Polyfunctional group binuclear morpholine ionic liquid and preparation method thereof

Abstract

The invention discloses a multifunctional binuclear morpholine ionic liquid and a preparation method thereof. According to the invention, glycol, phosphorus trichloride or phosphorus tribromide, morpholine, alkyl sultone and a sulfonic acid derivative are used as raw materials to prepare the multifunctional binuclear morpholine ionic liquid. The method comprises the following steps: preparing dibromo (chloro) glycol by taking glycol, phosphorus trichloride or phosphorus tribromide as a raw material; the preparation method comprises the following steps: reacting morpholine with dibromo (chloro) glycol to prepare a binuclear morpholine intermediate; reacting the binuclear morpholine intermediate with alkyl sultone to prepare binuclear morpholine sulfonic acid inner salt; the polyfunctional group binuclear morpholine ionic liquid is prepared by taking binuclear morpholine sulfonic acid inner salt and a sulfonic acid derivative as raw materials. The invention provides a new scheme for preparing the multi-functional group morpholine ionic liquid.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of multi-functional double-core morpholine ionic liquid and its preparation method. BACKGROUND

[0002] Ionic liquids are a kind of salt compounds composed of organic cations and inorganic or organic anions, generally with a melting point of no more than 100℃; Ionic liquids are liquid at room temperature and have a wide temperature range, and their physical and chemical properties can be adjusted by modifying the structure of anions and cations or adjusting the types of anions and cations to meet specific application requirements. The cation unit of ionic liquid usually includes imidazole, pyridine, pyrrole, and morpholine, and the anion includes chloride, acetate, tetrafluoroborate, hexafluorophosphate, and bis-trifluoromethyl sulfonimide ion.

[0003] Acidic ionic liquids (AILs) are a branch of functional ionic liquids, which have both acidic and ionic liquid properties. Acidic groups can be introduced in two ways: one method is to introduce carboxylic acid or sulfonic acid on the cation part of the ionic liquid, such as on the imidazole ring; the other method is to introduce acidic groups on the anion part, such as sulfate, p-toluenesulfonate, and methylsulfonate. The physical and chemical properties of acidic ionic liquids can be adjusted by modifying the structure of anions and cations or adjusting the types of anions and cations, especially by adjusting the pH value to meet specific requirements.

[0004] Patent CN200910206550.8 reports a kind of acidic ionic liquid with twin double cations. The preparation raw materials include double heterocyclic alkane, 1,3-propane sulfonic acid lactone or 1,4-butane sulfonic acid lactone, organic acid or inorganic acid. Organic acid or inorganic acid includes p-toluenesulfonic acid, benzoic acid, trifluoromethyl sulfonic acid, methyl sulfonic acid, acetic acid, trifluoroacetic acid, tetrafluoroboric acid, hexafluorophosphoric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid. The specific steps are as follows: double heterocyclic alkane, 1,3-propane sulfonic acid lactone or 1,4-butane sulfonic acid lactone are stirred and refluxed in an organic solvent for 48-72 hours, and white solid is obtained by separation, which is double heterocyclic alkane sulfonic acid inner salt; double heterocyclic alkane sulfonic acid inner salt is mixed with organic acid or inorganic acid, stirred at 70-90℃ for 6-12 hours, and acidic ionic liquid with twin double cations is obtained by separation. The patent does not provide the preparation method of double heterocyclic alkane. From the structure analysis, the heterocyclic raw material includes imidazole, piperidine, pyrrole, and morpholine.

[0005] Patent ZL201010503499.X reports a sulfonic acid type binuclear imidazole hydrogen sulfate ionic liquid catalyst. The preparation raw materials include imidazole, sodium or potassium ethoxide, halogenated alkane, 1,3-propane sulfonic acid lactone or 1,4-butane sulfonic acid lactone, concentrated sulfuric acid, etc. The halogenated alkane is 1,2-dibromo(chloro, iodo)ethane, 1,3-dibromo(chloro, iodo)propane, 1,4-dibromo(chloro, iodo)butane, 1,5-dibromo(chloro, iodo)pentane, 1,6-dibromo(chloro, iodo)hexane, 1,7-dibromo(chloro, iodo)heptane, 1,8-dibromo(chloro, iodo)octane. The concentrated sulfuric acid is a concentrated sulfuric acid with a mass percentage of more than 98%. The specific steps are as follows: equal molar mass of imidazole and sodium or potassium ethoxide are mixed, stirred and refluxed, 0.5 molar mass of halogenated alkane is added to the bath, stirred and refluxed, the precipitate is separated and removed, equal molar mass of 1,3-propane sulfonic acid lactone or 1,4-butane sulfonic acid lactone is added to the filtrate, stirred and refluxed at 100-140℃ for 7-12h, equal molar mass of concentrated sulfuric acid is added, stirred and refluxed at 110-140℃ for 3-7h, the solvent is removed by rotary evaporation under reduced pressure, and a sulfonic acid type binuclear imidazole hydrogen sulfate ionic liquid catalyst is obtained.

