrobromic acid may be mixed with respect to 1 molar ratio of the compound represented by the above chemical formula 4. Preferably, 50 to 100 molar ratios of the acetic acid and 10 to 30 molar ratios of the hydrobromic acid may be mixed with respect to 1 molar ratio of the compound represented by the above chemical formula 4, but the present invention is not limited thereto. If acetic acid and hydrobromic acid below the above range are mixed, the resultant yield may decrease.

[0075] The concentration of the hydrobromic acid may be 40 to 60%, preferably 48%, but is not limited thereto.

[0076]

[0077] Hereinafter, the present invention will be described in detail using examples. However, the examples according to the present invention may be modified in various ways, and the scope of the present invention is not limited to the examples described below. The examples in this specification are provided to more fully explain the present invention to those of ordinary skill in the art.

[0078]

[0079] Examples and Comparative Examples. Preparation of Cardanol-Based Precursors

[0080] STEP 1.

[0081] Using hydrogenated cardanol as a raw material, potassium hydroxide, methyl iodide, and dimethyl sulfoxide were added in molar ratios, and the synthesis reaction was carried out by stirring at room temperature. At this time, the molar ratios of the raw materials used in the synthesis and the synthesis time are as shown in [Table 1] below.

[0082] Next, after the synthetic reaction is completed, extraction is performed using ethyl acetate and distilled water, only the ethyl acetate layer is separated, then sodium sulfate is added separately, the resulting solid is filtered, and only the solution is vacuum concentrated.

[0083] Next, the concentrated solution was passed through a chromatography column using a hexane developing solution to remove unreacted substances, thereby isolating only product 1.

[0084] In relation to this, Table 1 below confirms the yield according to the molar ratio of raw materials used in synthesis.

[0085] Molar ratioResultYield(%)Hydrogenated cardanoliodideMethyl potassium hydroxideDimethyl sulfoxideExample 1-11.01.12.06.099.0Example 1-21.01.12.012.099.0Example 1-31.01.12.53.095.0Example 1-41.01.12.56.099.0Example 1-51.01.14.06.099.0Comparative Example 1-11.01.11.16.070.0Comparative Example 1-21.01.11.118.090.0Comparative Example 1-31.01.11.56.090.0Comparative Example 1-41.01.12.0-UnreactedComparative Example 1-51.01.12.01.580.0Comparative example 1-61.01.12.02.085.0Comparative example 1-71.01.12.02.590.0

[0086] As confirmed by the test results above, it was confirmed that the yield was 95% or higher when 2.0 mol or more of potassium hydroxide and 3 mol or more of dimethyl sulfoxide were included based on 1.1 mol of methyl iodide based on 1 mol of hydrogenated cardanol. In other words, when the molar ratio of hydrogenated cardanol and methyl iodide is as above, it was confirmed that the highest yield was obtained when the molar ratio of potassium hydroxide was 2 mol or more. However, even if the above condition of including 2 mol or more of potassium hydroxide was satisfied, it was confirmed that the yield decreased when the solvent dimethyl sulfoxide was less than 3 mol. In relation to this, NMR data for product 1 generated through the STEP 1 manufacturing method is shown in Fig. 1.

[0087]

[0088] STEP 2.

[0089] 1) Manufacturing method of Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-4

[0090] The product 1 generated through STEP 1 was used, and N-bromosuccinimide, hydrogen chloride, and acetone were added, followed by stirring at room temperature for 1 hour to carry out the synthesis reaction. The molar ratios of the raw materials used in the synthesis are as shown in [Table 2] below.

[0091] Next, after the reaction was carried out, acetone was removed by vacuum concentration, and only the solution was vacuum concentrated, and unreacted substances (product 1) were removed through a flash chromatography column using a hexane developing solution, and only product 2 was isolated.

[0092] In relation to this, Table 2 below confirms the yield according to the molar ratio of raw materials used in synthesis.

[0093] 2) Comparative Example 2-5 Manufacturing Method

[0094] Using the product 1 generated through STEP 1, a synthesis reaction was carried out by adding 1.0 molar ratio of N-bromosuccinimide, 0.01 molar ratio of hydrogen chloride, and 25.5 molar ratio of acetone, and stirring at room temperature. At this time, the synthesis reaction was carried out until the yellow solution lost its color, and the synthetic product manufactured through the above process was concentrated in vacuum to remove acetone, and then 12.5 molar ratio of hexane was added.

