Polyfunctional group four-season ammonium ion liquid and preparation method thereof

Abstract

The invention discloses polyfunctional group four-season ammonium ionic liquid and a preparation method thereof. According to the invention, 1, 4-diazido-bicyclo [2, 2, 2] octane, glycol, phosphorus trichloride or phosphorus tribromide, alkyl sultone and a sulfonic acid derivative are used as raw materials to prepare the polyfunctional group four-season ammonium ionic liquid; the method comprises the following steps: preparing dibromo (chloro) glycol by taking glycol, phosphorus trichloride or phosphorus tribromide as raw materials; the preparation method comprises the following steps: reacting 1, 4-diazido-bicyclo [2, 2, 2] octane with dibromo (chloro) glycol to prepare a tetranuclear quaternary ammonium intermediate; reacting the tetranuclear quaternary ammonium intermediate with alkyl sultone to prepare tetranuclear quaternary ammonium sulfonic acid inner salt; the polyfunctional group four-season ammonium ionic liquid is prepared by taking tetranuclear quaternary ammonium sulfonic acid inner salt and a sulfonic acid derivative as raw materials. The invention provides a new scheme for preparing the multifunctional ionic liquid.

Description

Technical Field

[0001] This invention relates to a multifunctional four-season ammonium ionic liquid and its preparation method. Background Technology

[0002] Ionic liquids are salt compounds composed of organic cations and inorganic or organic anions, generally with melting points not exceeding 100°C. They remain liquid over a wide temperature range near room temperature and possess flexible, designable structures. Their physicochemical properties can be controlled by modifying the structure or type of cations and anions to meet specific application requirements. Common cation units constituting ionic liquids include imidazole, pyridine, pyrrole, and morpholine, while anions include chloride, acetate, tetrafluoroborate, hexafluorophosphate, and bis(trifluoromethanesulfonyl)imide ions.

[0003] Acidic ionic liquids (AILs) are a branch of functionalized ionic liquids, possessing both acidic and ionic liquid properties. Acidic groups can be introduced in two ways: one is by introducing them into the cation moiety of the ionic liquid, such as introducing carboxylic acids or sulfonic acids onto the imidazole ring; the other is by introducing acidic groups into the anion moiety, such as introducing sulfate, p-toluenesulfonate, or methanesulfonate groups. The physicochemical properties of acidic ionic liquids, especially pH values, can be controlled by modifying the structure of the anions and cations or adjusting their types to meet specific requirements.

[0004] Patent CN200910206550.8 discloses an acidic ionic liquid with twinned dications. The raw materials for preparation include diheterocyclic alkanes, 1,3-propanesulfonate lactones or 1,4-butanesulfonate lactones, and organic or inorganic acids. The organic or inorganic acids include p-toluenesulfonic acid, benzoic acid, trifluoromethanesulfonic acid, methanesulfonic acid, acetic acid, trifluoroacetic acid, tetrafluoroboric acid, hexafluorophosphoric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid. The specific steps are as follows: Diheterocyclic alkanes, 1,3-propanesulfonate lactones or 1,4-butanesulfonate lactones are stirred and refluxed in an organic solvent for 48-72 hours, and a white solid, the diheterocyclic alkane sulfonate inner salt, is obtained. The diheterocyclic alkane sulfonate inner salt is then mixed with an organic or inorganic acid and stirred at 70-90°C for 6-12 hours, and the acidic ionic liquid with twinned dications is obtained. This patent does not provide a method for preparing diheterocyclic alkanes. Structural analysis revealed that the heterocyclic feedstocks included imidazole, piperidine, pyrrole, and morpholine.

[0005] Patent ZL201010503499.X reports a sulfonic acid-type binuclear imidazole hydrogen sulfate ionic liquid catalyst. The raw materials for preparation include imidazole, sodium ethoxide or potassium ethoxide, haloalkanes, 1,3-propanesulfonate lactone or 1,4-butanesulfonate lactone, and concentrated sulfuric acid. The haloalkanes are 1,2-dibromo(chloro,iodine)ethane, 1,3-dibromo(chloro,iodine)propane, 1,4-dibromo(chloro,iodine)butane, 1,5-dibromo(chloro,iodine)pentane, 1,6-dibromo(chloro,iodine)hexane, 1,7-dibromo(chloro,iodine)heptane, and 1,8-dibromo(chloro,iodine)octane. The concentrated sulfuric acid is a concentrated sulfuric acid with a mass percentage concentration greater than 98%. Specific steps: Mix equimolar amounts of imidazole with sodium ethoxide or potassium ethoxide, stir and reflux, add 0.5 molar amounts of haloalkanes to the same bath, stir and reflux, separate and remove the precipitate, add equimolar amounts of 1,3-propanesulfonate lactone or 1,4-butanesulfonate lactone to the filtrate, stir and reflux at 100-140℃ for 7-12 h, add equimolar amounts of concentrated sulfuric acid, stir and reflux at 110-140℃ for 3-7 h, remove the solvent by rotary evaporation under reduced pressure, and obtain a sulfonic acid-type dinuclear imidazole hydrogen sulfate ionic liquid catalyst.

