Phenolic epoxy resin and method for producing the same

Abstract

To provide a phenol epoxy resin and a method for producing the same.SOLUTION: A method for producing a phenol epoxy resin includes: conducting a polycondensation reaction of cardanol and vanillin at a temperature of 60°C to 90°C, and thereby forming a phenol resin; adding the phenol resin, epichlorohydrin, and a surface active agent which is an alcohol ether-based solvent to a reaction tank; adding first alkali solution thereto at a temperature of 55°C to 65°C, and conducting an alkoxide reaction; and adding second alkali solution thereto and conducting a ring closure reaction at a temperature of 60°C to 70°C, when a hydroxyl equivalent of the phenol resin is lower than an original hydroxyl equivalent of the phenol resin by 3%, and forming a phenol epoxy resin.SELECTED DRAWING: Figure 1

Description

【Technical Field】 【0001】 The present invention relates to a phenolic epoxy resin and a method for producing the same, and particularly to a phenolic epoxy resin produced using biomass materials and a method for producing the same. 【Background Art】 【0002】 Thermosetting epoxy resins have excellent comprehensive properties and are thus widely applied to paints, adhesives, encapsulating adhesives, and composite materials. However, the main supply sources of conventional epoxy resins are petrochemical products. 【0003】 Taking the bisphenol-type epoxy resin, which currently has the highest yield, as an example, although there is already a mature biomass technology for epichlorohydrin, which is a major raw material for producing bisphenol-type epoxy resins, the raw material for bisphenol is still a petroleum product and is derived from the cracking of petroleum. Furthermore, bisphenol is known to be biologically toxic, and many countries have clearly prohibited the use of bisphenol in materials that come into contact with food or the human body. 【0004】 Therefore, facing the shortage of petroleum, the increasing environmental awareness, and the restrictions on uses due to biological toxicity, research departments are conducting research on monomers used as substitutes for bisphenol in order to overcome the above problems and produce environmentally friendly products made entirely from biomass materials. 【0005】 Therefore, improving materials to produce epoxy resins using biomass materials as raw materials to overcome the above-mentioned drawbacks has become an important issue for those in the industry. 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0006】 The technical problem to be solved by the present invention is to provide a phenolic epoxy resin and a method for producing the same in view of the deficiencies of the prior art. [Means for solving the problem] 【0007】 To solve the above technical problems, one technical means employed by the present invention is to provide a method for producing a phenol epoxy resin. The method for producing the phenol epoxy resin includes forming a phenol resin by carrying out a polycondensation reaction between cardanol and vanillin at a temperature of 60°C to 90°C; adding the phenol resin, epichlorohydrin, and a surfactant which is an alcohol ether solvent to a reaction tank; carrying out an alkoxide reaction by adding a first alkaline solution at a temperature of 55°C to 65°C; and when the hydroxyl group equivalent of the phenol resin becomes lower than 3% of the original hydroxyl group equivalent of the phenol resin, carrying out a ring-closing reaction by adding a second alkaline solution at a temperature of 60°C to 70°C to form an epoxy ring. 【0008】 In one embodiment, the amount of epichlorohydrin added per 100 parts by weight of phenolic resin is 400 to 800 parts by weight. 【0009】 In one embodiment, the weight-average molecular weight of the phenolic resin is 4,000 g / mol to 10,000 g / mol. 【0010】 In one embodiment, the surfactant may be selected from the group consisting of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. 【0011】 In one embodiment, the first alkaline solution is added dropwise, and the addition time of the first alkaline solution is 1.5 hours to 3.5 hours. 【0012】 In one embodiment, the second alkaline solution is added dropwise, and the addition time of the second alkaline solution is 1 to 2.5 hours. 【0013】 In one embodiment, after the alkoxide reaction is complete, the temperature is raised to 65°C and dehydration is performed for 30 minutes under a pressure of 5 torr to 400 torr. 【0014】 In one embodiment, after the ring-closing reaction is complete, the temperature is raised to 75°C within 30 minutes, and dehydration is performed under a pressure of 5 torr to 400 torr. 【0015】 In one embodiment, after the dehydration, the remaining epichlorohydrin is removed at a temperature of 120°C to 130°C. 【0016】 In one embodiment, after removing epichlorohydrin, an extraction solvent is added at a temperature of 70°C to 80°C to obtain a phenol epoxy resin. 【0017】 In one embodiment, the extraction solvent is selected from the group consisting of ethyl acetate, toluene, and methyl isobutyl ketone. 