[0095] Next, the solution was cooled in an ice bath to recrystallize, and the resulting succinimide solid was filtered off.

[0096] Finally, only the solution was vacuum concentrated and the desired substance was separated through a chromatography column using petroleum ether developing solution.

[0097] Molar specific reaction time (hr) Result yield (%) Product 1N-bromosuccinimide hydrogen chloride Example 2-11.01.00.011.098.0 Example 2-21.01.50.011.098.0 Example 2-31.02.00.010.599.0 Example 2-41.02.50.010.599.0 Example 2-51.03.00.010.599.0 Example 2-61.02.50.50.599.0 Example 2-71.04.00.010.599.0 Example 2-81.02.50.10.599.0 Comparative example 2-11.01.0-6.092.0Comparative example 2-21.01.5-5.093.0Comparative example 2-31.02.0-5.092.0Comparative example 2-41.02.5-4.096.0Comparative example 2-51.01.00.011.084.0

[0098] As shown in the test results above, it was confirmed that the yield was at least 92% when N-bromosuccinimide was 1 mol or more based on the molar ratio of product 1 to 1. However, it was confirmed that the reaction time took at least 4 hours when hydrogen chloride was not included, and it was confirmed that the reaction time was shortened to about 1 hour when at least 0.01 mol of hydrogen chloride was included. Meanwhile, it was confirmed that the form in which the synthetic product was vacuum concentrated to remove acetone, as in Example 2-1, had a better yield than the method of recrystallization, as in Comparative Example 2-7.

[0099] In addition, it was confirmed that applying a flash chromatography column rather than a general chromatography column not only allows for the application of a smaller amount of silica gel by lowering the silica gel stack, but also shortens the column time by increasing the flow rate through pressurization.

[0100] Figure 2 shows NMR data for product 2 produced through the STEP 2 manufacturing method.

[0101]

[0102] STEP 3.

[0103] 1) Examples 3-1 to 3-13 and Comparative Examples 3-1 to 3-2

[0104] After installing a distillation trap and a reflux device in a three-port reactor, mequinol, potassium hydroxide, dimethylacetamide, and toluene were added and stirred at 130°C for 7 hours to carry out the first synthetic reaction. The molar ratios of the raw materials used in the synthesis are as shown in [Table 3] below. In this regard, the acetone-water azeotrope generated during the synthesis process was separately separated using a distillation trap.

[0105] After the reaction was completed, the product 2 generated through STEP 2, copper, and dimethylacetamide were added to the composition cooled to room temperature, and the mixture was stirred at 190 degrees for 8 hours to carry out the second synthetic reaction. At this time, the molar ratio of the raw materials used in the synthesis is as shown in [Table 3] below.

[0106] Meanwhile, during the third synthetic reaction, dimethylacetamide was added in 5-6 portions every 2 hours. This is because the solvent evaporates as the reaction progresses due to the high temperature reaction. Therefore, the fluidity of the synthetic composition decreases due to solvent evaporation, lowering the reaction rate and conversion rate. However, by continuously adding the solvent in portions, the fluidity was increased, thereby controlling the reaction rate and conversion rate.

[0107] After the reaction was completed, the copper salt was removed using a diatomaceous earth filter. Next, the filtered composition was extracted using dichloromethane and distilled water, and only the dichloromethane layer was separated. After adding sodium sulfate, the resulting composition was filtered and only the solution was concentrated under vacuum.

[0108] Finally, the concentrated solution was separated from the unreacted material using a chromatography column using hexane developing solution to isolate only product 3.

[0109] 2) Comparative Example 3-3

[0110] After installing a distillation trap and a reflux device in a three-port reactor, mequinol, potassium hydroxide, dimethylacetamide, and toluene were added and stirred at 130°C for 7 hours to carry out the first synthetic reaction. The molar ratios of the raw materials used in the synthesis are shown in Table 3 below. In this regard, the acetone-water azeotrope generated during the synthesis process was separated separately using a distillation trap.

[0111] After the reaction was completed, the product 2 generated through STEP 2, copper, and dimethylacetamide were added to the composition cooled to room temperature, and the mixture was stirred at 190°C for 8 hours to carry out the second synthetic reaction. At this time, the molar ratio of the raw materials used in the synthesis is as shown in Table 3 below. At this time, the third synthetic reaction was carried out without additional addition of a separate solvent.

