Dodecahydrododecaboronic acid bis (tetramethylammonium) as well as synthesis method and application thereof
By employing a simplified synthesis method, using a tetramethylammonium borohydride and a dimethyl sulfide borane complex in an ether solvent under heating, followed by vacuum filtration and drying, the complex and costly synthesis of dodecyl dodecyl borate bis(tetramethylammonium) in existing technologies has been solved. This method achieves high purity and high yield, and is applicable to multiple technical fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SUN YAT SEN UNIV
- Filing Date
- 2025-03-31
- Publication Date
- 2026-05-01
AI Technical Summary
Existing methods for synthesizing dodecahydroborate bis(tetramethylammonium) are complex, costly, and difficult to meet commercial needs, and the purity and yield are not ideal.
A simplified one-step synthesis of tetramethylammonium dodecanoate was achieved by heating a tetramethylammonium borohydride and a dimethyl sulfide borane complex in an ether solvent, followed by vacuum filtration and drying.
The synthesis of bis(tetramethylammonium) dodecylhydroborate was achieved with high yield and high purity, suitable for large-scale industrial production, and can meet the needs of applications in energy, polymer chemistry, cancer treatment, nuclear waste extraction and solid electrolytes.
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Figure CN121949128A_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of materials synthesis technology, and in particular relates to a tetramethylammonium dodecylhydroborate, its synthesis method and application. Background Technology
[0002] In recent years, the efficient synthesis of borane compounds has attracted widespread attention in energy-related applications; especially the dodecoborate anion (borane anion). ), It has a highly symmetric closed icosahedral boron cluster structure with terminal hydrogen atoms. Its structure was first predicted by Longuet-Higgins and Roberts through calculations in 1955. In 1960, Hawthorn successfully isolated the compound experimentally for the first time, which triggered large-scale synthetic research in the following decades.
[0003] Borane anion Its unique chemical bonding structure and remarkable chemical and thermal stability make it increasingly important for applications in energy, polymer chemistry, cancer treatment, nuclear waste extraction, and solid electrolytes; for example, Professor P. Ravindran's team at the Central University of Tamil Nadu, India, in collaboration with the University of Oslo, Norway, has developed (NH4)2(B 12 H 12 ) is considered a potential boron-based hydrogen storage material; Associate Professor Zhang Haibo's team at Wuhan University, in collaboration with Associate Professor Liu Wenjing at Nanjing University of Technology, has identified dodecanoic acid anion ( ) forms boron organopolymer (BOPs) supramolecular assemblies with 4,4'-bipyridine, used for loading noble metals such as Pd and Pt, and for hydrogen desorption from ammonia borane; meanwhile, boron neutron capture therapy (BNCT) is considered one of the most promising methods for treating serious cancers, utilizing the fission of boron-10 isotopes after absorbing neutrons to release high-energy alpha particles that selectively kill cancer cells. Salts can serve as targeted drug carriers; additionally, the team led by Luo Feng at East China University of Science and Technology discovered that boron-functionalized covalent organic frameworks have significant potential in treating cations, anions, and gaseous nuclear waste; and hydroborates are promising solid electrolytes with liquid-like room-temperature ionic conductivity, which can be used in solid-state batteries. The Swiss Federal Laboratory for Materials Science and Technology is developing Li2B... 10 H 10 and Li2B 12 H 12 The equimolar mixture was ball-milled to obtain a single phase, which had ionic conductivity of 4.10 at 25 °C and 60 °C, respectively. -4 S cm -1 and 4.10 -3 S cm -1This indicates that it can be used as an ion conductor in solid-state lithium batteries.
[0004] Borane anion While possessing potential applications in multiple technological fields, the high cost of compound preparation remains a significant limiting factor for widespread commercial application; traditional borane anions... The synthesis methods for borane compounds are not only complex and costly, but also suffer from low yields and numerous byproducts; for example, in the synthesis process using solution methods or non-solventothermal methods, solution methods typically use compounds such as B2H6, B5H9, or B... 10 H 14 The borane precursor reacts with a triethylamineborane complex to form a water-insoluble borane compound [(CH3)3NH]2B. 12 H 12 However, this method requires the use of B2H6, B5H9, or B. 10 H 14 Expensive borane precursors and complex processes make industrialization difficult and fail to meet commercial needs; while solvent methods such as ball milling or annealing easily generate other boron-rich compound impurities, resulting in less than ideal purity and yield of borane compounds.