[0006] Patent ZL202110029766.2 reports an acidic ionic liquid catalyst for biimidazole in the preparation of levulinic acid from biomass. The raw materials include imidazole or benzimidazole, sodium hydroxide, dichloroalkanes or dibromoalkanes, 1,3-propanesulfonate lactone or 1,4-butanesulfonate lactone, and Brønsted acid. The dihaloalkanes are 1,2-dibromo(chloro)ethane, 1,3-dibromo(chloro)propane, 1,4-dibromo(chloro)butane, 1,5-dibromo(chloro)pentane, 1,6-dibromo(chloro)hexane, 1,7-dibromo(chloro)heptane, 1,8-dibromo(chloro)octane, 1,9-dibromo(chloro)nonane, and 1,10-dibromo(chloro)decane.

[0007] Patent CN202311291918.1 reports the preparation process of the organic template agent DABC02-diquat-m dibromide, and the preparation and application of SSZ-16 zeolite molecular sieve, as well as its selective adsorption and separation performance for carbon dioxide. Using 1,4-diazidobicyclo[2,2,2]octane (DABCO) and dibromoalkanes as raw materials, a series of organic template agents DABC02-diquat-mdibromide (bis(1,4-diazidobicyclo[2,2,2]octane)m alkane dibromo derivatives) were prepared in one step, with m = 2~10, corresponding to the Chinese names ethyl, propane, butane, pentane, hexane, heptane, octane, nonane, and decane. The dibromoalkanes are 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, 1,9-dibromononane, and 1,10-dibromodecane.

[0008] This invention provides a multifunctional quaternary ammonium ionic liquid and its preparation method. The invention uses glycol, phosphorus trichloride or phosphorus tribromide, 1,4-diazidobicyclo[2,2,2]octane, alkyl sulfonate lactone, and sulfonic acid derivatives as raw materials to prepare the multifunctional quaternary ammonium ionic liquid; uses glycol, phosphorus trichloride or phosphorus tribromide as raw materials to prepare dibromo(chloro)glycol; uses 1,4-diazidobicyclo[2,2,2]octane and dibromo(chloro)glycol as raw materials to prepare a tetranuclear quaternary ammonium salt intermediate; uses the tetranuclear quaternary ammonium salt intermediate and alkyl sulfonate lactone as raw materials to prepare a tetranuclear quaternary ammonium sulfonic acid inner salt; and reacts the tetranuclear quaternary ammonium sulfonic acid inner salt with a sulfonic acid derivative to prepare the multifunctional quaternary ammonium ionic liquid. This invention provides a new method for preparing multifunctional ionic liquids. Summary of the Invention

[0009] Objective of the invention: The first objective of the present invention is to provide a multifunctional quaternary ammonium ionic liquid, and the second objective of the present invention is to provide a method for preparing the multifunctional quaternary ammonium ionic liquid.

[0010] Technical solution: The multifunctional quaternary ammonium ionic liquid of the present invention is prepared from glycol, 1,4-diazidobicyclo[2,2,2]octane (triethylenediamine), alkyl sulfonate lactone, and sulfonic acid derivative, and its molecular structure is as follows:

[0011]

[0012] m=1, 2, 3, 4, 5, 6, 7, 8, 9; n= 3, 4

[0013] The preparation method of the multifunctional four-season ammonium ionic liquid of the present invention includes the following steps:

[0014] (1) Preparation of dibromo(chloro)glycol

[0015] Dibromo(chloro)glycol was prepared by reacting glycol, phosphorus trichloride or phosphorus tribromide in an organic solvent at 80℃-120℃ for 12-24h.

[0016] (2) Preparation of tetranuclear quaternary ammonium salt

[0017] Tetranuclear quaternary ammonium salts were prepared by reacting 1,4-diazidobicyclo[2,2,2]octane and dibromo(chloro)glycol in an organic solvent at 80℃-120℃ for 12-24 h.

[0018] (3) Preparation of tetranuclear quaternary ammonium sulfonate inner salt

[0019] Tetranuclear quaternary ammonium sulfonate was prepared by reacting tetranuclear quaternary ammonium salt and sulfonate lactone in an organic solvent at 40℃-60℃ for 6-12 hours.

[0020] (4) Multifunctional ammonium ion liquid

[0021] The tetranuclear quaternary ammonium sulfonic acid inner salt intermediate was mixed with a sulfonic acid derivative and reacted at 60℃-80℃ for 6-8 hours to obtain a multifunctional quaternary ammonium ionic liquid.

[0022] Further, the glycol mentioned in step (1) is one of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, and decaethylene glycol; the dibromo(chloro)glycol is one of dibromo(chloro)diethylene glycol, dibromo(chloro)triethylene glycol, dibromo(chloro)tetraethylene glycol, dibromo(chloro)pentaethylene glycol, dibromo(chloro)hexaethylene glycol, dibromo(chloro)heptaethylene glycol, dibromo(chloro)octaethylene glycol, dibromo(chloro)nonaethylene glycol, and dibromo(chloro)decaethylene glycol.