【0018】 In one embodiment, a phenol epoxy resin epoxy The equivalent weight is between 250g / equivalent and 350g / equivalent. 【0019】 In one embodiment, the viscosity of the phenol epoxy resin is 10,000 cps to 15,000 cps at 25°C. 【0020】 To solve the above technical problems, another technical means employed by the present invention is to provide a phenol epoxy resin. The phenol epoxy resin is manufactured by the method described above. [Effects of the Invention] 【0021】 As an advantageous effect of the present invention, the phenolic epoxy resin and its manufacturing method according to the present invention can produce a phenolic epoxy resin manufactured from biomass materials, which can be used as an alternative to conventional petrochemical-derived phenolic epoxy resins, due to technical features such as "adding a phenolic resin, epichlorohydrin, and a surfactant to a reaction tank", "performing an alkoxylation reaction by adding a first alkaline solution at a temperature of 55°C to 65°C", and "performing a ring-closure reaction by adding a second alkaline solution at a temperature of 60°C to 70°C". 【Brief Description of the Drawings】 【0022】 [Figure 1] It is a flowchart of a method for manufacturing a phenolic epoxy resin according to an embodiment of the present invention. [Figure 2] It is a schematic diagram showing the reaction mechanism between the phenolic resin and epichlorohydrin of the present invention. 【Modes for Carrying Out the Invention】 【0023】 To better understand the features and technical content of the present invention, please refer to the following detailed description of the present invention and the accompanying drawings. However, the provided accompanying drawings are for reference and explanation purposes only and are not intended to limit the scope of the claims of the present invention. 【0024】 The following describes the "phenolic epoxy resin and its manufacturing method" according to the embodiments of the present invention by specific embodiments. Those skilled in the art can understand the advantages and effects of the present invention based on the content disclosed in this specification. The present invention can be implemented or applied by other different specific embodiments, and for each detail in this specification, various modifications and changes can be made based on different viewpoints and uses without departing from the concept of the present invention. Also, as described in advance, the attached drawings of the present invention are simple schematic explanations and are not drawn based on actual sizes. The technical content related to the present invention will be described in more detail based on the following embodiments, but the disclosed content does not limit the protection scope of the present invention. Also, the term "or" used in this specification may include any one or a combination of multiple items listed in relation according to the actual situation. 【0025】 To overcome the problems of the toxicity of the above-mentioned raw materials and the shortage of petrochemical raw materials, the present invention manufactures a phenolic epoxy resin consisting entirely of biomass materials by selecting synthetic monomers to contribute to environmental protection. After selecting specific biomass materials, it is necessary to adjust the synthesis process according to their characteristics in order to synthesize commercially available materials. 【0026】 Specifically, in the present invention, cardanol and vanillin are used as raw materials, and after performing a polycondensation reaction, a phenolic resin is synthesized (Steps S1 to S5), and then a substitution reaction is carried out between the phenolic resin and epichlorohydrin (Steps S6 to S10) to obtain a phenolic epoxy resin completely manufactured from biomass materials. Therefore, the phenolic epoxy resin of the present invention is used as an alternative to the conventional bisphenol A type phenolic epoxy resin. 【0027】 Both cardanol and vanillin are derived from biomass materials. Cardanol is used as a substitute for currently used phenols (e.g., bisphenol A), and vanillin is used as a substitute for formaldehyde, which is highly toxic. Therefore, the structural formula of the phenol resin of the present invention can also be expressed as follows. [ka] Here, n is a positive integer between 5 and 25. 【0028】 As shown in Figure 1, the method for producing phenol epoxy resin according to the present invention includes steps S1 to S10 described later. Specifically, these steps are: mixing cardanol and vanillin (step S1), adding an acidic catalyst to carry out a polycondensation reaction (step S2), adding an alkaline solution to stop the polycondensation reaction (step S3), adding an acidic substance to control the pH to neutral (step S4), adding an extraction solvent to obtain a phenol resin (step S5), mixing the phenol resin with epichlorohydrin and a surfactant (step S6), adding a first alkaline solution to carry out an alkoxide reaction (step S7), adding a second alkaline solution to carry out a ring-closing reaction (step S8), removing residual epichlorohydrin (step S9), and adding an extraction solvent to obtain a phenol epoxy resin (step S10). 