[0005] [(CH3)4N]2B 12 H 12 It includes borane anions ( ) and organoborane compounds with organic cations; existing reports [(CH3)4N]2B 12 H 12 The synthesis is a two-step reaction. The first step involves using sodium borohydride (NaBH4) with B... 10 H 14 Reaction synthesis of Na2B 12 H 12 The second step involves using a strongly acidic ion exchange resin with an aqueous solution of tetramethylamino hydroxide pentahydrate [(CH3)4NOH∙5H2O] to obtain [(CH3)4N]2B. 12 H 12 The solvent was then removed under low-pressure heat treatment to obtain anhydrous [(CH3)4N]2B. 12 H 12 However, this method requires an ion exchange step, making the preparation process cumbersome and costly, unsuitable for large-scale production. Therefore, existing methods urgently need improvement to achieve a simpler, lower-cost, and more scalable synthesis process. Thus, developing a simple, economical, and high-yield efficient synthesis method is crucial for advancing the synthesis of borane anions (…). It is of great significance to further expand its application. Summary of the Invention
[0006] In view of this, this application provides a method for synthesizing bis(tetramethylammonium) dodecylhydroborate, its application, and its synthesis, in order to solve the technical problem of the lack of an efficient synthesis process for bis(tetramethylammonium) dodecylhydroborate.
[0007] The first aspect of this application provides a method for synthesizing bis(tetramethylammonium) dodecylhydroborate, the method comprising the following steps:
[0008] Step S1: Complex tetramethylammonium borohydride (CH3)4NBH4 with dimethyl sulfide borane. Ether solvents are added to the reaction vessel to dissolve and obtain a mixed solution;
[0009] Step S2: The mixed solution in the reactor is heated under an inert atmosphere to obtain a suspension of dodecylhydroborate bis(tetramethylammonium)
[0010] Step S3: The suspension of dodecanoic acid bis(tetramethylammonium) was subjected to vacuum filtration, washing and drying to obtain dodecanoic acid bis(tetramethylammonium) in sequence.
[0011] Preferably, in step S1, the tetramethylammonium borohydride (CH3)4NBH4 and borane dimethyl sulfide complex The molar ratio is 1:5~15.
[0012] Preferably, in step S1, the molar volume ratio of the tetramethylammonium borohydride (CH3)4NBH4 to the ether solvent is 5 mmol: 12~20 mL.
[0013] Preferably, in step S1, the ether solvent is selected from at least one of diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol dimethyl ether, 1,4-oxane cyclic ether, and tetrahydrofuran cyclic ether.
[0014] Preferably, in step S2, the heating reaction temperature is 100ºC~200ºC and the time is 12h~36h.
[0015] Preferably, in step S2, the inert atmosphere used for the heating reaction is at least one of argon, helium, and neon.
[0016] Preferably, in step S3, the vacuum filtration process is as follows: the dodecyl borate bis(tetramethylammonium) suspension is naturally cooled to room temperature and then added to the Schelek flask of the Schelek vacuum filtration device for vacuum filtration.
[0017] The washing process is as follows: wash 1 to 5 times with an ether solvent;
[0018] The drying process is as follows: vacuum drying at 100ºC~200ºC for 2h~6h.
[0019] The second aspect of this application provides bis(tetramethylammonium) dodecylhydroborate, which is prepared by the method described in the first aspect.
[0020] The third aspect of this application provides the application of the dodecyldodecylborate bis(tetramethylammonium) as described in the second aspect of this application in the fields of energy, polymer chemistry, cancer treatment, nuclear waste extraction, or solid electrolytes.
[0021] The fourth aspect of this application provides a solid-state lithium battery, characterized in that the solid electrolyte of the solid-state lithium battery includes the tetramethylammonium dodecylhydroborate described in the second aspect.
[0022] Compared with the prior art, the method for synthesizing dodecahydroborate bis(tetramethylammonium) provided in this application has at least the following beneficial effects.
[0023] 1. This application provides a method for synthesizing dodecanoic acid bis(tetramethylammonium) in one step in a high-pressure reactor. The reaction steps are simple, and the yield and purity of the synthesized dodecanoic acid bis(tetramethylammonium) are excellent.
[0024] 2. The method for synthesizing dodecahydroborate bis(tetramethylammonium) provided in this application uses readily available reaction substrates, which is beneficial for large-scale industrial synthesis.
