Ammonium salt catalyst for producing modified natural oil and method for producing modified natural oil using same

Abstract

The present invention relates to a method for producing modified natural oil using an ammonium salt catalyst, and modified natural oil produced by using same. The ammonium salt catalyst, according to the present invention, acts as a homogeneous catalyst during a reaction for producing modified natural oil to cause the reaction to proceed within a short period of time, and after completion of the reaction, a solvent is added to recrystallize and recover the catalyst, thereby allowing for reuse.

Description

Ammonium salt catalyst for producing modified natural oil and method for producing modified natural oil using the same

[0001] The present invention relates to an ammonium salt catalyst for producing modified natural oil and a method for producing modified natural oil using the same.

[0002] Modified natural oils can be used as additives, such as plasticizers, compatibilizers, or reinforcing agents, for various polymers, such as polyvinyl chloride, styrene butadiene rubber, polylactic acid, and other polymers (such as natural rubber and acrylates). They can also function as compatibilizers or secondary plasticizers in polymer blending. Furthermore, they can be used to produce polyols containing a high content of hydroxyl groups, making them a key component of polyurethane.

[0003] These modified natural oils can be produced through the reaction of natural oil with a nucleophile. However, conventional techniques have made it difficult to recover the catalyst due to the use of a homogeneous organic catalyst in the reaction. Consequently, reusing this homogeneous organic catalyst requires an additional purification process, resulting in complexity and inefficiency. Furthermore, there is a risk of the homogeneous organic catalyst being denatured during the reaction, limiting its reuse efficiency.

[0004] Considering these points, the inventors of the present invention have developed an ammonium salt catalyst for producing modified natural oil, which acts as a homogeneous catalyst during the reaction for producing modified natural oil, allowing the reaction to proceed within a short period of time, and which can be reused by recrystallizing and recovering the catalyst by adding a solvent after the reaction is completed, and a method for producing modified natural oil using the same.

[0005] The purpose of the present invention is to provide a recyclable ammonium salt catalyst and a method for producing modified natural oil using the same.

[0006] Another object of the present invention is to provide a catalyst for producing modified natural oil that can be easily separated and recovered by adding an organic solvent, and a method for producing modified natural oil using the same.

[0007] Another object of the present invention is to provide a catalyst for producing modified natural oil, which has a high conversion rate and selectivity (main product monomer) to modified natural oil and a high recovery rate of the catalyst, and which also maintains the high conversion rate, selectivity and recovery rate of the catalyst even when repeatedly reused, and a method for producing modified natural oil using the same.

[0008] Another object of the present invention is to provide a method for producing a modified natural oil, which can selectively introduce a functional group by applying an ammonium salt catalyst and various nucleophiles during a ring-opening reaction of an epoxidized natural oil in the above-described production method.

[0009] The problems to be solved by the present invention are not limited to the problem(s) mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0010] According to one aspect of the present invention, the present invention provides an ammonium salt catalyst for producing modified natural oil represented by the following chemical formula 3:

[0011] [Chemical Formula 3]

[0012]

[0013] In the above formula,

[0014] R 5 is hydrogen or a substitutable hydrocarbon group, a C1-C10 alkyl group, a benzyl group or a C3-C10 aryl group, and the substituent of the alkyl group, benzyl group or aryl group is selected from C1-C10 alkyl, C3-C10 aryl or halogen element (Cl, Br, I or F),

[0015] R 6is hydrogen, a C1-C10 alkyl group, a C1-C10 alkylamino group, a C1-C10 dialkylamino group, or a C3-C10 aryl group,

[0016] X - is Cl - , Br - , I - , F - This or RCOO, the anion of carboxylic acid - (wherein, R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkylene group, or a substituted or unsubstituted C3-C10 aryl group) or C7H4O3NS, which is an anion of saccharin. - am.

[0017] The above ammonium salt catalyst is characterized in that it is reused after being recrystallized using a solvent.

[0018] According to another aspect of the present invention, the present invention provides a method for producing a modified natural oil represented by the following chemical formula 2 by reacting a nucleophile with an epoxidized natural oil represented by the following chemical formula 1, characterized in that an ammonium salt catalyst is used:

[0019] [Chemical Formula 1]

[0020]

[0021] [Chemical Formula 2]

[0022]

[0023] In the above formula,

[0024] R 1 , R 2are each a substitutable hydrocarbon group, a C1-C50 alkyl group, a C3-C10 aryl group or a heteroaryl group, and the substituents of the alkyl group, aryl group and heteroaryl group are one or a combination of two or more selected from the group consisting of hydroxy, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino, heteroaryl, alkoxy, epoxy, carbonyl and carboxylic acid ester.