[0006] Patent ZL202110029766.2 reports an acid ionic liquid catalyst of biimidazole for preparing acetylpic acid from biomass. The preparation raw materials include imidazole or benzimidazole, sodium hydroxide, dichloroalkane or dibromoalkane, 1,3-propane sulfonic acid lactone or 1,4-butane sulfonic acid lactone, and Bronsted acid. The dichloroalkane is 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] The present application provides a kind of multi-functional binuclear morpholine ionic liquid and preparation method thereof;The present application uses glycol, phosphorus trichloride or tribromide, morpholine, alkyl sulfonic acid lactone, sulfonic acid derivative as raw material, to prepare multi-functional binuclear morpholine ionic liquid;Glycol, phosphorus trichloride or tribromide is used as raw material to prepare dibromo(chloro) glycol;Morpholine and dibromo(chloro) glycol are used as raw material to prepare binuclear morpholine intermediate;Binuclear morpholine intermediate and alkyl sulfonic acid lactone are used as raw material to prepare binuclear morpholine sulfonic acid inner salt;Multi-functional binuclear morpholine ionic liquid is prepared by mixing reaction of binuclear morpholine sulfonic acid inner salt and sulfonic acid derivative.The present application provides a new scheme for preparing multi-functional morpholine ionic liquid. SUMMARY

[0008] The first object of the present application is to provide a multi-functional binuclear morpholine ionic liquid, and the second object of the present application is to provide a preparation method of the multi-functional binuclear morpholine ionic liquid.

[0009] Technical solution: The multifunctional double-core morpholine ionic liquid of the present application is prepared from glycol, phosphorus trichloride or phosphorus tribromide, morpholine, alkyl sulfonic acid lactone and sulfonic acid derivative, and the molecular structure is as follows:

[0010]

[0011] m=3, 4; n=1, 2, 3, 4, 5, 6, 7;

[0012] The preparation method of the multifunctional double-core morpholine ionic liquid comprises the following steps:

[0013] (1) Preparation of dibromo(chloro) glycol

[0014] Dibromo(chloro) glycol is prepared from glycol, phosphorus trichloride or phosphorus tribromide in an organic solvent at 80-120°C for 12-24h;

[0015] (2) Preparation of double-core morpholine intermediate

[0016] Double-core morpholine intermediate is synthesized from morpholine and dibromo(chloro) glycol in an organic solvent at 80-120°C for 12-24h;

[0017] (3) Preparation of double-core morpholine sulfonic acid inner salt

[0018] Double-core morpholine sulfonic acid inner salt is synthesized from double-core morpholine intermediate and alkyl sulfonic acid lactone in an organic solvent at 40-60°C for 6-12h;

[0019] (4) Preparation of multifunctional double-core morpholine ionic liquid

[0020] Multifunctional double-core morpholine ionic liquid is prepared from double-core morpholine sulfonic acid inner salt and sulfonic acid derivative at 60-80°C for 6-8h.

[0021] Further, the glycol in step (1) is one of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol and octaethylene 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 and dibromo(chloro) octaethylene glycol; the organic solvent is one of acetonitrile, n-hexane, cyclohexane, dimethylbenzene, toluene and 1, 4-dioxane; and the molar ratio of glycol to phosphorus trichloride or phosphorus tribromide is 1:(1.95-2.05).

[0022] Further, the organic solvent in step (2) is one of methanol, ethanol, isopropanol, acetonitrile, n-hexane, cyclohexane, dimethylbenzene, toluene, 1,4-dioxane; the molar ratio of the morpholine to dibromo(chloro)glycol is 1:(1.95-2.05).