【0029】 In step S1, cardanol and vanillin are added to the reaction tank, where vanillin is a limiting reagent; that is, the number of moles of cardanol added exceeds the number of moles of vanillin added. In this way, it is possible to ensure that both ends of the synthesized phenolic resin are hydroxyl groups, which is advantageous for subsequent substitution reactions. 【0030】 In one preferred embodiment, nitrogen can be introduced into the reaction tank to ensure the specificity of the reaction, and the polycondensation reaction between cardanol and vanillin can be carried out under a nitrogen atmosphere. 【0031】 In step S2, in order to accelerate the polycondensation reaction between cardanol and vanillin, the reaction tank is heated to a temperature of 60°C to 90°C, and an acidic catalyst is further added to carry out the polycondensation reaction between cardanol and vanillin, thereby forming a phenolic resin. 【0032】 It is worth noting that conventional polycondensation reactions between formaldehyde and phenol use a weak acid. On the other hand, because the reactivity between cardanol and vanillin is relatively low, the present invention uses a strongly acidic catalyst to accelerate the polycondensation reaction. Specifically, the acidity coefficient pKa of the acidic catalyst at 25°C in water is less than 3.1. 【0033】 When the acidity coefficient pKa of the acid catalyst is low (for example, hydrochloric acid, sulfuric acid, or phosphoric acid), a relatively large amount of hydrogen ions can be dissociated from the acid catalyst. This leads to intense heat generation during the polycondensation reaction, making it difficult to control the reaction's progress and resulting in a wide distribution range for the weight-average molecular weight of the phenolic resin (i.e., a high dispersion index of the polymer). 【0034】 When the acidity coefficient pKa of the acidic catalyst is relatively high (for example, citric acid, oxalic acid), it is relatively difficult for the acidic catalyst to dissociate into hydrogen ions. This results in low reactivity of cardanol and vanillin, and consequently, a relatively low molecular weight of the phenolic resin. 【0035】 Experiments have shown that the acidity coefficient pKa of the acid catalyst in water at 25°C is preferably -2.9 to 1.5, and more preferably -2.0 to -1.5. For example, the acid catalyst may be methanesulfonic acid or p-toluenesulfonic acid, where methanesulfonic acid is most preferred. 【0036】 In order to control the reaction stability of the polycondensation reaction, in addition to temperature and the type of acidic catalyst, the amount of acidic catalyst added is also controlled in this invention. Assuming a total weight of cardanol and vanillin of 100 parts by weight, the amount of acidic catalyst added is 0.25 parts by weight to 1 part by weight, preferably 0.5 parts by weight to 0.6 parts by weight. 【0037】 In step S3, the vanillin content in the reaction tank is measured using a liquid chromatograph (LC), and when the weight percentage concentration of vanillin in the reaction tank falls below 0.1%, an alkaline solution is added to stop the polycondensation reaction. In one exemplary case, the polycondensation reaction in step S2 is allowed to proceed for approximately 3.5 to 4.5 hours. 【0038】 Specifically, the addition of an alkaline solution can neutralize the acidic catalyst, thereby stopping the polycondensation reaction. The alkaline solution may be a 40 wt% to 60 wt% aqueous sodium hydroxide solution or a 40 wt% to 60 wt% aqueous potassium hydroxide solution, but the present invention is not limited to these. 【0039】 In step S4, the decomposition of the manufactured phenolic resin is avoided by adding an acidic substance to control the pH to neutral (i.e., pH 6.5-7.5). For example, the acidic substance may be oxalic acid. However, there is no limit to the amount of acidic substance added, as it is used to control the pH in the reaction tank to neutral. 【0040】 After the above steps S1 to S4, the reaction tank contains various substances in multiple organic and aqueous phases, and the phenolic resin can be purified by washing and extraction. 【0041】 In step S5, the mixture is washed with water using an extraction solvent, and the reaction tank separates into an organic phase and an aqueous phase, with the phenolic resin present in the organic phase. Therefore, the aqueous phase can be removed by reflux dehydration at a temperature of 110°C to 130°C, and then the extraction solvent can be removed under a pressure of 5 torr to 400 torr to obtain the phenolic resin. 【0042】 Experiments have shown that the extraction solvent may be selected from the group consisting of ethyl acetate, toluene, and methyl isobutyl ketone. When the extraction solvent is one of the aforementioned substances, a relatively good extraction effect is achieved with respect to phenolic resin, and methyl isobutyl ketone is most preferred. 