[0025] R 3 is -OH or and R 4 Is and,

[0026] The above R 3 and R 4 In , R' is each a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, alkylene, aryl, and alkoxy.

[0027] n is an integer from 1 to 50.

[0028] The above ammonium salt catalyst is characterized by being represented by the following chemical formula 3:

[0029] [Chemical Formula 3]

[0030]

[0031] In the above formula,

[0032] R 5 is hydrogen or a substitutable hydrocarbon group, a C1-C10 alkyl group, a benzyl group or a C3-C10 aryl group, and the substituent of the alkyl group, benzyl group or aryl group is selected from C1-C10 alkyl, C3-C10 aryl or halogen element (Cl, Br, I or F),

[0033] R 6is a C1-C10 alkyl group, a C1-C10 alkylamino group, a C1-C10 dialkylamino group or a C3-C10 aryl group,

[0034] X - is Cl - , Br - , I - , F - This or RCOO, the anion of carboxylic acid - (wherein, R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkylene group, or a substituted or unsubstituted C3-C10 aryl group) or C7H4O3NS, which is an anion of saccharin. - am.

[0035] The nucleophile is characterized by being represented by the following chemical formula 4 or an anhydride thereof:

[0036] [Chemical Formula 4]

[0037]

[0038] In the above formula,

[0039] R is a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, alkylene, aryl, and alkoxy.

[0040] The nucleophile is characterized in that it is one or a combination of two or more selected from the group consisting of palmitic acid, undecanoic acid, valeric acid, p-anisic acid, cinnamic acid, trans-cinnamic acid, undecylenic acid, acetic acid, palmitic anhydride, p-anisic anhydride, caproleic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, brassic acid, benzoic acid, and phenylacetic acid. Do it.

[0041] The above ammonium salt catalyst is characterized in that it acts as a homogeneous catalyst during the above reaction.

[0042] The above ammonium salt catalyst is characterized in that it is reused after being recrystallized using a solvent after the reaction.

[0043] The solvent is characterized in that it is selected from the group consisting of ethyl acetate, methylethyl ketone, 2-methyltetrahydrofuran, tetrahydrofuran, toluene, hexane, chloroform, and combinations thereof.

[0044] The above ammonium salt catalyst is characterized in that it is used in an amount of 1 to 20 mol%.

[0045] The above reaction is characterized in that it is carried out at 80 to 150°C.

[0046] The above reaction is characterized by reacting for 1 to 30 hours.

[0047] In addition, the present invention provides a method for producing a natural modified oil, characterized by comprising the steps of: (a) reacting an epoxidized natural oil represented by the following chemical formula 1 with a nucleophile and an ammonium salt catalyst to produce a modified natural oil represented by the following chemical formula 2; and (b) recrystallizing the ammonium salt catalyst by adding a solvent to the reactant of step (a).

[0048] [Chemical Formula 1]

[0049]

[0050] [Chemical Formula 2]

[0051]

[0052] In the above formula,

[0053] R 1 , R 2 are each a substitutable hydrocarbon group, an alkyl group having 1 to 50 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the substituents of the alkyl group, aryl group and heteroaryl group are one or a combination of two or more selected from the group consisting of hydroxy, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino, heteroaryl, alkoxy, epoxy, carbonyl and carboxylic acid ester.

[0054] R 3 is -OH or and R 4 Is and,

[0055] The above R 3 and R 4In , R' is each a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, alkylene, aryl, and alkoxy.

[0056] n is an integer from 1 to 50.

[0057] The above ammonium salt catalyst is characterized by being represented by the following chemical formula 3:

[0058] [Chemical Formula 3]

[0059]

[0060] In the above formula,

[0061] R 5 is hydrogen or a substitutable hydrocarbon group, a C1-C10 alkyl group, a benzyl group or a C3-C10 aryl group, and the substituent of the alkyl group, benzyl group or aryl group is selected from C1-C10 alkyl, C3-C10 aryl or halogen element (Cl, Br, I or F),

[0062] R 6 is a C1-C10 alkyl group, a C1-C10 alkylamino group, a C1-C10 dialkylamino group or a C3-C10 aryl group,

[0063] X - is Cl - , Br - , I - , F - This or RCOO, the anion of carboxylic acid - (wherein, R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkylene group, or a substituted or unsubstituted C3-C10 aryl group) or C7H4O3NS, which is an anion of saccharin. - am.