[0023] Further, the organic solvent in step (3) is one of dichloromethane, 1,2-dichloroethane, petroleum ether, n-hexane, cyclohexane, toluene, dimethylbenzene; the alkylsulfonic acid lactone is 1,3-propane sulfonic acid lactone, 1,4-butane sulfonic acid lactone; the molar ratio of the binuclear morpholine intermediate to alkylsulfonic acid lactone is 1:(1.95-2.10).

[0024] Further, the sulfonic acid derivative in step (4) is morpholine ethanesulfonic acid, morpholine propanesulfonic acid, 3-morpholine-2-hydroxypropanesulfonic acid, morpholine butanesulfonic acid, piperidine ethanesulfonic acid, piperidine propanesulfonic acid, piperidine butanesulfonic acid, piperazine ethanesulfonic acid, piperazine propanesulfonic acid, piperazine butanesulfonic acid, N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid, 4-(2-hydroxyethyl)-1-piperazine propanesulfonic acid, N-(2-hydroxyethyl)piperazine-N'-4-butanesulfonic acid, pyrrole ethanesulfonic 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 binuclear morpholine sulfonic acid inner salt to the sulfonic acid derivative is 1:(1.95-2.10).

[0025] Beneficial effects: compared with the prior art, the present application has the following remarkable advantages:

[0026] (1) The preparation process of the multi-functional binuclear morpholine ionic liquid of the present application is simple, and the yield is high;

[0027] (2) The multi-functional binuclear morpholine ionic liquid of the present application contains 2 morpholine units, and has excellent performance;

[0028] (2) The multi-functional binuclear morpholine ionic liquid of the present application contains morpholine cation, ether bond and 3-4 sulfonate groups, and has a broader application prospect.

[0029] Drawings of the specification

[0030] Figure 1 Structure diagram of the multi-functional binuclear morpholine ionic liquid Specific implementation

[0031] The present application will be further described in detail below in combination with examples, but the implementation of the present application is not limited thereto.

[0032] Example 1

[0033] (1) Dibromodiethylene glycol

[0034] In a 250 mL four-necked flask, add acetonitrile 100 mL, add 0.1 mol and 0.2 mol phosphorus tribromide, stir, reflux for 12 h, filter to obtain white solid, dibromodiethylene glycol, yield 98%; the product structure is as follows:

[0035]

[0036] (2) Binuclear morpholine intermediate

[0037] In a 250 mL four-necked flask, add acetonitrile 100 mL, add 0.1 mol morpholine and 0.05 mol dibromodiethylene glycol, stir, reflux for 12 h, filter to obtain white solid, binuclear morpholine intermediate, yield 98%; the product structure is as follows:

[0038]

[0039] (3) Binuclear morpholine sulfonic acid inner salt

[0040] In a 250 mL four-necked flask, add petroleum ether 100 mL, add 0.1 mol binuclear morpholine intermediate and 0.2 mol 1,3-propane sulfonic acid inner ester, stir, react at 60°C for 6 h, filter to obtain white solid, binuclear morpholine sulfonic acid inner salt, yield 97%; the product structure is as follows:

[0041]

[0042] (4) Synthesis of binuclear morpholine sulfonic acid morpholine ethanesulfonic acid ionic liquid

[0043] Add binuclear morpholine sulfonic acid inner salt and morpholine ethanesulfonic acid (molar ratio 1:1.95) to a four-necked flask, stir at 60°C for 6 h, gradually form a homogeneous viscous liquid, which is binuclear morpholine sulfonic acid morpholine ethanesulfonic acid ionic liquid, yield 96%; the product structure is as follows:

[0044]

[0045] Binuclear morpholine intermediate (C 12 H 24 N2θ3) nuclear magnetic hydrogen spectrum: 1 H NMR (400 MHz, CDCl3)

[0046] δ (ppm) 3.76 (t, 8H, NCH CH2 O), 3.56 (t, 4H, NCH2 CH2 O CH2 CH2N), 2.56 (t, 4H, NCH2 CH2OCH2 CH2 N), 2.42 (t, 8H, N CH2 CH2O).