【0043】 When tests were conducted with cardanol of different purities, the results showed that the higher the purity of the cardanol, the lighter the color of the resulting phenolic resin. Specifically, cardanol with product number NX-2024 from Cardolite has a purity of 87% or higher, and the phenolic resin produced with it is relatively dark in color, while cardanol with product number NX-2026 from Cardolite has a purity of 96% or higher, and the phenolic resin produced with it is relatively light in color. 【0044】 In step S6, the phenol resin obtained in step S5 is mixed with epichlorohydrin (ECH) and a surfactant. The surfactant improves the compatibility between the phenol resin and epichlorohydrin, promotes the reaction between epichlorohydrin and phenol resin, and replaces the hydroxyl groups of the phenol resin with epoxy groups. 【0045】 To be more specific, the surfactant may be an alcohol ether-based solvent. For example, the surfactant may be selected from the group consisting of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. 【0046】 In one preferred embodiment, the amount of epichlorohydrin added is 400 to 800 parts by weight per 100 parts by weight of phenol resin. For example, the amount of epichlorohydrin added may be 450, 500, 550, 600, 650, 700, or 750 parts by weight. More preferably, the amount of epichlorohydrin added may be 600 to 700 parts by weight per 100 parts by weight of phenol resin. 【0047】 In steps S7 and S8, the reaction tank is heated to 55°C to 70°C, and first, a first alkaline solution is added to carry out an alkoxide reaction in which the phenolic OH group is alkoxideized, and then, a second alkaline solution is added to carry out a ring-closing reaction in which the chlorohydrin is ring-closed to an epoxy group, thereby obtaining a phenol epoxy resin. In one preferred embodiment, the reaction temperature of the ring-closing reaction is higher than the reaction temperature of the alkoxide reaction, and the temperature difference between the reaction temperature of the ring-closing reaction and the reaction temperature of the alkoxide reaction is 5°C to 10°C. 【0048】 Refer to Figure 2 to explain the reaction mechanism between the phenol resin and epichlorohydrin in steps S7 and S8. In the exemplary example shown in Figure 2, the first alkaline solution is a 50 wt% aqueous sodium hydroxide solution, and the addition of the first alkaline solution removes hydrogen atoms from the hydroxyl groups in the phenol resin. The presence of a surfactant is advantageous in the reaction between epichlorohydrin and the phenol resin, as it converts the hydroxyl groups originally present in the phenol resin into glycidyloxy groups. The second alkaline solution is a 50 wt% aqueous sodium hydroxide solution, and the addition of the second alkaline solution promotes the cyclization reaction to the epoxy ring by removing HCl from chlorohydrin (-CH(OH)-CH2Cl), completing the substitution reaction. 【0049】 The types of the first alkaline solution and the second alkaline solution are not limited to those described above, and the first alkaline solution and the second alkaline solution may be the same or different. For example, the first alkaline solution and the second alkaline solution may independently be a 50 wt% potassium hydroxide aqueous solution. 【0050】 In one example, the amount of the first alkaline solution added is greater than the amount of the second alkaline solution added; for example, the amount of the first alkaline solution added is 2.5 to 4 times the amount of the second alkaline solution added. 【0051】 In step S7, the reaction tank is heated to a temperature of 55°C to 65°C, and then the first alkaline solution is added dropwise to carry out the alkoxide reaction, thereby removing hydrogen atoms from the hydroxyl groups in the phenol resin. For example, the dropping rate of the first alkaline solution is 0.1 g / min to 0.4 g / min. To observe the degree of the alkoxide reaction, the phenol resin is irradiated with ultraviolet light with a wavelength of 310 nm, and the hydroxyl group content in the phenol resin is quantified from the absorbance result. When the hydroxyl group equivalent of the phenol resin falls below 3% of the original hydroxyl group equivalent of the phenol resin, the second alkaline solution is added and step S8 is carried out. 【0052】 In one demonstration example, the dropwise addition time of the first alkaline solution is 1.5 to 3.5 hours, so the time it takes for the alkoxide reaction to proceed in step S7 is approximately 1.5 to 3.5 hours. Furthermore, after the dropwise addition of the first alkaline solution is complete, stirring is continued for 30 minutes to ensure that the hydroxyl groups in the phenol resin are completely dehydrogenated. Next, the temperature is raised to 65°C and dehydration is performed for 30 minutes under a pressure of 5 torr to 400 torr. Water is produced during the alkoxide reaction, and the presence of water leads to the hydrolysis of the phenol resin. Therefore, after the alkoxide reaction is complete, dehydration is performed once before proceeding to step S8. 