[0064] The above step (a) is characterized in that it is performed at 80 to 150°C, and the above step (b) is characterized in that it is performed at 0 to 50°C.

[0065] According to the present invention, there is provided an effect of providing a recyclable ammonium salt catalyst and a method for producing modified natural oil using the same.

[0066] In addition, according to the present invention, there is an effect of providing a catalyst for producing modified natural oil that can be easily separated and recovered by adding an organic solvent, and a method for producing modified natural oil using the same.

[0067] In addition, according to the present invention, the conversion rate and selectivity (main product monomer) to modified natural oil are high, the recovery rate of the catalyst is maintained, and even when the catalyst is repeatedly reused, the conversion rate, selectivity, and recovery rate of the catalyst are maintained high.

[0068] In addition, according to the present invention, there is an effect of selectively introducing a functional group by applying an ammonium salt catalyst and various nucleophiles during the ring-opening reaction of the epoxidized natural oil in the above manufacturing method.

[0069] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the composition of the invention described in the claims.

[0070] Figure 1 shows a process flow diagram of a method for producing modified natural oil using an ammonium salt catalyst according to one embodiment of the present invention.

[0071] Figure 2 is a diagram of modified natural oil, epoxidized soybean oil, and cinnamic acid produced using an ammonium salt catalyst according to one embodiment of the present invention. 1 This shows the results of H NMR analysis.

[0072] Figure 3 shows the selectivity of the main product / by-product of the modified natural oil manufactured using an ammonium salt catalyst according to one embodiment of the present invention and the results of gel permeation chromatography (GPC) analysis of epoxidized soybean oil.

[0073] Figure 4 illustrates a process for recovering and recycling an ammonium salt catalyst according to one embodiment of the present invention.

[0074] Figure 5 shows the recovery and reuse of an ammonium salt catalyst according to one embodiment. 1 This shows the results of H NMR analysis.

[0075] Before describing the present invention in detail, it should be understood that the terms or words used in this specification should not be interpreted as being unconditionally limited to their usual or dictionary meanings, and that the inventor of the present invention may appropriately define and use the concepts of various terms in order to explain his or her invention in the best possible manner, and further, that these terms or words should be interpreted as meanings and concepts that are consistent with the technical idea of ​​the present invention.

[0076] That is, it should be noted that the terms used in this specification are only used to describe preferred embodiments of the present invention, and are not intended to specifically limit the contents of the present invention, and that these terms are defined in consideration of various possibilities of the present invention.

[0077] Additionally, in this specification, it should be noted that singular expressions may include plural expressions unless the context clearly indicates a different meaning, and similarly, even if expressed in plural, may include a singular meaning.

[0078] Throughout this specification, whenever a component is described as "including" another component, it may mean that the component may further include any other component, rather than excluding any other component, unless specifically stated otherwise.

[0079] In addition, in the following description of the present invention, a detailed description of a configuration that is judged to unnecessarily obscure the gist of the present invention, for example, a known technology including a prior art, may be omitted.

[0080] Hereinafter, the present invention will be described in more detail.

[0081]

[0082] Ammonium salt for manufacturing modified natural oil

[0083] The present invention provides an ammonium salt catalyst for producing modified natural oil represented by the following chemical formula 3:

[0084] [Chemical Formula 3]

[0085]

[0086] In the above formula,

[0087] R 5 is hydrogen or a substitutable hydrocarbon group, a C1-C10 alkyl group, a benzyl group or a C3-C10 aryl group, and the substituent of the alkyl group, benzyl group or aryl group is selected from C1-C10 alkyl, C3-C10 aryl or halogen element (Cl, Br, I or F),

[0088] R 6 is hydrogen, a C1-C10 alkyl group, a C1-C10 alkylamino group, a C1-C10 dialkylamino group, or a C3-C10 aryl group,

[0089] X - is Cl - , Br - , I - , F - This is RCOO, the anion of carboxylic acid (acetic acid derivative). - Or C7H4O3NS, the anion of saccharin -Here, R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, aryl, amino, and carboxyl groups.

[0090] The above ammonium salt catalyst may preferably be selected from the group consisting of 4-(N,N-dimethylamino)pyridine cinnamic acid salt, 4-(N,N-dimethylamino)pyridine saccharin salt, 4-(dimethylamino)pyridine benzyl chloride salt, 4-(N,N-dimethylamino)pyridine-1-(p-fluorobenzyl) chloride salt, and 4-(N,N-dimethylamino)pyridine benzyl bromide salt.