[0025] 3. The method for synthesizing dodecyldodecylborate bis(tetramethylammonium) provided in this application is expected to provide high-purity dodecyldodecylborate bis(tetramethylammonium) on a large scale, meeting the application needs of multiple fields such as energy, polymer chemistry, cancer treatment, nuclear waste extraction, or solid electrolytes. Attached Figure Description
[0026] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0027] Figure 1 The X-ray diffraction patterns of the solid product synthesized in Example 1 of this application and the standard spectra of bis(tetramethylammonium)dodecanoateborate.
[0028] Figure 2 The infrared spectrum of bis(tetramethylammonium) dodecylhydroborate synthesized in Example 1 of this application;
[0029] Figure 3 Hydrogen coupling of bis(tetramethylammonium) dodecylhydroborate synthesized in Example 1 of this application.11 B-NMR spectrum;
[0030] Figure 4 The dodecylhydroborate bis(tetramethylammonium) synthesized in Example 1 of this application 1 H-NMR spectrum;
[0031] Figure 5 This is a schematic diagram of the structure of the Schleck vacuum filtration device used in the post-processing step of Embodiment 1 of this application. Detailed Implementation
[0032] This application provides a method for synthesizing bis(tetramethyl)dodecanoic acid, a method for synthesizing it, and its application, in order to solve the technical problem of the lack of an efficient synthesis process for bis(tetramethyl)dodecanoic acid.
[0033] The technical solutions of this application will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0034] Given the current boron-containing anions ( The synthesis of borane compounds requires the use of relatively expensive B2H6, B5H9, or B... 10 H 14 Borane precursors have drawbacks such as easy formation of boron-rich compound impurities and cumbersome procedures, resulting in the synthesis of boron-containing anions ( The purity and yield of borane compounds are not ideal, making it difficult to efficiently synthesize bis(tetramethyl)dodecanoate. This application provides a bis(tetramethyl)dodecanoate complex. The bis(tetramethyl)dodecanoate complex provided in this application comprises: firstly, tetramethylammonium borohydride (CH3)4NBH4 and a borane dimethyl sulfide complex. An ether solvent is added to a reaction vessel to dissolve the solution and obtain a mixed solution. The mixed solution in the reaction vessel is then heated to obtain a suspension of dodecanoic acid bis(tetramethylammonium) methylammonium. Subsequent post-processing steps such as vacuum filtration, washing, and drying are performed to remove solvents and other impurities from the dodecanoic acid bis(tetramethylammonium) methylammonium suspension, thus obtaining dodecanoic acid bis(tetramethylammonium) methylammonium.
[0035] The method for synthesizing bis(tetramethyl)monium dodecylborate provided in this application uses tetramethylammonium borohydride (CH3)4NBH4 and a dimethyl sulfide boronate complex as the reaction substrate. B2H6, B5H9, or B were not used. 10 H 14This avoids the drawbacks of flammable borane precursors, such as poor market liquidity, difficulty in obtaining them, high prices, and potential hazards; simultaneously, the tetramethylammonium borohydride (CH3)4NBH4 and borane dimethyl sulfide complex... The borane compound bis(tetramethylammonium) dodecylhydrododecylboronic acid is dissolved in a reaction vessel containing an ether solvent and heated. This single-step reaction yields the borane compound bis(tetramethylammonium) dodecylhydrododecylboronic acid, avoiding cumbersome synthesis steps. The removal of the ether solvent using the Schieleck vacuum filtration device is also relatively simple, which is beneficial for increasing the yield. Simultaneously, the reaction vessel, as a high-pressure, closed space, can confine the gaseous active substances generated during the reaction within the reaction system and increase the solubility of the reaction substrate, thereby improving the reaction yield. The technical solution provided in this application can increase the yield of the borane compound bis(tetramethylammonium) dodecylhydrododecylboronic acid to 85%–90%. Furthermore, this technical solution uses ether solvents such as diethylene glycol dimethyl ether, which can remove intermediate products during the reaction process, improving the purity of the borane compound. Moreover, the bis(tetramethylammonium) dodecylhydrododecylboronic acid synthesized in this application is an organoborane compound, including an organic cation (CH3)4N. + Organic cation (CH3)4N + Due to its large size, it is difficult for it to undergo coordination reactions with ether solvents. Therefore, this application can directly obtain dodecanoic acid bis(tetramethylammonium) without coordination solvent. Infrared spectroscopy, X-ray diffraction and nuclear magnetic resonance spectra show that the technical solution provided in this application has successfully synthesized high-purity dodecanoic acid bis(tetramethylammonium)
[0036] As a preferred technical solution, the method for synthesizing dodecaborate bis(tetramethylammonium)hydride provided in this application requires controlling the reaction substrate to be tetramethylammonium borohydride (CH3)4NBH4 and a borane dimethyl sulfide complex. The dosage depends on the reaction route of the method for synthesizing bis(tetramethylammonium) dodecylhydroborate provided in this application, as shown below:
[0037] ;
[0038] Therefore, to ensure the complete and sufficient reaction of tetramethylammonium borohydride (CH3)4NBH4, this application should control the borane dimethyl sulfide complex. If the amount is excessive, the molar ratio of the two can be controlled within the range of 1:5 to 15.