[0112] After the reaction was completed, the copper salt was removed using a diatomaceous earth filter. Next, the filtered composition was extracted using dichloromethane and distilled water, and only the dichloromethane layer was separated. After adding sodium sulfate, the resulting composition was filtered and only the solution was concentrated under vacuum.

[0113] Finally, the concentrated solution was separated from the unreacted material using a chromatography column using hexane developing solution to isolate only product 3.

[0114] 1st synthesis molar ratio2nd synthesis molar ratioAdditional solvent during reactionReaction time(hr)ResultYield(%)Methylene quinolPotassium hydroxideDimethylacetamideTolueneProductDi-copperDimethylacetamideExample 3-11.13.012.05.51.00.084O8.065.0Example 3-22.03.012.05.51.00.084O8.065.0Example 3-33.03.012.05.51.00.084O8.065.0Example 3-42.01.112.05.51.00.084O8.065.0Example 3-52.05.012.05.51.00.084O8.065.0Example 3-62.03.010.05.51.00.084O8.065.0Example 3-72.03.020.05.51.00.084O8.065.0Example 3-82.03.012.04.01.00.084O8.065.0Example 3-92.03.012.010.01.00.084O8.065.0Example 3-102.03.012.05.51.00.024O8.065.0Example 3-112.03.012.05.51.00.24O8.065.0Example 3-122.03.012.05.51.00.08208.065.0Example 3-132.03.012.05.51.00.081008.065.0Comparative Example 3-12.03.01.02.01.00.08408.040.0Comparative Example 3-22.03.012.05.51.00.081008.050.0Comparative Example 3-32.03.012.05.51.00.084X12.060.0

[0115] As shown in the test results above, it was confirmed that the reaction time and the result yield were constant within the molar ratio range of the examples in [Table 3]. On the other hand, in the case of Comparative Examples 3-1 and 3-2, where the content of the solvent dimethylacetamide or toluene was low, it was confirmed that the final result yield decreased. In addition, in the case of Comparative Example 3-3, when no additional solvent was included during the reaction, it was confirmed that the reaction time increased rapidly and the result yield decreased somewhat as the conversion rate decreased due to the decrease in fluidity.

[0116] Figure 3 shows NMR data for product 3 produced through the STEP 3 manufacturing method.

[0117]

[0118] STEP 4.

[0119] 1) Examples 4-1 to 4-4 and Comparative Examples 4-1 to 4-6

[0120] Acetic acid and 48% hydrobromic acid were added to product 3 manufactured through STEP 3, and the synthesis reaction was carried out by stirring at 140°C. At this time, the reaction time is as shown in [Table 4] below.

[0121] Meanwhile, after the reaction had progressed, extraction was performed using ethyl acetate and brine solution (saturated sodium chloride solution), and only the ethyl acetate layer was separated. After sodium sulfate was added until no hydrate lumps were formed, the resulting solid was filtered and only the solution was concentrated under vacuum. Afterwards, the concentrated solution was passed through a chromatography column tube using a hexane:ethyl acetate 85:15 volume ratio developing solution to remove unreacted substances and isolate only the product 4.

[0122] 2) Comparative examples 4-7 to 4-15

[0123] N-tetrabutylphosphonium bromide and 48% hydrobromic acid were added to product 3 manufactured through STEP 3, and the synthesis reaction was carried out by stirring at 140°C. At this time, the reaction time is as shown in [Table 4] below.

[0124] Meanwhile, after the reaction had progressed, extraction was performed using ethyl acetate and brine solution (saturated sodium chloride solution), and only the ethyl acetate layer was separated. After sodium sulfate was added until no hydrate lumps were formed, the resulting solid was filtered and only the solution was concentrated under vacuum. Afterwards, the concentrated solution was passed through a chromatography column tube using a hexane:ethyl acetate 85:15 volume ratio developing solution to remove unreacted substances and isolate only the product 4.