[0047] dinuclear morpholine intermediate (C 12 H 24 C NMR (100 MHz, CDC13) of the dinuclear morpholine intermediate (C 13 C NMR (100 MHz, CDC13) of the dinuclear morpholine intermediate (C

[0048] δ (ppm) 72.5, 70.3, 57.8, 55.6.

[0049] dinuclear morpholine intermediate (C 12 H 24 Elemental analysis of the dinuclear morpholine intermediate (C

[0050] Calculated (%) : C, 58.99; H, 9.90; N, 11.47.

[0051] Found (%) : C, 58.97; H, 9.92; N, 11.46.

[0052] dinuclear morpholine sulfonic acid inner salt (C 18 H 36 H NMR (400 MHz, D20) of the dinuclear morpholine sulfonic acid inner salt (C 1 H NMR (400 MHz, D20) of the dinuclear morpholine sulfonic acid inner salt (C

[0053] δ (ppm) 3.89 (t, 4H, NCH2 CH2 O CH2 CH2N), 3.85 (t, 8H, NCH2 CH2 O), 3.48 (t, 4H, N CH2 CH2OCH2 CH2 N), 3.42 (t, 8H, N CH2 CH2O), 3.39 (t, 4H, NCH2CH2 CH2 SO3), 3.29 (t, 4H, N CH2 CH2CH2SO3), 2.32 (m, 4H, NCH2 CH2 CH2SO3).

[0054] dinuclear morpholine sulfonic acid inner salt (C 18 H 36 C NMR (100 MHz, D20) of the dinuclear morpholine sulfonic acid inner salt (C

[0055] δ (ppm) 67.9, 64.8, 63.6, 62.2, 61.8, 60.2, 18.2.

[0056] dinuclear morpholine sulfonic acid inner salt (C18 H 36 Elemental analysis of N2O9S2)

[0057] Theoretical values ​​(%): C, 44.25; H, 7.43; N, 5.73; S, 13.12.

[0058] Measured values ​​(%): C, 44.27; H, 7.41; N, 5.72; S, 13.14.

[0059] Binonomorpholine sulfonic acid ionic liquid (C 18 H 38 N₂O₉S₂.₂C₆H 12 The 1H NMR spectrum of NO4S: 1 H NMR (400MHz, D2O)

[0060] 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), 3.0I(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 ).

[0061] Binonomorpholine sulfonic acid ionic liquid (C 18 H 38 N₂O₉S₂.₂C₆H 12 The carbon NMR spectra of NO4S (100MHz, D2O) δ (ppm) are 69.9, 67.1, 63.9, 62.4, 60.3, 57.9, 55.4, 55.2, 50.7, 24.0, 22.4, 18.3.

[0062] Binonomorpholine sulfonic acid ionic liquid (C 18 H 38 N₂O₉S₂.₂C₆H 12 Elemental analysis of NO4S

[0063] Theoretical value (%): C, 40.99; H, 7.11; N, 6.37; S, 14.59.

[0064] Actual value (%): C, 40.97; H, 7.13; N, 6.39; S, 14.57.

[0065] Example 2

[0066] (1) Dibromo diethylene glycol

[0067] In a 250 mL four-necked flask, add acetonitrile 100 mL, add 0.1 mol diethylene glycol and 0.2 mol phosphorus tribromide, stir, reflux for 12 h, filter to obtain white solid, dibromo diethylene glycol, yield 98%; the product structure is as follows:

[0068]

[0069] (2) Binuclear morpholine intermediate

[0070] In a 250 mL four-necked flask, add acetonitrile 100 mL, add 0.1 mol diethylene glycol and 0.2 mol phosphorus tribromide, stir, reflux for 12 h, filter to obtain white solid, dibromo diethylene glycol, yield 98%; the product structure is as follows:

[0071]

[0072] (3) Binuclear morpholine sulfonic acid inner salt

[0073] In a 250 mL four-necked flask, add cyclohexane 100 mL, add 0.1 mol binuclear morpholine intermediate and 0.2 mol 1,4-butane sulfonic acid inner ester, stir, 60°C for 6 h, filter to obtain white solid, binuclear morpholine sulfonic acid inner salt, yield 97%; the product structure is as follows:

[0074]

[0075] (4) Synthesis of binuclear morpholine sulfonic acid morpholine propyl sulfonic acid ionic liquid