[0039] As a preferred technical solution, in the method for synthesizing dodecylborate bis(tetramethylammonium)-dodecylhydroborate provided in this application, the ether solvent used can be selected from at least one of diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol dimethyl ether, 1,4-oxane cyclic ether, and tetrahydrofuran cyclic ether, and the reaction temperature can be controlled at 100~200ºC.
[0040] As a preferred technical solution, in the method for synthesizing dodecylborate bis(tetramethylammonium)-dodecylhydroborate provided in this application, air needs to be removed from the reactor, and the gas used to maintain the inert atmosphere can be argon, helium, neon, or other inert atmospheres.
[0041] Meanwhile, this application also provides a bis(tetramethyl)dodecanoic acid, a high-purity borane compound prepared by the above method. Because the bis(tetramethyl)dodecanoic acid provided by this application has high purity and relatively stable performance, it can be applied in multiple technical fields such as energy, polymer chemistry, cancer treatment, nuclear waste extraction, or solid electrolytes; for example, as a solid electrolyte in solid lithium batteries, or as an ion conductor.
[0042] The following will provide a detailed description of the dodecylhydroborate bis(tetramethylammonium)amine provided in this application, in conjunction with embodiments and experimental examples.
[0043] Example 1
[0044] Example 1 of this application provides a method for preparing dodecanoic acid bis(tetramethylammonium)borate. The preparation method includes the steps of preparing a mixed solution in a reaction vessel, heating and reacting to synthesize a dodecanoic acid bis(tetramethylammonium)borate suspension, and post-treatment.
[0045] The steps for preparing the mixed solution in the reactor include: placing 0.89 g (CH3)4NBH4 (5 mmol) and an electromagnetic stirring rotor into the quartz liner of the high-pressure reactor in an argon-filled glove box, and sealing it with a sealing film to prevent air from entering; then removing the sealing film, and adding 16 mL of diethylene glycol dimethyl ether and 5.5 mL (55 mmol) The reactants were added to the quartz liner. After the high-pressure reactor was sealed, an argon gas flow was continuously introduced for 30 seconds to purge the residual air in the high-pressure reactor container. The mixture was then stirred for 5 minutes at room temperature using an electromagnetic stirrer to fully dissolve and mix the reactants, resulting in a high-pressure reactor experimental apparatus containing the mixed solution.
[0046] The steps for synthesizing a dodecyldodecylborate bis(tetramethylammonium) suspension by heating include: heating from room temperature to 150°C at a rate of 2°C / min using a temperature control device, maintaining the temperature at that temperature for 24 hours to obtain a dodecyldodecylborate bis(tetramethylammonium) suspension, and then naturally cooling to room temperature.
[0047] The post-processing steps include: adding the naturally cooled suspension of dodecylborate bis(tetramethylammonium) to a Schiller vacuum filtration apparatus (such as...). Figure 5The product was filtered under vacuum in a specially made Schiller flask with a filter cartridge (as shown), and the filtered product was washed three times with 15 mL of diethylene glycol dimethyl ether. It was then dried under vacuum at 150ºC for 4 hours to remove excess solvent, yielding the dried solid product, bis(tetramethylammonium)dodecanoate ([(CH3)4N]2B). 12 H 12 ).
[0048] Experimental Example 1
[0049] Experimental Example 1 of this application uses synchrotron X-ray diffraction (SR-PXD), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). 1 H-NMR, 11 B-NMR was used to analyze the tetramethylammonium dodecylhydroborate synthesized in Example 1 ([(CH3)4N]2B). 12 H 12 Characterization was performed to determine the purity and structure of bis(tetramethylammonium) dodecylhydroborate.