[0023] Further, the organic solvent mentioned in step (2) is one of methanol, ethanol, acetonitrile, diethyl ether, n-hexane, cyclohexane, or 1,4-dioxane; the molar ratio of 1,4-diazidobicyclo[2,2,2]octane and dibromo(chloro)glycol is (1.95-2.15):1.

[0024] Further, the low-polarity aprotic organic solvent in step (3) is one of dichloromethane, 1,2-dichloroethane, petroleum ether, n-hexane, cyclohexane, toluene, and xylene; the alkyl sulfonate lactone is 1,3-propane sulfonate lactone or 1,4-butane sulfonate lactone; the molar ratio of the tetranuclear quaternary ammonium salt intermediate to the alkyl sulfonate lactone is 1:(1.95-2.15). Further, the sulfonic acid derivative in step (4) is morpholine ethanesulfonic acid, morpholine propanesulfonic acid, 3-morpholine-2-hydroxypropanesulfonic acid, morpholine butyric acid, piperidine ethanesulfonic acid, piperidine propanesulfonic acid, piperidine butyric acid, piperazine ethanesulfonic acid, piperazine propanesulfonic acid, piperazine butyric acid, N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid, 4-(2-hydroxyethyl)-1-piperazine propanesulfonic acid, N-(2-hydroxyethyl)piperazine-N'-4-butyric acid, pyridine Pyrrole sulfonic acid, pyrrole propanesulfonic acid, pyrrole butanesulfonic acid, 2-pyridine sulfonic acid, 3-pyridine sulfonic acid, 4-pyridine sulfonic acid, 2-(4-pyridyl)ethanesulfonic acid, 2-(2-pyridyl)ethanesulfonic acid, 2-(3-pyridyl)ethanesulfonic acid, cyclohexylaminosulfonic acid, cyclohexylaminomethanesulfonic acid, cyclohexylaminoethanesulfonic acid, cyclohexylaminopropanesulfonic acid; the molar ratio of the tetranuclear quaternary ammonium sulfonic acid intermediate to the sulfonic acid derivative is 1:(0.9-2.1).

[0025] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0026] (1) The preparation process of the multifunctional four-season ammonium ionic liquid of the present invention is simple and has a high yield;

[0027] (2) The multifunctional quaternary ammonium ionic liquid of the present invention contains four quaternary ammonium salt units and has excellent performance;

[0028] (2) The multifunctional ammonium ionic liquid of the present invention contains ether bonds and 3-4 sulfonate groups, has typical acidity, and has a broader application prospect. Attached Figure Description

[0029] Figure 1 Schematic diagram of the structure of a multifunctional four-season ammonium ionic liquid Detailed Implementation

[0030] The present invention will be further described in detail below with reference to embodiments, but the embodiments of the invention are not limited thereto.

[0031] Example 1

[0032] (1) Dibromodiethylene glycol

[0033] 100 mL of acetonitrile was added to a 250 mL four-necked flask, followed by 0.1 mol of diethylene glycol and 0.2 mol of phosphorus tribromide. The mixture was stirred and refluxed for 12 h. Filtration yielded a white solid, dibromodiethylene glycol, in 96% yield. The structural formula of the product is as follows:

[0034]

[0035] (2) Tetranuclear quaternary ammonium salt intermediate

[0036] 100 mL of acetonitrile was added to a 250 mL four-necked flask, followed by 0.1 mol of 4-diazidobicyclo[2,2,2]octane and 0.05 mol of dibromodiethylene glycol. The mixture was stirred and refluxed for 12 h. Filtration yielded a white solid, a tetranuclear quaternary ammonium salt intermediate, with a yield of 95%. The structural formula of the product is as follows:

[0037]

[0038] (3) Tetranuclear quaternary ammonium sulfonate inner salt

[0039] 100 mL of petroleum ether was added to a 250 mL four-necked flask, followed by 0.1 mol of a tetranuclear quaternary ammonium salt intermediate and 0.2 mol of 1,3-propanesulfonate lactone. The mixture was stirred and reacted at 60 °C for 6 h. Filtration yielded a white solid, which was the tetranuclear quaternary ammonium sulfonate inner salt, with a yield of 96%. The structural formula of the product is as follows:

[0040]

[0041] (4) Synthesis of tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate

[0042] Tetranuclear quaternary ammonium sulfonic acid inner salt and morpholine ethanesulfonic acid (molar ratio 1:1.95) were added to a four-necked flask and stirred at 60°C for 6 hours, gradually forming a homogeneous viscous liquid, which is the tetranuclear quaternary ammonium sulfonic acid morpholine ethanesulfonic acid salt, with a yield of 96%; the structural formula of the product is as follows:

[0043]

[0044] Tetranuclear quaternary ammonium salt intermediate (C 16 H 32 The 1H NMR spectrum of N4O.2Br: 1 H NMR (400MHz, CDCl3) δ (ppm) 3.92 (t, 4H, NCH2 CH2 O), 3.51(t, 4H, N CH2 CH2O), 3.38 (t, 12H, NCH2) CH2 N), 2.78(t, 12H, N) CH2 CH2N).