[0091] The above ammonium salt catalyst is characterized in that it is reused after being recrystallized using a solvent.

[0092] The solvent is not limited as long as it can precipitate and recrystallize the ammonium salt catalyst, and is preferably selected from the group consisting of ethyl acetate, methylethyl ketone, 2-methyltetrahydrofuran, tetrahydrofuran, toluene, hexane, chloroform, and combinations thereof.

[0093] The above-mentioned modified natural oil production is performed by reacting a nucleophile with an epoxidized natural oil represented by the following chemical formula 1 to produce a modified natural oil represented by the following chemical formula 2, and the details thereof are described below.

[0094]

[0095] Method for producing modified natural oil

[0096] The present invention provides a method for producing a modified natural oil represented by the following chemical formula 2 by reacting a nucleophile with an epoxidized natural oil represented by the following chemical formula 1, characterized in that an ammonium salt catalyst is used.

[0097] Figure 1 is a process flow diagram of a method for manufacturing a modified natural oil of the present invention.

[0098] Referring to FIG. 1, the method for producing a modified natural oil of the present invention includes a step (S100) of producing a modified natural oil by reacting an epoxidized natural oil with a nucleophile and an ammonium salt catalyst; and a step (S200) of recrystallizing the ammonium salt catalyst by adding a solvent to the reactants of the step.

[0099] Below, we will explain in detail step by step.

[0100] (a) A modified natural oil represented by chemical formula 2 is produced by reacting an epoxidized natural oil represented by chemical formula 1 with a nucleophile and an ammonium salt catalyst (S100).

[0101] [Chemical Formula 1]

[0102]

[0103] [Chemical Formula 2]

[0104]

[0105] In the above formula,

[0106] R 1 , R 2 are each a substitutable hydrocarbon group, a C1-C50 alkyl group, a C3-C10 aryl group or a heteroaryl group, and the substituents of the alkyl group, aryl group and heteroaryl group are one or a combination of two or more selected from the group consisting of hydroxy, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino, heteroaryl, alkoxy, epoxy, carbonyl and carboxylic acid ester.

[0107] R 3 is -OH or and R 4 Is and,

[0108] The above R 3 and R 4 In , R' is each a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, alkylene, aryl, and alkoxy.

[0109] n is an integer from 1 to 50.

[0110] The epoxidized natural oil represented by the above chemical formula 1 may preferably be epoxidized soybean oil (ESO or ESBO), but is not limited thereto. Epoxidized soybean oil is a non-toxic, transparent, yellow liquid used as a plasticizer or stabilizer in PVC and its copolymers.

[0111] The monomer of the above epoxidized soybean oil contains an average of about 4 epoxy functional groups (oxirane rings).

[0112] By using various nucleophiles in the ring-opening reaction of the above reaction scheme 1, functional groups can be selectively introduced into the modified natural oil (Table 2).

[0113] The above ammonium salt catalyst may be represented by the following chemical formula 3.

[0114] [Chemical Formula 3]

[0115]

[0116] In the above formula,

[0117] R 5is hydrogen or a substitutable hydrocarbon group, a C1-C10 alkyl group, a benzyl group or a C3-C10 aryl group, and the substituent of the alkyl group, benzyl group or aryl group is selected from C1-C10 alkyl, C3-C10 aryl or halogen element (Cl, Br, I or F),

[0118] R 6 is a C1-C10 alkyl group, a C1-C10 alkylamino group, a C1-C10 dialkylamino group or a C3-C10 aryl group,

[0119] X - is Cl - , Br - , I - , F - This or RCOO, the anion of carboxylic acid - (wherein, R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkylene group, or a substituted or unsubstituted C3-C10 aryl group) or C7H4O3NS, which is an anion of saccharin. - am.

[0120] Examples of ammonium salt catalysts according to one embodiment of the present invention include 4-(N,N-dimethylamino)pyridine cinnamic acid salt, 4-(N,N-dimethylamino)pyridine saccharin salt, 4-(dimethylamino)pyridine benzyl chloride salt, 4-(N,N-dimethylamino)pyridine-1-(p-fluorobenzyl) chloride salt, or 4-(N,N-dimethylamino)pyridine benzyl bromide salt, which are represented by the chemical formulas below.