[0050] The X-ray diffraction pattern (λ=0.77509) of the solid product bis(tetramethylammonium) dodecahydroborate synthesized in Example 1 is shown below. Figure 1 As shown, after [(CH3)4N]2B 12 H 12 A comparison with standard spectra shows that the two are basically consistent; simultaneously, the dodecylhydrododecylborate bis(tetramethylammonium) synthesized in Example 1 was characterized by Fourier transform infrared spectroscopy, and the results are as follows. Figure 2 As shown, from Figure 2 It can be seen that at 2450 cm -1 1053 cm -1 713 cm -1 and 451 cm -1 Borane anions appeared at the location. The characteristic peak is at 3025 cm⁻¹. -1 1490 cm -1 1290 cm -1 and 945 cm -1 An organic cation ((CH3)4N) appeared at the location. + The characteristic peak is absent, and there are no other characteristic absorption peaks for other functional groups.
[0051] Meanwhile, the bis(tetramethylammonium) dodecylhydroborate synthesized in Example 1 was characterized using nuclear magnetic resonance spectroscopy, hydrogen coupling... 11 B-NMR spectrum, bis(tetramethylammonium) 1 H-NMR spectrum as shown Figure 3-4 As shown, from Figure 3-4It can be seen that this application successfully synthesized high-purity bis(tetramethylammonium) dodecylhydroborate ([(CH3)4N]2B). 12 H 12 No high-boron compounds were generated during the process, indicating high purity.
[0052] The above experiments demonstrate that the method for synthesizing bis(tetramethyl)dodecanoate provided in this application can synthesize high-purity bis(tetramethyl)dodecanoate in high yield. The reactants used are tetramethylammonium borohydride (CH3)4NBH4 and a boran dimethyl sulfide complex. It is readily available, which facilitates the large-scale industrial production of bis(tetramethylammonium) dodecylhydroborate to meet applications in the energy sector, polymer chemistry, cancer treatment, nuclear waste extraction, or solid electrolytes, and has high commercial value.
[0053] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.
Claims
1. A method for synthesizing bis(tetramethylammonium) dodecylhydroborate, characterized in that, Includes the following steps: Step S1: Complex tetramethylammonium borohydride (CH3)4NBH4 with dimethyl sulfide borane. Ether solvents are added to the reaction vessel to dissolve and obtain a mixed solution; Step S2: The mixed solution in the reactor is heated under an inert atmosphere to obtain a suspension of dodecylhydroborate bis(tetramethylammonium) Step S3: The suspension of dodecanoic acid bis(tetramethylammonium) was subjected to vacuum filtration, washing and drying to obtain dodecanoic acid bis(tetramethylammonium) in sequence.
2. The method for synthesizing bis(tetramethylammonium) dodecylhydroborate according to claim 1, characterized in that, In step S1, the tetramethylammonium borohydride (CH3)4NBH4 and borane dimethyl sulfide complex The molar ratio is 1:5~15.
3. The method for synthesizing bis(tetramethylammonium) dodecylhydroborate according to claim 1, characterized in that, In step S1, the molar volume ratio of the tetramethylammonium borohydride (CH3)4NBH4 to the ether solvent is 5 mmol: 12~20 mL.
4. The method for synthesizing bis(tetramethylammonium) dodecylhydroborate according to claim 1, characterized in that, In step S1, the ether solvent is selected from at least one of diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol dimethyl ether, 1,4-oxane cyclic ether, and tetrahydrofuran cyclic ether.
5. The method for synthesizing bis(tetramethylammonium) dodecylhydroborate according to claim 1, characterized in that, In step S2, the heating reaction is carried out at a temperature of 100ºC to 200ºC for a duration of 12h to 36h.
6. The method for synthesizing bis(tetramethylammonium) dodecylhydroborate according to claim 1, characterized in that, In step S2, the inert atmosphere used for the heating reaction is at least one of argon, helium, and neon.
7. The method for synthesizing bis(tetramethylammonium) dodecylhydroborate according to claim 1, characterized in that, In step S3, the vacuum filtration process is as follows: after the dodecyl borate bis(tetramethylammonium) suspension is naturally cooled to room temperature, it is added to the Schelek flask of the Schelek vacuum filtration device for vacuum filtration. The washing process is as follows: wash 1 to 5 times with an ether solvent; The drying process is as follows: vacuum drying at 100ºC~200ºC for 2h~6h.
8. A tetramethylammonium dodecylhydroborate, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.
9. The application of the dodecyldodecylborate bis(tetramethylammonium) as described in claim 8 in the fields of energy, polymer chemistry, cancer treatment, nuclear waste extraction, or solid electrolytes.
10. A solid-state lithium battery, characterized in that, The solid electrolyte of the solid-state lithium battery includes the tetramethylammonium dodecylhydroborate as described in claim 8.