[0045] Tetranuclear quaternary ammonium salt intermediate (C 16 H 32 Carbon NMR spectrum of N4O.2Br: 13 C NMR (100MHz, CDCl3) δ (ppm) 69.5, 65.5, 61.8, 52.6.

[0046] Tetranuclear quaternary ammonium salt intermediate (C 16 H 32 Theoretical elemental analysis values ​​(%) of N4O.2Br: C, 42.12; H, 7.07; N, 12.28; Br, 35.03.

[0047] Measured values ​​(%): C, 42.14; H, 7.08; N, 12.26; Br, 35.01.

[0048] Tetranuclear quaternary ammonium sulfonate inner salt (C 22 H 44 The 1H NMR spectrum of N4O7S2.2Br: 1 H NMR (400MHz, D2O) δ (ppm) 3.92 (t, 4H, NCH2 CH2 O), 3.78(t, 12H, N) CH2 CH2N), 3.69 (t, 12H, N) CH2 CH2N), 3.49(t, 4H, NCH2CH2) CH2 SO3), 3.42(t, 4H, N) CH2 CH2O), 3.26(t, 4H, N) CH2 CH2CH2SO3), 2.22(m, 4H, NCH2 CH2 CH2SO3).

[0049] Tetranuclear quaternary ammonium sulfonate inner salt (C 22 H 44 The carbon NMR spectrum (100MHz, D2O) of N4O7S2.2Br) is as follows: δ (ppm) 68.9, 65.2, 60.3, 59.1, 57.0, 43.2, 18.3.

[0050] Tetranuclear quaternary ammonium sulfonate inner salt (C 22 H 44 Elemental analysis of N4O7S2.2Br

[0051] Theoretical values ​​(%): C, 37.72; H, 6.33; N, 8.00; S, 9.15; Br, 22.81.

[0052] Measured values ​​(%): C, 37.74; H, 6.32; N, 8.02; S, 9.13; Br, 22.83.

[0053] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 22 H 46 N4O7S2.2Br.2C6H 12 The 1H NMR spectrum of NO4S: 1 H NMR (400MHz, D2O)

[0054] δ(ppm) 8.50 (s, 2H, CH2SO3) H ), 3.81(t, 4H, NCH2) CH2 O), 3.55(t, 8H, O) CH2 CH2N), 3.41(t, 4H, N) CH2 CH2O), 3.22(t, 12H, N) CH2 CH2), 3.01(t, 4H, CH2) CH2 SO3H), 2.55(t, 4H, CH2) CH2 SO3), 2.46 (t, 4H, N) CH2 CH2), 2.33(t, 8H, OCH2) CH2 N), 2.17 (m, 4H, NCH2) CH2 CH2), 1.95 (m, 4H, CH2) CH2 CH2), 1.71 (m, 8H, NCH2) CH2 ).

[0055] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 22 H 46 N4O7S2.2Br.2C6H 12The carbon NMR spectra of NO4S (100MHz, D2O) δ (ppm) are 67.9, 66.7, 62.9, 60.3, 57.9, 55.4, 55.2, 50.7, 24.0, 22.4, 16.8.

[0056] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 22 H 46 N4O7S2.2Br.2C6H 12 Elemental analysis of NO4S

[0057] Theoretical values ​​(%): C, 37.43; H, 6.47; N, 7.70; S, 11.76; Br, 14.65.

[0058] Measured values ​​(%): C, 37.45; H, 6.48; N, 7.72; S, 11.75; Br, 14.64.

[0059] Example 2

[0060] (1) Dibromodiethylene glycol

[0061] 100 mL of acetonitrile was added to a 250 mL four-necked flask, followed by 0.1 mol of diethylene glycol and 0.2 mol of phosphorus tribromide. The mixture was stirred and refluxed for 12 h. Filtering yielded a white solid, which was dibromodiethylene glycol, in 98% yield. The structural formula of the product is as follows:

[0062]

[0063] (2) Tetranuclear quaternary ammonium salt intermediate

[0064] 100 mL of acetonitrile was added to a 250 mL four-necked flask, followed by 0.1 mol of 4-diazidadicyclo[2,2,2]octane and 0.05 mol of dibromodiethylene glycol. The mixture was stirred and refluxed for 12 h. Filtration yielded a white solid, a tetranuclear quaternary ammonium salt intermediate, with a yield of 98%. The structural formula of the product is as follows:

[0065]

[0066] (3) Tetranuclear quaternary ammonium sulfonate inner salt

[0067] 100 mL of cyclohexane was added to a 250 mL four-necked flask, followed by 0.1 mol of a tetranuclear quaternary ammonium salt intermediate and 0.2 mol of 1,4-butanesulfonate lactone. The mixture was stirred and reacted at 60 °C for 6 h. The product was filtered to obtain a white solid, which was the tetranuclear quaternary ammonium sulfonate lactone, with a yield of 97%. The structural formula of the product is as follows:

[0068]

[0069] (4) Synthesis of tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate

[0070] Tetranuclear quaternary ammonium sulfonic acid inner salt and morpholine ethanesulfonic acid (molar ratio 1:2.05) were added to a four-necked flask and stirred at 60°C for 6 hours, gradually forming a homogeneous viscous liquid, which is the tetranuclear quaternary ammonium sulfonic acid morpholine ethanesulfonic acid salt, with a yield of 95%; the structural formula of the product is as follows:

[0071]

[0072] Tetranuclear quaternary ammonium sulfonate inner salt (C 24 H 48 The 1H NMR spectrum of N4O7S2.2Br: 1 H NMR (400MHz, D2O) δ (ppm) 3.89 (t, 4H, NCH2 CH2 O), 3.72(t, 12H, N) CH2 CH2N), 3.66 (t, 12H, N) CH2 CH2N), 3.45 (t, 4H, N) CH2 CHO), 3.29(t, 4H, NCH2CH2CH2 CH2 SO3), 3.29 (t, 4H, N) CH2 CH2CH2CH2SO3), 1.86(m, 4H, NCH2CH2 CH2 CH2SO3), 1.76 (m, 4H, NCH2) CH2 CH2CH2SO3).

[0073] Tetranuclear quaternary ammonium sulfonate inner salt (C 24 H 48 The carbon NMR spectrum (100MHz, D2O) of N4O7S2.2Br) is as follows: δ (ppm): 68.5, 65.0, 60.7, 59.3, 57.0, 43.2, 23.4, 18.3.

[0074] Tetranuclear quaternary ammonium sulfonate inner salt (C 24 H 48 Elemental analysis of N4O7S2.2Br

[0075] Theoretical values ​​(%): C, 39.56; H, 6.64; N, 7.69; S, 8.80; Br, 21.93.

[0076] Measured values ​​(%): C, 39.58; H, 6.63; N, 7.67; S, 8.82; Br, 21.95.

[0077] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 24 H 50 N4O7S2.2Br.2C6H12 The 1H NMR spectrum of NO4S: 1 H NMR (400MHz, D2O)

[0078] δ(ppm) 8.50 (s, 2H, CH2SO3) H ), 3.81(t, 4H, NCH2) CH2 O), 3.55(t, 8H, O) CH2 CH2N), 3.41(t, 4H, N) CH2 CH2O), 3.22(t, 12H, N) CH2 CH2), 3.01(t, 4H, CH2) CH2 SO3H), 2.55(t, 4H, CH2) CH2 SO3), 2.46 (t, 4H, N) CH2 CH2), 2.33(t, 8H, OCH2) CH2 N), 2.17 (m, 4H, NCH2) CH2 CH2), 1.95 (m, 4H, CH2) CH2 CH2), 1.71 (m, 8H, NCH2) CH2 ).

[0079] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 24 H 50 N4O7S2.2Br.2C6H 12 The carbon NMR spectra of NO4S (100MHz, D2O) δ (ppm) are 67.9, 66.7, 62.9, 60.3, 57.9, 55.4, 55.2, 50.7, 24.0, 22.4, 16.8.

[0080] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 24 H 50 Elemental analysis of N4O7S2.2Br.2C6H12NO4S)

[0081] Theoretical values ​​(%): C, 38.64; H, 6.67; N, 7.51; S, 11.46; Br, 14.28.

[0082] Measured values ​​(%): C, 38.62; H, 6.69; N, 7.53; S, 11.45; Br, 14.26.

[0083] Example 3

[0084] (1) Dibromotriethylene glycol

[0085] 100 mL of acetonitrile was added to a 250 mL four-necked flask, followed by 0.1 mol of triethylene glycol and 0.2 mol of phosphorus tribromide. The mixture was stirred and refluxed for 12 h. Filtering yielded a white solid, which was dibromotriethylene glycol, in 96% yield. The structural formula of the product is as follows:

[0086]

[0087] (2) Tetranuclear quaternary ammonium salt intermediate

[0088] 100 mL of acetonitrile was added to a 250 mL four-necked flask, followed by 0.1 mol of 1,4-diazidobicyclo[2,2,2]octane and 0.05 mol of dibromotriethylene glycol. The mixture was stirred and refluxed for 12 h. Filtration yielded a white solid, a tetranuclear quaternary ammonium salt intermediate, with a yield of 98%. The structural formula of the product is as follows:

[0089]

[0090] (3) Tetranuclear quaternary ammonium sulfonate inner salt

[0091] 100 mL of petroleum ether was added to a 250 mL four-necked flask, followed by 0.1 mol of a tetranuclear quaternary ammonium salt intermediate and 0.2 mol of 1,3-propanesulfonate lactone. The mixture was stirred and reacted at 60 °C for 6 h. The product was filtered to obtain a white solid, which was the tetranuclear quaternary ammonium sulfonate inner salt, with a yield of 97%. The structural formula of the product is as follows:

[0092]

[0093] (4) Synthesis of tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate

[0094] Tetranuclear quaternary ammonium sulfonic acid inner salt and morpholine ethanesulfonic acid (molar ratio 1:1.95) were added to a four-necked flask and stirred at 60°C for 6 hours, gradually forming a homogeneous viscous liquid, which is the tetranuclear quaternary ammonium sulfonic acid morpholine ethanesulfonic acid salt, with a yield of 99%; the structural formula of the product is as follows:

[0095]

[0096] Tetranuclear quaternary ammonium salt intermediate (C 18 H 36 The 1H NMR spectrum of N4O2.2Br: 1 H NMR (400MHz, CDCl3) δ (ppm) 3.89 (t, 4H, NCH2 CH2 O), 3.56(t, 4H, O) CH2CH2 O), 3.43(t, 4H, N) CH2 CH2O), 3.36 (t, 12H, NCH2) CH2 N), 2.76(t, 12H, N) CH2 CH2N).

[0097] Tetranuclear quaternary ammonium salt intermediate (C 18 H 36 Carbon NMR spectrum of N4O2.2Br: 13 C NMR (100MHz, CDCl3) δ (ppm) 72.5, 66.8, 64.2, 62.5, 51.8.

[0098] Tetranuclear quaternary ammonium salt intermediate (C 18 H 36 Elemental analysis of N4O2.2Br

[0099] Theoretical values ​​(%): C, 43.21; H, 7.25; N, 11.20; Br, 31.94.

[0100] Measured values ​​(%): C, 43.23; H, 7.24; N, 11.22; Br, 31.93.

[0101] Tetranuclear quaternary ammonium sulfonate inner salt (C 24 H 48 The 1H NMR spectrum of N4O8S2.2Br: 1 H NMR (400MHz, D2O) δ (ppm) 3.90 (t, 4H, NCH2 CH2 O), 3.76(t, 12H, N) CH2 CH2N), 3.68 (t, 12H, N) CH2 CH2N), 3.52(t, 4H, O) CH2CH2 O), 3.43(t, 4H, N) CH2 CH2O), 3.38 (t, 4H, NCH2CH2) CH2 SO3), 3.23 (t, 4H, N) CH2 CH2CH2SO3), 2.27(m, 4H, NCH2 CH2 CH2SO3).

[0102] Tetranuclear quaternary ammonium sulfonate inner salt (C 24 H 48 The carbon NMR spectrum (100MHz, D2O) of N4O8S2.2Br) is as follows: δ (ppm): 70.2, 65.2, 62.3, 59.4, 59.1, 58.3, 43.3, 18.4.

[0103] Tetranuclear quaternary ammonium sulfonate inner salt (C 24 H 48 Elemental analysis of N4O8S2.2Br

[0104] Theoretical values ​​(%): C, 38.71; H, 6.50; N, 7.52; S, 8.61; Br, 21.46.

[0105] Measured values ​​(%): C, 38.73; H, 6.48; N, 7.53; S, 8.59; Br, 21.44.

[0106] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 24 H 50 N4O8S2.2Br.2C6H 12 The 1H NMR spectrum of NO4S: 1 H NMR (400MHz, D2O)

[0107] δ(ppm) 8.50 (s, 2H, CH2SO3) H ), 3.81(t, 4H, NCH2) CH2 O), 3.55(t, 8H, O) CH2 CH2N), 3.41(t, 4H, N) CH2 CH2O), 3.22(t, 12H, N) CH2 CH2), 3.01(t, 4H, CH2) CH2 SO3H), 2.55(t, 4H, CH2) CH2 SO3), 2.46 (t, 4H, N) CH2 CH2), 2.33(t, 8H, OCH2) CH2 N), 2.17 (m, 4H, NCH2) CH2 CH2), 1.95 (m, 4H, CH2) CH2 CH2), 1.71 (m, 8H, NCH2) CH2 ).

[0108] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 24 H 50 N4O8S2.2Br.2C6H 12 The carbon NMR spectra of NO4S (100MHz, D2O) δ (ppm) are 67.9, 66.7, 62.9, 60.3, 57.9, 55.4, 55.2, 50.7, 24.0, 22.4, 16.8.

[0109] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 24 H 50 N4O8S2.2Br.2C6H 12 Elemental analysis of NO4S

[0110] Theoretical values ​​(%): C, 38.09; H, 6.57; N, 7.40; S, 11.30; Br, 14.08.

[0111] Measured values ​​(%): C, 38.07; H, 6.59; N, 7.42; S, 11.28; Br, 14.07.