[0125] Molar specific reaction time (hr) Result yield (%) Product 3 Acetic acid 48% Hydrobromic acid N-Tetrabutylphosphonium bromide Example 4-115020-685 Example 4-215030-685 Example 4-3110010-685 Example 4-4110020-685 Comparative Example 4-11255-620 Comparative Example 4-212510-620 Comparative Example 4-312520-650 Comparative Example 4-41505-640 Comparative Example 4-515010-640 Comparative Example 4-611005-640 Comparative Example 4-71-401.1680 Comparative Example 4-81-402680 Comparative Example Comparative Example 4-91-404680 Comparative Example 4-101-502680 Comparative Example 4-111-602680 Comparative Example 4-121-702680 Comparative Example 4-131-522460 Comparative Example 4-141-2021270 Comparative Example 4-151-302975

[0126] As shown in the test results above, it was confirmed that the reaction time and the result yield were constant in the molar ratio range of Examples 4-1 to 4-4 in Table 4. This confirms that a constant result yield is observed when acetic acid and 48% hydrobromic acid reach the appropriate amount. On the other hand, in the case of Comparative Examples 4-1 to 4-3, where the content of acetic acid as a solvent and catalyst was low, it was confirmed that the result yield tended to decrease further. In addition, in the case of Comparative Examples 4-1, 4-4, and 4-6, where the content of 48% hydrobromic acid as a solvent and substituent was low, it was confirmed that the result yield tended to decrease further.

[0127] On the other hand, in Comparative Examples 4-7 to 4-12, when N-tetrabutylphosphonium bromide was included instead of acetic acid, a 48% hydrobromic acid content showed an 80% result yield at a molar ratio more than four times that of Example 4-3, which was confirmed to be a somewhat lower result yield compared to Examples 4-1 to 4-4. In addition, in Comparative Examples 4-13 to 4-15, where the 48% hydrobromic acid content was low, it was confirmed that the reaction time tended to increase and the result yield tended to decrease.

[0128] Figure 4 shows NMR data for product 4 produced through the STEP 4 manufacturing method.

[0129]

[0130] We have discussed specific embodiments of the present invention. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than restrictive. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. (A) A step of mixing cardanol, potassium hydroxide, methyl iodide and dimethyl sulfoxide represented by the following chemical formula 1 and stirring at room temperature to synthesize a compound represented by the following chemical formula 2; (B) A step of synthesizing a compound represented by the following chemical formula 3 by mixing the compound represented by the following chemical formula 2, N-bromosuccinimide, hydrogen chloride and acetone prepared in step (A) and stirring at room temperature; (C) A step of synthesizing a first product by mixing and stirring mequinol, potassium hydroxide, dimethylacetide, and toluene; (D) a step of synthesizing a compound represented by the following chemical formula 4 by mixing and stirring the compound represented by the following chemical formula 3 manufactured in the above step (B), the first product, copper, and dimethylacetimide; and (E) A method for producing a cardanol-based precursor, characterized in that it comprises a step of mixing and stirring the compound represented by the following chemical formula 4, acetic acid and hydrobromic acid manufactured in the above step (D) to synthesize a compound represented by the following chemical formula 5. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] In the above chemical formulas 1 to 5, R is as follows:

2. In paragraph 1, In the above step (A), A method for producing a cardanol-based precursor, characterized in that a molar ratio of 2 to 5 of the potassium hydroxide and a molar ratio of 3 to 15 of the dimethyl sulfoxide are mixed with respect to the molar ratio of 1 of the cardanol.

3. In paragraph 1, Step (B) above, A step of mixing the compound represented by the chemical formula 2 manufactured in the above step (A), N-bromosuccinimide, hydrogen chloride and acetone and stirring at room temperature to carry out a synthesis reaction; and A method for producing a cardanol-based precursor, characterized by comprising the step of vacuum concentrating the mixture in which the above synthetic reaction has been performed to remove acetone and then removing unreacted substances through a flash chromatography column tube.

4. In paragraph 1, A method for producing a cardanol-based precursor, characterized in that in the step (C), 2 to 15 molar ratios of the dimethylacetamide and 1 to 5 molar ratios of the toluene are mixed with respect to 1 molar ratio of the mequinol.

5. In paragraph 1, A method for producing a cardanol-based precursor, characterized in that the above step (D) is stirred at 170 to 210°C for 7 to 10 hours.

6. In paragraph 1, A method for producing a cardanol-based precursor, characterized in that in the above step (D), the dimethylacetamide is divided into 5 to 10 parts and additionally added every 1 to 3 hours during the synthetic reaction.

7. In paragraph 1, A method for producing a cardanol-based precursor, characterized in that in the step (E), 40 to 110 molar ratios of the acetic acid and 8 to 33 molar ratios of the hydrobromic acid are mixed with respect to 1 molar ratio of the compound represented by the chemical formula 4.

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