Methods for producing monomers, methods for producing polymers, and compounds
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- HONDA MOTOR CO LTD
- Filing Date
- 2025-01-22
- Publication Date
- 2026-08-03
Smart Images
Figure 2026125257000030 
Figure 2026125257000001 
Figure 2026125257000002
Abstract
Description
Technical Field
[0001] The present invention relates to a method for producing a monomer, a method for producing a polymer, and a compound.
Background Art
[0002] In recent years, efforts have been actively made to significantly reduce the generation of waste through prevention, reduction, recycling, and reuse of waste. Toward this realization, research and development on the recycling of polypropylene have been carried out.
[0003] Patent Document 1 describes synthesizing polypropylene having vinylidene groups at both ends by thermally decomposing polypropylene, and then synthesizing terminal aminoated polypropylene through terminal hydroxylation and terminal tosylation. Further, Patent Document 1 describes polymerizing terminal aminoated polyolefin. <000001四>
Prior Art Documents
Patent Documents
[0004]
Patent Document 1
Summary of the Invention
Problems to be Solved by the Invention
[0005] However, in the method described in Patent Document 1, since polypropylene is thermally decomposed, it is difficult to produce terminal aminoated polypropylene having a homogeneous molecular weight.
[0006] An object of the present invention is to provide a method for producing a monomer capable of producing a terminal-modified propylene oligomer having a homogeneous molecular weight.
Means for Solving the Problems
[0007] <00四0037>[1] General formula (1) [ka] (In the formula, R1, R2, and R3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and n is an integer of 0 or more.) By reacting the compound represented by general formula (2), [ka] A step to obtain a winerebamide represented by the formula (3), and a step to react the winerebamide with an organometallic compound to obtain a winerebamide represented by the formula (3). [ka] A step to obtain a ketone represented by the formula (4), and a step to methyleneate the ketone to obtain the general formula (4) [ka] A step to obtain a compound represented by the above general formula (4), and a compound represented by the general formula (5) [ka] (In the formula, R4 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and X is a halo group or a tosyloxy group.) The compound represented by is subjected to a reductive hydrocarbon reaction, resulting in the general formula (6). [ka] A method for producing a monomer, comprising the step of obtaining a compound represented by .
[0008] A method for producing a polymer, comprising the steps of producing a monomer using the monomer production method described in [2][1] and polymerizing the monomer.
[0009] [3] General formula (6) [ka] (In the formula, R1, R2 and R4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, and n is an integer of 0 or more.) A compound represented by [Advantages of the Invention]
[0010] According to the present invention, it is possible to provide a method for producing a monomer capable of producing a terminally modified propylene oligomer having a homogeneous molecular weight. [Brief Description of the Drawings]
[0011] [Figure 1] 1H-NMR spectrum of compound 7 in Example 1[[ID=???]] [Embodiments for Carrying Out the Invention]
[0012] Hereinafter, embodiments of the present invention will be described.
[0013] [Method for Producing Monomer] When the method for producing a monomer of the present embodiment is used, the general formula (6) [Chemical Formula] (In the formula, R1, R2 and R4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, and n is an integer of 0 or more.) A compound can be obtained. Hereinafter, the case where n = 0 will be described.
[0014] First, the general formula (1-1) [Chemical Formula] <By reacting the compound represented by the general formula (2-1), [ka] A winerebamide represented by the formula (1-1) is obtained. A commercially available compound can be used as the compound represented by the general formula (1-1). When obtaining winerebamide, for example, methyl(methoxy)amine hydrochloride is reacted.
[0015] Here, if R1 and R2 are phenyl or benzyl groups, reaction monitoring by thin-layer chromatography (TLC) becomes easier. Also, if R1 and R2 are methyl or ethyl groups, steric hindrance is less likely, allowing the reaction to proceed more easily.
[0016] Next, a compound represented by general formula (2-1) is reacted with an organometallic compound to form general formula (3-1). [ka] A ketone represented by the formula (3-1) is obtained. The organometallic compound is not particularly limited as long as it is possible to obtain a ketone represented by the general formula (3-1), but examples include Grignard reagents (methylmagnesium halide) and methyllithium.
[0017] Next, the ketone represented by general formula (3-1) is subjected to a methylene reaction to obtain general formula (4-1). [ka] A compound represented by is obtained. The methylene agent is not particularly limited as long as it can react to methylate the ketone, but examples include 1-methyl-2-(methylsulfonyl)benzimidazole (see, for example, K. Ando, T. Kobayashi, N. Uchida, Org. Lett., 2015, 17, 2554).