[0112] Example 4

[0113] (1) Dibromotriethylene glycol

[0114] 100 mL of acetonitrile was added to a 250 mL four-necked flask, followed by 0.1 mol of triethylene glycol and 0.2 mol of phosphorus tribromide. The mixture was stirred and refluxed for 12 h. Filtering yielded a white solid, which was dibromotriethylene glycol, in 96% yield. The structural formula of the product is as follows:

[0115]

[0116] (2) Tetranuclear quaternary ammonium salt intermediate

[0117] 100 mL of acetonitrile was added to a 250 mL four-necked flask, followed by 0.1 mol of 1,4-diazidobicyclo[2,2,2]octane and 0.05 mol of dibromotriethylene glycol. The mixture was stirred and refluxed for 12 h. Filtration yielded a white solid, a tetranuclear quaternary ammonium salt intermediate, with a yield of 98%. The structural formula of the product is as follows:

[0118]

[0119] (3) Tetranuclear quaternary ammonium sulfonate inner salt

[0120] 100 mL of petroleum ether was added to a 250 mL four-necked flask, followed by 0.1 mol of a tetranuclear quaternary ammonium salt intermediate and 0.2 mol of 1,4-butanesulfonate lactone. The mixture was stirred and reacted at 60 °C for 6 h. Filtration yielded a white solid, which was the tetranuclear quaternary ammonium sulfonate inner salt, with a yield of 97%. The structural formula of the product is as follows:

[0121]

[0122] (4) Synthesis of tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate

[0123] Tetranuclear quaternary ammonium sulfonic acid inner salt and morpholine ethanesulfonic acid (molar ratio 1:1.95) were added to a four-necked flask and stirred at 60°C for 6 hours, gradually forming a homogeneous viscous liquid, which is the tetranuclear quaternary ammonium sulfonic acid morpholine ethanesulfonic acid salt, with a yield of 99%; the structural formula of the product is as follows:

[0124]

[0125] Tetranuclear quaternary ammonium sulfonate inner salt (C 26 H 52The 1H NMR spectrum of N4O8S2.2Br: 1 H NMR (400MHz, D2O) δ (ppm) 3.87 (t, 4H, NCH2 CH2 O), 3.75(t, 12H, N) CH2 CH2N), 3.67 (t, 12H, N) CH2 CH2N), 3.56 (t, 4H, O) CH2CH2 O), 3.45(t, 4H, N) CH2 CHO), 3.39(t, 4H, NCH2CH2CH2 CH2 SO3), 3.27 (t, 4H, N) CH2 CH2CH2CH2SO3), 1.87(m, 4H, NCH2CH2 CH2 CH2SO3), 1.75 (m, 4H, NCH2) CH2 CH2CH2SO3).

[0126] Tetranuclear quaternary ammonium sulfonate inner salt (C 26 H 52 The carbon NMR spectrum (100MHz, D2O) of N4O8S2.2Br) is as follows: δ (ppm): 68.5, 65.0, 61.8, 60.7, 59.3, 58.0, 44.3, 23.6, 21.3.

[0127] Tetranuclear quaternary ammonium sulfonate inner salt (C 26 H 52 Elemental analysis of N4O8S2.2Br

[0128] Theoretical values ​​(%): C, 40.42; H, 6.78; N, 7.25; S, 8.30; Br, 20.68.

[0129] Measured values ​​(%): C, 40.44; H, 6.76; N, 7.23; S, 8.32; Br, 20.67.

[0130] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 26 H 54 N4O8S2.2Br.2C6H 12 The 1H NMR spectrum of NO4S: 1 H NMR (400MHz, D2O)

[0131] δ(ppm) 8.50 (s, 2H, CH2SO3) H ), 3.81(t, 4H, NCH2) CH2 O), 3.55(t, 8H, O) CH2 CH2N), 3.41(t, 4H, N) CH2CH2O), 3.22(t, 12H, N) CH2 CH2), 3.01(t, 4H, CH2) CH2 SO3H), 2.55(t, 4H, CH2) CH2 SO3), 2.46 (t, 4H, N) CH2 CH2), 2.33(t, 8H, OCH2) CH2 N), 2.17 (m, 4H, NCH2) CH2 CH2), 1.95 (m, 4H, CH2) CH2 CH2), 1.71 (m, 8H, NCH2) CH2 ).

[0132] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 26 H 54 N4O8S2.2Br.2C6H 12 The carbon NMR spectra of NO4S (100MHz, D2O) δ (ppm) are 67.9, 66.7, 62.9, 60.3, 57.9, 55.4, 55.2, 50.7, 24.0, 22.4, 16.8.

[0133] Tetranuclear quaternary ammonium sulfonate morpholine ethanesulfonate (C 26 H 54 N4O8S2.2Br.2C6H 12 Elemental analysis of NO4S

[0134] Theoretical values ​​(%): C, 39.24; H, 6.76; N, 7.23; S, 11.03; Br, 13.74.

[0135] Measured values ​​(%): C, 39.26; H, 6.75; N, 7.25; S, 11.01; Br, 13.76.

[0136] The acidity of the multifunctional quaternary ammonium ionic liquid was calculated using the Hammett acidity method. Multifunctional quaternary ammonium ionic liquids were prepared using different glycols, alkyl sulfonates, and sulfonic acid derivatives as raw materials. Their yields and Hammett acidities are summarized in Table 1.