[0121] [DMAP-CA: 4-(N,N-dimethylamino)pyridine cinnamate]

[0122]

[0123] [DMAP-SA: 4-(N,N-dimethylamino)pyridine saccharin salt]

[0124]

[0125] [DMAP-BC: 4-(dimethylamino)pyridine benzyl chloride salt]

[0126]

[0127] [DMAP-B f C: 4-(N,N-dimethylamino)pyridine-1-(p-fluorobenzyl) chloride salt]

[0128]

[0129] [DMAP-BB: 4-(N,N-dimethylamino)pyridine benzyl bromide salt]

[0130]

[0131] The nucleophile may be a compound of the following chemical formula 4 or an anhydride thereof.

[0132] [Chemical Formula 4]

[0133]

[0134] In the above formula,

[0135] R is a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, alkylene, aryl, and alkoxy.

[0136] The nucleophile is preferably an organic acid, and the nucleophile is selected from the group consisting of palmitic acid, undecanoic acid, valeric acid, p-anisic acid, cinnamic acid, trans-cinnamic acid, undecylenic acid, acetic acid, palmitic anhydride, p-anisic anhydride, caproleic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, brassic acid, benzoic acid, and phenylacetic acid. It could be one or a combination of two or more.

[0137] The content of the nucleophile may be 0.5 to 2 equivalents relative to the epoxidized natural oil, and more preferably 0.75 to 1.5 equivalents. It is preferable that one nucleophile molecule reacts per epoxy functional group. Since the epoxidized soybean oil monomer contains an average of 4 oxirane rings, 1 equivalent of the nucleophile can be calculated as [mmol of epoxidized natural oil x 4 (the number of epoxy rings of ESO)].

[0138] The ammonium salt catalyst may be used in an amount of 1 to 20 mol%, preferably 3 to 10 mol%. Below the above range, there is a problem of weak reaction, and above the above range, there is a problem of poor economic feasibility.

[0139] The above reaction may be carried out at 80 to 150°C. In the above temperature range, the ammonium salt catalyst acts as a homogeneous catalyst during the reaction of this step, and after the reaction of this step is completed, the temperature is lowered to room temperature and a solvent is added to recrystallize it into a heterogeneous catalyst. Below the above range, the reaction does not proceed well, which causes a problem of low conversion rate, and above the above range, a side reaction in which two vegetable oil molecules combine occurs, which causes a problem of low selectivity.

[0140] The above reaction may be carried out for 1 to 30 hours, and preferably for 1 to 10 hours. Below the above range, it is difficult to achieve 100% conversion, and above the above range, efficiency is reduced.

[0141] According to the manufacturing method of the present invention, the conversion rate and selectivity of the modified natural oil are excellent. According to an embodiment of the present invention, the conversion rate of the modified natural oil may be 90% or more, and preferably 95% to 99%, based on the starting material (Table 1). According to an embodiment of the present invention, the selectivity of the modified natural oil may be 65% or more, and preferably 70% to 99%, of the monomer content, which is the main product, with respect to the total modified natural oil (Table 1).

[0142] The main product to be produced in the present invention may be a monomer, and the side product may be a dimer (Fig. 3).

[0143] (b) A solvent is added to the reactants of step (a) to recrystallize the ammonium salt catalyst (S200).

[0144] This step can be performed by recrystallizing the ammonium salt catalyst used in the reaction of step (a), filtering it, recovering it, and reusing it. Preferably, the ammonium salt catalyst recovered by filtration can be dried and reused in the reaction of step (a).

[0145] The ammonium salt catalyst may act as a homogeneous catalyst during the reaction in step (a), and may be reused after recrystallization using a solvent in step (b) after the reaction. Specifically, it may act as a homogeneous catalyst during the reaction in step (a) to allow the reaction to proceed within a short period of time, and may be reused after recrystallization by adding an additional solvent and / or controlling the temperature in step (b) after the reaction.

[0146] The solvent may be selected from the group consisting of ethyl acetate, methylethyl ketone, 2-methyltetrahydrofuran, tetrahydrofuran, toluene, hexane, chloroform, and combinations thereof. For example, the solvents may be used individually, or various solvents may be mixed and used at various ratios, such as EA:Hexane = 1:1.

[0147] The amount of the solvent added may be 25 ml or less per 1 g of epoxidized natural oil, preferably 16 ml or less, and more preferably 2 to 16 ml. If less than the minimum amount is added, recrystallization of the catalyst does not occur well, and if more than the maximum amount is added, there is a problem that the efficiency is lowered compared to the amount of solvent added.

[0148] This step (b) may be performed at 0 to 50°C, and if the temperature is outside this range, there is a problem that the recrystallization efficiency decreases.