【0053】 In step S8, the reaction tank is heated to a temperature of 60°C to 70°C, and then the second alkaline solution is added dropwise to carry out the ring-closing reaction, thereby promoting the dechlorination of epichlorohydrin and the closing of the loop. For example, the dropping rate of the second alkaline solution is 0.05 g / min to 0.15 g / min. In one example, the dropping time of the second alkaline solution is 1 hour to 2.5 hours, so the time it takes for the ring-closing reaction to proceed in step S8 is approximately 1 hour to 2.5 hours. Furthermore, after the dropping of the second alkaline solution is completed, the temperature is raised to 75°C within 30 minutes and dehydration is performed for 30 minutes. 【0054】 In step S9, unreacted epichlorohydrin is removed at a temperature of 120°C to 130°C to prevent epichlorohydrin from affecting the purity of the phenol epoxy resin. 【0055】 In step S10, after the reaction tank has cooled to a temperature of 70°C to 80°C, the extraction solvent and neutralization solution are added at atmospheric pressure and washed with water, causing the organic and aqueous phases to separate in the reaction tank. The extraction solvent can extract the phenol epoxy resin into the organic phase, and the neutralization solution can form a sodium chloride salt together with the chloride ions removed from epichlorohydrin. Next, the aqueous phase is removed by reflux dehydration at a temperature of 110°C to 130°C, and then the extraction solvent is removed under a pressure of 5 torr to 400 torr to obtain the phenol resin. 【0056】 Experiments have shown that the extraction solvent may be selected from the group consisting of ethyl acetate, toluene, and methyl isobutyl ketone. Here, methyl isobutyl ketone is preferred. The neutralization solution may be a 35 wt% aqueous sodium hydroxide solution. However, the present invention is not limited thereto. 【0057】 [Synthesis of phenol epoxy resin] To prove that the manufacturing method of the present invention can produce phenol epoxy resin, the phenol resins of Examples 1 to 3 were produced according to steps S1 to S5 described above. After production, the weight-average molecular weight of the phenol resin was measured by gel permeation chromatography (GPC), and the hydroxyl group equivalent of the phenol resin was measured by potentiometric titration. The results are shown in Table 1. 【0058】 Based on steps S6 to S10 described above, the phenolic epoxy resins of Examples 4 to 6 were produced by mixing the phenolic resin of Example 1 with epichlorohydrin and a surfactant. After production, the epoxy equivalent of the phenolic epoxy resin was measured using a potentiometric titrator, and the viscosity of the phenolic epoxy resin was measured using a viscometer at a temperature of 25°C. The results are shown in Table 2. 【0059】 [Example 1] 190 g (equivalent to 0.63 mol) of cardanol and 76 g (equivalent to 0.5 mol) of vanillin were added to the reaction tank, and nitrogen gas was introduced to maintain a nitrogen atmosphere. The reaction tank was heated, and when the temperature reached 70°C, 1.5 g of methanesulfonic acid (acidic catalyst) was added, and the polycondensation reaction was carried out for 4 hours. 【0060】 After the reaction was complete, 1 g of 50 wt% aqueous sodium hydroxide solution (alkaline solution) and 0.1 g of oxalic acid (acidic substance) were added to stop the polycondensation reaction, and the mixture was extracted with methyl isobutyl ketone (extraction solvent) and washed with water. After washing with water, the reaction tank was heated to 120°C and dehydrated under reflux, and then the extraction solvent was removed under a pressure of 10 torr to obtain the phenolic resin. 【0061】 In Example 1, the phenolic resin was a pale yellow liquid, its weight-average molecular weight was 7406 g / mol, and its hydroxyl group equivalent was 230 g / equivalent. 【0062】 [Example 2] The operating conditions for Example 2 were similar to those for Example 1, the only difference being that the polycondensation reaction was carried out at a temperature of 65°C in Example 2. The phenolic resin in Example 2 was a pale yellow liquid, the weight-average molecular weight of the phenolic resin was 5329 g / mol, and the hydroxyl group equivalent of the phenolic resin was 242 g / equivalent. 【0063】 [Example 3] The operating conditions for Example 3 were similar to those for Example 1, the only difference being that the polycondensation reaction in Example 3 was carried out at a temperature of 85°C. The phenolic resin in Example 3 was a pale yellow liquid, the weight-average molecular weight of the phenolic resin was 9593 g / mol, and the hydroxyl group equivalent of the phenolic resin was 223 g / equivalent. 