[0137] Table 1 Examples of the preparation of multifunctional quaternary ammonium ionic liquids

[0138] Raw material 1 Raw material 2 Raw material 3 Yield (%) Hammet acidity Example 1 Diethylene glycol 1,3-Propanesulfonate lactone Morpholine ethanesulfonic acid 91.0 3.48 Example 2 Diethylene glycol 1,4-Butanesulfonyl lactone Morpholine ethanesulfonic acid 87.0 3.76 Example 3 Triethylene glycol 1,3-Propanesulfonate lactone Morpholine ethanesulfonic acid 90.0 4.02 Example 4 Triethylene glycol 1,4-Butanesulfonyl lactone Morpholine ethanesulfonic acid 86.0 4.22

Claims

1. A multifunctional quaternary ammonium ionic liquid and its preparation method, characterized in that: The structural formula of the multifunctional four-season ammonium ionic liquid is as follows: The preparation method of the multifunctional quaternary ammonium ionic liquid includes the following steps: (1) Preparation of dibromo(chloro)glycol Dibromo(chloro)glycol was prepared by reacting glycol, phosphorus trichloride or phosphorus tribromide in an organic solvent at 80℃-120℃ for 12-24h. (2) Preparation of tetranuclear quaternary ammonium salt Tetranuclear quaternary ammonium salts were prepared by reacting 1,4-diazidobicyclo[2,2,2]octane and dibromo(chloro)glycol in an organic solvent at 80℃-120℃ for 12-24 h. (3) Preparation of tetranuclear quaternary ammonium sulfonate inner salt Tetranuclear quaternary ammonium sulfonate was prepared by reacting tetranuclear quaternary ammonium salt and sulfonate lactone in an organic solvent at 40℃-60℃ for 6-12 hours. (4) Multifunctional ammonium ion liquid The tetranuclear quaternary ammonium sulfonic acid inner salt intermediate was mixed with a sulfonic acid derivative and reacted at 60℃-80℃ for 6-8 hours to obtain a multifunctional quaternary ammonium ionic liquid.

2. The multifunctional quaternary ammonium ionic liquid and its preparation method according to claim 1, characterized in that: The glycol mentioned in step (1) is one of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, and decaethylene glycol; the dibromo(chloro)glycol is one of dibromo(chloro)diethylene glycol, dibromo(chloro)triethylene glycol, dibromo(chloro)tetraethylene glycol, dibromo(chloro)pentaethylene glycol, dibromo(chloro)hexaethylene glycol, dibromo(chloro)heptaethylene glycol, dibromo(chloro)octaethylene glycol, dibromo(chloro)nonaethylene glycol, and dibromo(chloro)decaethylene glycol.

3. The multifunctional quaternary ammonium ionic liquid and its preparation method according to claim 1, characterized in that: The organic solvent mentioned in step (2) is one of methanol, ethanol, acetonitrile, diethyl ether, n-hexane, cyclohexane, or 1,4-dioxane; the molar ratio of 1,4-diazidobicyclo[2,2,2]octane to dibromo(chloro)glycol is (1.95-2.15):

1.

4. The multifunctional quaternary ammonium ionic liquid and its preparation method according to claim 1, characterized in that: The low-polarity aprotic organic solvent mentioned in step (3) is one of dichloromethane, 1,2-dichloroethane, petroleum ether, n-hexane, cyclohexane, toluene, and xylene; the alkyl sulfonate lactone is 1,3-propane sulfonate lactone or 1,4-butane sulfonate lactone; the molar ratio of the tetranuclear quaternary ammonium salt intermediate and the alkyl sulfonate lactone is 1:(1.95-2.15).

5. The multifunctional quaternary ammonium ionic liquid and its preparation method according to claim 1, characterized in that: The sulfonic acid derivatives mentioned in step (4) are morpholine ethanesulfonic acid, morpholine propanesulfonic acid, 3-morpholine-2-hydroxypropanesulfonic acid, morpholine butyric acid, piperidine ethanesulfonic acid, piperidine propanesulfonic acid, piperidine butyric acid, piperazine ethanesulfonic acid, piperazine propanesulfonic acid, piperazine butyric acid, N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid, 4-(2-hydroxyethyl)-1-piperazine propanesulfonic acid, N-(2-hydroxyethyl)piperazine-N'-4-butyric acid, and pyrrole ethanesulfonic acid. The following are listed: pyrrole propanesulfonic acid, pyrrole butanesulfonic acid, 2-pyridinesulfonic acid, 3-pyridinesulfonic acid, 4-pyridinesulfonic acid, 2-(4-pyridyl)ethanesulfonic acid, 2-(2-pyridyl)ethanesulfonic acid, 2-(3-pyridyl)ethanesulfonic acid, cyclohexylaminosulfonic acid, cyclohexylaminomethanesulfonic acid, cyclohexylaminoethanesulfonic acid, and cyclohexylaminopropanesulfonic acid; the molar ratio of the tetranuclear quaternary ammonium sulfonic acid inner salt intermediate to the sulfonic acid derivative is 1:(0.9-2.1).

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