[0149] In the embodiments of the present invention, referring to Table 3, it can be seen that there is little difference in the conversion rate to modified natural oil and the selectivity between main product and byproduct depending on the type of solvent used for catalyst recrystallization. Furthermore, referring to Table 4, it can be confirmed that there is no change in the conversion rate and selectivity even when the ammonium salt catalyst according to the present invention is repeatedly reused.

[0150] Example

[0151] Hereinafter, the present invention will be described in detail with examples to specifically illustrate it. However, the examples according to the present invention may be modified in various ways, and the scope of the present invention should not be construed as being limited to the examples described below. These examples are provided to more fully explain the present invention to those of average skill in the art.

[0152] <Materials>

[0153] Epoxidized soybean oil (ESO) was purchased from Sajo, and cinnamic acid was used as the nucleophile, which was purchased from Sigma-Aldrich. The chemical formulas of the epoxidized soybean oil, organic acid, and ammonium salt catalyst used in this example are as follows.

[0154] [Epoxidized soybean oil]

[0155]

[0156] [Shinnamsan]

[0157]

[0158] [Ammonium salt catalyst]

[0159]

[0160] <Example 1>

[0161] The reaction formula of Example 1 is as follows.

[0162]

[0163] Example 1 was performed as follows. A stirring bar, ESO (epoxidized soybean oil, 2.50 g, 2.63 mmol = 10.5 mmol [1.0 eq.] of epoxy ring), a catalyst described in Table 1, and cinnamic acid (1.0 eq. = 10.5 mmol) were placed in a 20 mL vial.

[0164] Next, the vial was placed in an oil bath heated to 130°C and the reaction was allowed to proceed for 3 hours. After the reaction was completed, the vial was cooled to room temperature, then opened and a sample was collected. About this sample 1 The conversion rate was analyzed through H NMR, and the selectivity of the main product / by-product of the modified natural oil was analyzed through GPC, and the results are shown in Figs. 2 and 3.

[0165] The nucleophile, catalyst, solvent, and reaction conditions of Examples 1-1 to 1-13 were performed as shown in Table 1 below.

[0166]

[0167] b Concentrated sulfuric acid (35%) is used. A side reaction occurs due to the sulfuric acid catalyst, resulting in a complex 1 H NMR spectra generated

[0168] c The reaction was observed to have a conversion of 53% at 80°C. The selectivity of the reaction at 80°C could not be calculated due to overlap with the starting material.

[0169] * PPh3: Triphenylphosphine, NMP: N-Methyl-2-pyrrolidone, DMAP: 4-(DiMethylAmino)Pyridine, PS: Polystyrene, PS-DMAP: DMAP catalyst supported on polymer (polystyrene) (see Patent Application No. 10-2022-0079542)

[0170] Figure 2 shows the cinnamic acid esterified soybean oil (CASO) produced by Example 1-13. 1 H NMR of epoxidized soybean oil (ESO) and cinnamic acid (CA) 1 This was compared with H NMR analysis. Through this, the number of epoxy rings per molecule of the starting material ESO before the reaction and the number of epoxy rings remaining after the reaction were compared to calculate the conversion rate, and the conversion rate was calculated using the same method in the examples below.

[0171] Figure 3 shows the GPC analysis results of CASO, the main product, compared with the GPC analysis results of ESO in Examples 1-13. Through this, selectivity was calculated by calculating the area ratio between the peaks of CASO, the main product, and the peaks of the byproducts, and selectivity was calculated using the same method in the following examples.

[0172] <Example 2>

[0173] The reaction formula of Example 2 is as follows.

[0174]

[0175] Examples 2-1 to 2-9 were performed in the same manner as Example 1, except that various organic acids or acid anhydrides (Table 2) were used as nucleophiles. The conversion rate to modified natural oil and the selectivity of main product:byproduct were analyzed, and the results are shown in Table 2.

[0176]

[0177]

[0178]

[0179] Referring to Table 2, the ammonium salt catalyst according to the present invention was used to react epoxidized natural oil with various acids or acid anhydrides to produce various types of esterified vegetable oils. Furthermore, using acids and acid anhydrides available in nature, eco-friendly modified natural oils with a bio-content of 51-100% were produced.

[0180] <Example 3>

[0181] The reaction formula of Example 3 is as follows.

[0182]

[0183] After the reaction of Example 1 was completed, the vial was cooled to room temperature, and the solvent listed in Table 3 was added to recrystallize the catalyst (DMAP-BB) and recover it through a filter (Fig. 4).