【0064】 [Table 1] 【0065】 According to the results in Table 1, a biomass phenol resin can be produced using cardanol and vanillin as raw materials based on steps S1 to S5 of the present invention. Furthermore, the weight-average molecular weight of the phenol resin increases as the temperature of the polycondensation reaction increases. When the temperature of the polycondensation reaction is 60°C to 90°C, the weight-average molecular weight of the phenol resin may be 4000 g / mol to 10000 g / mol. In other embodiments, the temperature of the polycondensation reaction may be 60°C to 90°C, and the weight-average molecular weight of the phenol resin may be 4000 g / mol to 10000 g / mol. 【0066】 Furthermore, the hydroxyl group equivalent of the phenolic resin may be 200 g / equivalent to 250 g / equivalent, for example, 210 g / equivalent, 220 g / equivalent, 230 g / equivalent, or 240 g / equivalent. 【0067】 [Example 4] 150 g of the phenolic resin obtained in Example 1, 990 g of epichlorohydrin, and 125 g of diethylene glycol monomethyl ether (surfactant) were added to the reaction tank. 【0068】 After heating the reaction tank to 60°C, 99 g of a 50 wt% sodium hydroxide aqueous solution (first alkaline solution) was added dropwise to carry out the alkoxide reaction, with a total addition time of 2.5 hours. After the addition was complete, the mixture was stirred for 30 minutes to ensure that the phenolic resin was completely dehydrogenated. After heating the reaction tank to 65°C, it was dehydrated at a pressure of 190 torr for 30 minutes. 【0069】 Next, 33 g of a 50 wt% sodium hydroxide aqueous solution (second alkaline solution) was added dropwise to carry out the ring-closing reaction, with a total addition time of 2 hours. After the addition was complete, the solution was dehydrated by raising the temperature to 75°C within 30 minutes, and then the temperature was further raised to 125°C to remove any remaining epichlorohydrin. 【0070】 When the reaction tank cooled to 75°C, 200g of ethyl acetate (extraction solvent) and 15g of 35wt% aqueous sodium hydroxide solution (neutralization solution) were added, and the mixture was washed with water. After washing, the reaction tank was heated to 120°C and reflux dehydration was performed. Furthermore, the extraction solvent was removed under a pressure of 10 torr to obtain a phenol epoxy resin. The epoxy equivalent of the phenol epoxy resin in Example 4 was 312g / equivalent, and its viscosity was 11000 cps at 25°C. 【0071】 [Example 5] The operating conditions for Example 5 were similar to those for Example 4, the only difference being that the amount of epichlorohydrin added in Example 5 was 1100 g, and the dropping time for the first alkaline solution was 1.5 hours. The epoxy equivalent of the phenol epoxy resin in Example 5 was 308 g / equivalent, and its viscosity was 11300 cps at 25°C. 【0072】 [Example 6] The operating conditions for Example 6 were similar to those for Example 4, the only difference being that the total dropping time for the first alkaline solution in Example 6 was 2 hours, while the total dropping time for the second alkaline solution was 1.5 hours. The extraction solvent used when washing the phenol epoxy resin with water was methyl isobutyl ketone. The epoxy equivalent of the phenol epoxy resin in Example 6 was 293 g / equivalent, and its viscosity was 12100 cps at 25°C. 【0073】 [Table 2] 【0074】 According to the results in Table 2, the end groups of the biomass phenol resin may be replaced with epoxy groups based on steps S6 to S10 of the present invention, and a biomass material that combines the excellent properties of both epoxy resin and phenol resin can be produced. 【0075】 Based on Examples 4 to 6, the epoxy equivalent of the phenol epoxy resin may be 250 g / equivalent to 350 g / equivalent, and the viscosity of the phenol epoxy resin may be 10,000 cps to 15,000 cps at 25°C. In other embodiments, the epoxy equivalent of the phenol epoxy resin may be 250 g / equivalent to 350 g / equivalent, and the viscosity of the phenol epoxy resin may be 10,000 cps to 15,000 cps at 25°C. 【0076】 [Advantageous effects of the embodiment] An advantageous effect of the present invention is that the phenol epoxy resin and its manufacturing method according to the present invention, through technical features such as "adding a phenol resin, epichlorohydrin, and a surfactant to a reaction tank," "adding a first alkaline solution at a temperature of 55°C to 65°C to carry out an alkoxide reaction," and "adding a second alkaline solution at a temperature of 60°C to 70°C to carry out a ring-closing reaction," can produce a phenol epoxy resin made from biomass material that can be used as a substitute for conventional petrochemical-derived phenol epoxy resins. 【0077】 The information disclosed herein represents only preferred and feasible embodiments of the present invention, and the claims of the present invention are not limited thereto. Therefore, all equivalent technical modifications made using the information in the specification and drawings of the present invention are included within the scope of the claims of the present invention.