[0018] Next, the compound represented by general formula (4-1) and general formula (5) [ka] (In the formula, R4 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and X is a halo group or a tosyloxy group.) The compound represented by is subjected to a reductive hydrocarbon reaction, resulting in the general formula (6-1). [ka] A compound represented by the formula (6-1) is obtained. Here, X in general formula (5) is not particularly limited as long as it can be subjected to a reductive hydrocarbon reaction, but for example, an iodine group is used. The compound represented by general formula (6-1) is a mixture of the syn and anti isomers. As a catalyst for the reductive hydrocarbon reaction, for example, NiBr2 diglyme can be used (see, for example, Xi Lu, et al., Nat.Commn., 2016, 7, 11129).
[0019] At this time, if the compound represented by general formula (6-1) is used instead of the compound represented by general formula (1-1) and the reaction is carried out as described above, the compound represented by general formula (6) (n=2), i.e., general formula (6-2) [ka] A compound represented by the formula (1-1) is obtained. Furthermore, if the compound represented by the general formula (6-2) is used instead of the compound represented by the general formula (1-1) and the reaction is carried out as described above, a compound represented by the general formula (6) (n=4) is obtained. Therefore, a terminally modified propylene oligomer with a homogeneous molecular weight can be produced. In addition, n can be controlled.
[0020] [Method for producing polymers] The polymer manufacturing method of this embodiment includes the steps of manufacturing a monomer using the monomer manufacturing method of this embodiment and polymerizing the monomer. Therefore, the physical properties of the polymer are stable. For example, when R1, R2 and R4 are hydrogen atoms, when a compound represented by general formula (6) is subjected to a polycondensation reaction, general formula (7) [ka] (In the formula, m is the degree of polymerization.) A polyamide represented by the formula (7) is obtained. Polyamides represented by the general formula (7) are easier to depolymerize than polypropylene and therefore have excellent chemical recyclability. Furthermore, when R1, R2, and R4 are alkyl groups, aralkyl groups, or aryl groups, R1, R2, and R4 may be hydrogenated by known methods before being subjected to polycondensation.
[0021] n is preferably 3 or greater. When n is 3 or greater, the properties of the polymer are expected to be equivalent to those of polypropylene.
[0022] Although embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and the above embodiments may be modified as appropriate within the scope of the spirit of the present invention. [Examples]
[0023] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.
[0024] [Example 1] (Synthesis of winelevamide) [ka] A solution of N,O-dimethylhydroxyamine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.; Compound 2) (6.89 g, 70.6 mmol, 2.3 eq.) dissolved in THF (60 mL) was cooled to -4°C with salt ice, and then a hexane solution of Me3Al (1.08 M, 68.0 mL, 76.8 mmol, 2.5 eq.) was added dropwise. Next, the mixture was stirred at room temperature for 30 minutes, and then a THF solution of N,N-dibenzylglycine ethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.; Compound 1) (8.33 g, 29.4 mmol) (23 mL) was added dropwise at room temperature, and the mixture was stirred for 20 hours. Next, under ice cooling, a 10% by mass aqueous solution of potassium sodium tartrate was added dropwise to stop the reaction, and the mixture was filtered. The filtrate was extracted with ethyl acetate (SiO2). Next, the extract was washed with brine, dried over magnesium sulfate (MgSO4), and then concentrated to obtain the crude compound 3 (5.29 g). Next, using silica (SiO2) gel as the packing material and a hexane / siRNA mixed solvent as the developing solvent, the crude compound 3 was purified by column chromatography to obtain compound 3 (yield: 2.81 g, yield: 32.0%, GC purity: 99.5%).
[0025] (Grignard reaction) [ka] Compound 3 (3.55 g, 11.9 mmol) was dissolved in THF (67 mL). Under ice cooling, a THF solution of MeMgBr (1.0 M, 42 mL, 3.5 eq.) was added, and the mixture was stirred at room temperature for 3 hours. Next, under ice cooling, an aqueous solution of saturated ammonium chloride (NH4Cl) was added dropwise to stop the reaction, and the mixture was extracted with phenylethylamine. The extract was then washed with brine, dried over MgSO4, and concentrated to obtain crude compound 4 (3.17 g). Next, crude compound 4 was purified by column chromatography using an SiO2 gel as the packing material and a hexane / phenylethylamine mixed solvent as the developing solvent to obtain compound 4 (yield: 2.58 g, yield: 85.7%). Here, compound 4 consists of 0.96 g of fraction with GC purity of 96.6% and 1.62 g of fraction with GC purity of 98.0%.