[0184] Examples 3-1 to 3-4 were carried out in the same manner as in Example 1, except that the catalyst DMAP-BB (4-(Dimethylamino) pyridine, 10.0 mol%) recovered after recrystallization using various solvents (Table 3) was used. The conversion rate to modified natural oil, the selectivity of main product:byproduct, and the recovery rate of the catalyst were analyzed, and the results are shown in Table 3.

[0185]

[0186] Referring to Table 3, the conversion rate to modified natural oil and the selectivity between main product and byproduct were excellent and did not differ significantly depending on the type of solvent used for catalyst recrystallization. The catalyst recovery rate was over 95% when tetrahydrofuran, 2-methyltetrahydrofuran, and ethyl acetate were used for catalyst recrystallization, but relatively low recovery rates were observed when methyl ethyl ketone was used.

[0187]

[0188] <Example 4>

[0189] The reaction formula of Example 4 is as follows.

[0190]

[0191] Example 4 was performed by repeating the same reaction as Example 1 from 1 to 5 times using the catalyst DMAP-BB (4-(Dimethylamino) pyridine, 10.0 mol%), and the conversion rate to modified natural oil, the selectivity of main product:byproduct, and the recovery rate of the catalyst were analyzed for each time, and the results are shown in Table 4.

[0192]

[0193] Referring to Table 4, it was found that the ammonium salt catalyst according to the present invention maintains the same conversion rate and selectivity as the initial value even when repeatedly reused, and the catalyst recovery rate is also maintained at a high level.

[0194] Also, referring to Figure 5, after repeatedly using the catalyst DMAP-BB up to 5 times, 1 As a result of measuring H NMR, it was confirmed that the ammonium salt catalyst according to the present invention did not show any change in the catalyst structure even when repeatedly reused.

[0195] So far, specific examples of an ammonium salt catalyst for producing modified natural oil according to one embodiment of the present invention and a method for producing modified natural oil using the same have been described, but it is obvious that various modifications are possible within the scope of the present invention.

[0196] Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined not only by the claims described below but also by equivalents of the claims.

[0197] That is, it should be understood that the above-described embodiments are exemplary in all respects and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

[0198] The present invention provides an ammonium salt catalyst for producing modified natural oil, which acts as a homogeneous catalyst during a reaction for producing modified natural oil, allowing the reaction to proceed within a short period of time, and which can be reused by recrystallizing and recovering the catalyst by adding a solvent after the reaction is completed, and a method for producing modified natural oil using the same.

Claims

1. Ammonium salt catalyst for producing modified natural oil represented by the following chemical formula 3: [Chemical Formula 3] In the above formula, R 5 is hydrogen or a substitutable hydrocarbon group, a C1-C10 alkyl group, a benzyl group or a C3-C10 aryl group, and the substituent of the alkyl group, benzyl group or aryl group is selected from C1-C10 alkyl, C3-C10 aryl or halogen element (Cl, Br, I or F). R 6 is hydrogen, a C1-C10 alkyl group, a C1-C10 alkylamino group, a C1-C10 dialkylamino group or a C3-C10 aryl group, X - is Cl - , Br - , I - , F - This is RCOO, the anion of carboxylic acid. - (wherein, R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkylene group, or a substituted or unsubstituted C3-C10 aryl group) or C7H4O3NS, which is an anion of saccharin. - am.

2. In paragraph 1, The above ammonium salt catalyst Characterized in that it is reused after being recrystallized using a solvent. Ammonium salt catalyst for producing modified natural oil.

3. A method for producing a modified natural oil represented by the following chemical formula 2 by reacting a nucleophile with an epoxidized natural oil represented by the following chemical formula 1, Characterized in that it uses an ammonium salt catalyst, Method for producing denatured natural oil: [Chemical Formula 1] [Chemical formula 2] In the above formula, R 1 , R 2 are each a substitutable hydrocarbon group, a C1-C50 alkyl group, a C3-C10 aryl group or a heteroaryl group, and the substituents of the alkyl group, the aryl group and the heteroaryl group are one or a combination of two or more selected from the group consisting of hydroxy, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino, heteroaryl, alkoxy, epoxy, carbonyl and carboxylic acid ester. R 3 is -OH or And, R 4 Is And, Above R 3 and R 4 In , R' is each a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, alkylene, aryl, and alkoxy. n is an integer from 1 to 50.