Claims

[Claim 1] The method involves forming a phenolic resin by carrying out a polycondensation reaction between cardanol and vanillin at a temperature of 60°C to 90°C, wherein the hydroxyl group equivalent of the phenolic resin is 200 g / equivalent to 250 g / equivalent. The phenolic resin, epichlorohydrin, and a surfactant which is an alcohol ether solvent are added to the reaction tank. The alkoxide reaction is carried out by adding the first alkaline solution at a temperature of 55°C to 65°C. A method for producing a phenol epoxy resin, characterized by comprising: when the hydroxyl group equivalent of the phenol resin becomes lower than 3% of the hydroxyl group equivalent of the original phenol resin, adding a second alkaline solution at a temperature of 60°C to 70°C to carry out a ring-closing reaction in which an epoxy ring is formed by ring closure, thereby forming a phenol epoxy resin, wherein the epoxy equivalent of the phenol epoxy resin is 250 g / equivalent to 350 g / equivalent. [Claim 2] The method for producing a phenol epoxy resin according to claim 1, wherein the amount of epichlorohydrin added is 400 to 800 parts by weight per 100 parts by weight of the phenol resin. [Claim 3] The method for producing a phenol epoxy resin according to claim 1, wherein the weight-average molecular weight of the phenol resin is 4,000 g / mol to 10,000 g / mol. [Claim 4] The method for producing a phenol epoxy resin according to claim 1, wherein the surfactant is selected from the group consisting of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. [Claim 5] The method for producing a phenol epoxy resin according to claim 1, wherein the first alkaline solution is added dropwise, and the dropwise addition time of the first alkaline solution is 1.5 hours to 3.5 hours. [Claim 6] The method for producing a phenol epoxy resin according to claim 1, wherein the second alkaline solution is added dropwise, and the dropwise addition time of the second alkaline solution is 1 hour to 2.5 hours. [Claim 7] A method for producing a phenol epoxy resin according to claim 1, wherein after the alkoxide reaction is completed, the temperature is raised to 65°C and dehydration is performed under a pressure environment of 5 to 400 to 400 to 45°C. [Claim 8] A method for producing a phenol epoxy resin according to claim 1, wherein, after the ring-closing reaction is completed, the temperature is raised to 75°C within 30 minutes and dehydration is performed in a pressure environment of 5 to 40 [Claim 9] A method for producing a phenol epoxy resin according to claim 8, wherein, after the dehydration, the remaining epichlorohydrin is removed at a temperature of 120°C to 130°C. [Claim 10] A method for producing a phenol epoxy resin according to claim 9, wherein after removing the epichlorohydrin, an extraction solvent is added at a temperature of 70°C to 80°C to obtain a phenol epoxy resin. [Claim 11] The method for producing a phenol epoxy resin according to claim 10, wherein the extraction solvent is selected from the group consisting of ethyl acetate, toluene, and methyl isobutyl ketone. [Claim 12] The method for producing a phenol epoxy resin according to claim 1, wherein the viscosity of the phenol epoxy resin is 10,000 cps to 15,000 cps.

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