[0026] (Methylene reaction) [ka] Compound 4 (0.760 g, 3.0 mmol) and 1-methyl-2-(methylsulfonyl)benzimidazole (0.755 g, 3.59 mmol, 1.2 eq.) were dissolved in dimethylformamide (DMF) (15 mL). Potassium t-butoxide (tBuOK) (0.47 g, 4.1 mL, 3.0 eq.) was added to the solution under ice cooling, and the mixture was stirred at room temperature for 2 hours. Next, saturated aqueous NH4Cl was added dropwise under ice cooling to stop the reaction, and the mixture was extracted with phenylethylamine. The solution was then washed with water and brine, dried over MgSO4, and concentrated to obtain the crude compound 5 (1.17 g). Next, the crude compound 5 was purified by column chromatography using an SiO2 gel as the packing material and a hexane / phenylethylamine mixed solvent as the developing solvent to obtain compound 5 (yield: 0.65 g, yield: 86.2%, GC purity: 99.6%).
[0027] (Reductive hydrocarbon reaction) [ka] NiBr2 diglyme (0.057 g, 0.19 mmol, 0.30 eq.), 4,4'-di-tert-butyl-2,2'-bipyridine (0.075 g, 0.28 mmol, 0.45 eq.), and sodium carbonate (Na2CO3) (0.131 g, 1.24 mmol, 2.0 eq.) were placed in a flask and degassed under reduced pressure. Next, a solution of compound 6 (0.312 g, 1.24 mmol, 2.0 eq.) and compound 5 (0.150 g, 0.62 mmol) dissolved in dimethylacetamide (DMAc) (4.0 mL) was added and the mixture was stirred for 10 minutes. Next, diethoxymethylsilane (DEMS) (0.20 mL, 1.24 mmol, 2.0 eq.) was added and the mixture was stirred at 30°C for 24 hours. Finally, the reaction mixture was stopped by adding water, filtered, and the filtrate was extracted with phenylethylamine. Next, the extract was washed with water and brine, dried over MgSO4, and then concentrated to obtain crude compound 7 (0.23 g). Then, crude compound 7 was purified by column chromatography using an SiO2 gel as the packing material and a hexane / SiO2 mixed solvent as the developing solvent to obtain compound 7 (yield: 0.0278 g, yield: 12.2%). Here, compound 7 consists of 0.0444 g of fraction with GC purity of 41.7% and 0.0114 g of fraction with GC purity of 81.6%.
[0028] Compound 6 was synthesized as follows.
[0029] (Synthesis of Compound 6) [ka] Ethyl DL-3-hydroxybutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.; compound 8) (12.00 g, 90.80 mmol) was dissolved in THF (240 ml). Under ice cooling, imidazole (15.46 g, 227.0 mmol, 2.5 eq.) and triphenylphosphine (PPh3) (47.63 g, 181.6 mmol, 2.0 eq.) were added, and the mixture was stirred for 30 minutes. Next, under ice cooling, iodine (I2) (46.09 g, 181.6 mmol, 2.0 eq.) was added, and the mixture was stirred for 2.5 hours after being shielded from light with aluminum foil. Next, under ice cooling, a 10% by mass aqueous solution of sodium thiosulfate (Na2S2O3) was added dropwise to stop the reaction, and the mixture was extracted with SiO2. The extract was then washed with water and brine, dried over MgSO4, and concentrated. Next, hexane was added and the mixture was filtered. The filtrate was then concentrated to obtain the crude compound 6 (22.10 g). Next, the crude compound 6 was purified by column chromatography using an SiO2 gel as the packing material and a hexane / siRNA mixed solvent as the developing solvent to obtain compound 6 (yield: 17.79 g, yield: 80.9%). At this time, the volume ratio of the hexane / siRNA mixed solvent was changed from 10 / 1 to 5 / 1.
[0030] (Identification of compound 7) Using a 600MHz nuclear magnetic resonance spectrometer (manufactured by JEOL), compound 7 was found in CDCl3. 1 Compound 7 was identified by measuring its 1H-NMR spectrum (see Figure 1).
Claims
1. General formula (1) 【Chemistry 1】 (In the formula, R １ , R ２ and R ３ Each of these is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and n is a non-negative integer. By reacting the compound represented by general formula (2), 【Chemistry 2】 A step to obtain a wine rebuamide represented by, The winelevamide is reacted with an organometallic compound to obtain general formula (3). 【Transformation 3】 The process of obtaining the ketone represented by, The ketone is subjected to a methylene reaction to obtain general formula (4). 【Chemistry 4】 A step to obtain a compound represented by, The compound represented by the general formula (4) and the general formula (5) 【Transformation 5】 (In the formula, R ４ (where X is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and X is a halo group or a tosyloxy group.) The compound represented by is subjected to a reductive hydrocarbon reaction to obtain the general formula (6). 【Transformation 6】 A method for producing a monomer, comprising the step of obtaining a compound represented by .
2. A step of producing a monomer using the monomer production method described in claim 1, A method for producing a polymer, comprising the step of polymerizing the monomer.
3. General formula (6) 【Transformation 7】 (In the formula, R １ , R ２ and R ４ Each of these is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and n is a non-negative integer. A compound represented by the formula.