4. In paragraph 3, The above ammonium salt catalyst Characterized by being represented by the following chemical formula 3, Method for producing denatured natural oil: [Chemical Formula 3] In the above formula, R 5 is hydrogen or a substitutable hydrocarbon group, a C1-C10 alkyl group, a benzyl group or a C3-C10 aryl group, and the substituent of the alkyl group, benzyl group or aryl group is selected from C1-C10 alkyl, C3-C10 aryl or halogen element (Cl, Br, I or F). R 6is hydrogen, a C1-C10 alkyl group, a C1-C10 alkylamino group, a C1-C10 dialkylamino group or a C3-C10 aryl group, X - is Cl - , Br - , I - , F - This is RCOO, the anion of carboxylic acid. - (wherein, R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkylene group, or a substituted or unsubstituted C3-C10 aryl group) or C7H4O3NS, which is an anion of saccharin. - am.

5. In paragraph 3, The nucleophile is characterized by being represented by the following chemical formula 4 or an anhydride thereof. Method for producing denatured natural oil: [Chemical Formula 4] In the above formula, R is a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, alkylene, aryl, and alkoxy.

6. In paragraph 3, The above nucleophile is A compound characterized by being one or a combination of two or more selected from the group consisting of palmitic acid, undecanoic acid, valeric acid, p-anisic acid, cinnamic acid, trans-cinnamic acid, undecylenic acid, acetic acid, palmitic anhydride, p-anisic anhydride, caprolecic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, brassic acid, benzoic acid and phenylacetic acid. Method for producing denatured natural oil.

7. In paragraph 3, The above ammonium salt catalyst Characterized in that it acts as a homogeneous catalyst during the above reaction. Method for producing denatured natural oil.

8. In paragraph 3, The above ammonium salt catalyst It is characterized in that it is reused after being recrystallized using a solvent after the above reaction. Method for producing denatured natural oil.

9. In paragraph 8, The above solvent is Characterized in that it is selected from the group consisting of ethyl acetate, methylethyl ketone, 2-methyltetrahydrofuran, tetrahydrofuran, toluene, hexane, chloroform and combinations thereof. Method for producing denatured natural oil.

10. In paragraph 3, The above ammonium salt catalyst Characterized in that it is used in an amount of 1 to 20 mol%, Method for producing denatured natural oil.

11. In paragraph 3, Characterized in that it reacts at 80 to 150 ℃, Method for producing denatured natural oil.

12. In paragraph 3, characterized by reacting for 1 to 30 hours; Method for producing denatured natural oil. 13.(a) a step of producing a modified natural oil represented by the following chemical formula 2 by reacting an epoxidized natural oil represented by the following chemical formula 1 with a nucleophile and an ammonium salt catalyst; and (b) a step of recrystallizing an ammonium salt catalyst by adding a solvent to the reactant of step (a); characterized in that it includes; Method for producing natural modified oil: [Chemical Formula 1] [Chemical formula 2] In the above formula, R 1 , R 2are each a substitutable hydrocarbon group, a C1-C50 alkyl group, a C3-C10 aryl group or a heteroaryl group, and the substituents of the alkyl group, the aryl group and the heteroaryl group are one or a combination of two or more selected from the group consisting of hydroxy, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino, heteroaryl, alkoxy, epoxy, carbonyl and carboxylic acid ester. R 3 is -OH or And, R 4 Is And, Above R 3 and R 4 In , R' is each a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkylene group, or a substituted or unsubstituted C3-C10 aryl group, and the substituent of the alkyl group, alkylene group, or aryl group is one or a combination of two or more selected from the group consisting of alkyl, alkylene, aryl, and alkoxy. n is an integer from 1 to 50.

14. In paragraph 13, The above ammonium salt catalyst Characterized by being represented by the following chemical formula 3, Method for producing denatured natural oil: [Chemical Formula 3] In the above formula, R 5 is hydrogen or a substitutable hydrocarbon group, a C1-C10 alkyl group, a benzyl group or a C3-C10 aryl group, and the substituent of the alkyl group, benzyl group or aryl group is selected from C1-C10 alkyl, C3-C10 aryl or halogen element (Cl, Br, I or F). R 6 is hydrogen, a C1-C10 alkyl group, a C1-C10 alkylamino group, a C1-C10 dialkylamino group or a C3-C10 aryl group, X - is Cl - , Br - , I - , F - This is RCOO, the anion of carboxylic acid. - (wherein, R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkylene group, or a substituted or unsubstituted C3-C10 aryl group) or C7H4O3NS, which is an anion of saccharin. - am.

15. In paragraph 13, The above step (a) is performed at 80 to 150°C, The above step (b) is characterized in that it is performed at 0 to 50°C. Method for producing denatured natural oil.

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