[0076] Add binuclear morpholine sulfonic acid inner salt and morpholine propyl sulfonic acid (molar ratio 1:2.05) to a four-necked flask, stir at 60°C for 6 h, gradually form a homogeneous viscous liquid, binuclear morpholine sulfonic acid morpholine propyl sulfonic acid ionic liquid, yield 94.6%; the product structure is as follows:

[0077]

[0078] NMR of binuclear morpholine sulfonic acid inner salt (C 20 H 40 N2O9S2)1 H NMR (400 MHz, D2O)

[0079] δ (ppm) 3.87 (t, 4H, NCH2 CH2 O CH2 CH2N), 3.83 (t, 8H, NCH2 CH2 O), 3.46 (t, 4H, N CH2 CH2OCH2 CH2 N), 3.41 (t, 8H, N CH2 CH2O), 3.37 (t, 4H, NCH2CH2CH2 CH2 SO3), 3.29 (t, 4H, N CH2 CH2CH2CH2SO3), 1.92 (m, 4H, NCH2CH2 CH2 CH2SO3), 1.56 (m, 4H, NCH2 CH2 CH2CH2SO3).

[0080] Nuclear magnetic carbon spectrum (100 MHz, D2O) of the dinuclear morpholinium sulfonate inner salt (C 20 H 40 N2O9S2)

[0081] δ (ppm) 67.7, 64.6, 63.5, 62.0, 61.5, 60.1, 26.3, 18.2.

[0082] Elemental analysis of the dinuclear morpholinium sulfonate inner salt (C 20 H 40 N2O9S2)

[0083] Theoretical values (%): C, 46.49; H, 7.80; N, 5.42; S, 12.41.

[0084] Found (%): C, 46.47; H, 7.82; N, 5.44; S, 12.39.

[0085] Nuclear magnetic hydrogen spectrum of the dinuclear morpholinium sulfonate morpholinium propanesulfonate ionic liquid (C 20 H 42 N2O9S2.2C7H 14 NO4S) 1 H NMR (400 MHz, D2O)

[0086] δ δ (ppm) 8.50 (s, 2H, CH2SO3 H ), 3.81 (t, 4H, NCH2 CH2 O), 3.41 (t, 4H, N CH2 CH2O), 3.22 (t, 12H, NCH2 CH2), 3.01 (t, 4H, CH2 CH2 SO3H), 2.55 (t, 4H, CH2 CH2 SO3), 2.51 (t, 8H, CH2 CH2 N), 2.46 (t, 4H, N CH2 CH2), 1.95 (m, 4H, CH2 CH2 CH2), 1.71 (m, 12H, NCH2 CH2 ), 1.68 (m, 8H, NCH2 CH2 ), 1.49 (m, 4H, CH2 CH2 CH2SO3).

[0087] Dicationic ionic liquid of bis-morpholinium sulfonate morpholinium propanesulfonate (C 20 H 42 N2O9S2.2C7H 14 NO4S) Elemental analysis

[0088] Dicationic ionic liquid of bis-morpholinium sulfonate morpholinium propanesulfonate (C 20 H 42 N2O9S2.2C7H 14 NO4S) Elemental analysis

[0089] Theoretical value (%): C, 43.67; H, 7.54; N, 5.99; S, 13.71.

[0090] Found (%): C, 43.65; H, 7.56; N, 5.97; S, 13.72.

[0091] Example 3

[0092] (1) Dibromo triethylene glycol

[0093] In a 250 mL four-necked flask, acetonitrile 100 mL was added, 0.1 mol of triethylene glycol and 0.2 mol of phosphorus tribromide were added, stirred, refluxed for 12 h, filtered to obtain white solid, dibromo triethylene glycol, yield 96%; the product structure is as follows:

[0094]

[0095] (2) Bis-morpholinium intermediate

[0096] In a 250 mL four-necked flask, add 100 mL of acetonitrile, add 0.1 mol of morpholine and 0.05 mol of dibromotriethylene glycol, stir, reflux for 12 h, filter to obtain white solid, which is a binuclear morpholine intermediate, with a yield of 98%; the product structure is as follows:

[0097]

[0098] (3) Synthesis of binuclear morpholine sulfonic acid inner salt

[0099] In a 250 mL four-necked flask, add 100 mL of cyclohexane, add 0.1 mol of binuclear morpholine intermediate and 0.2 mol of 1,3-propane sulfonic acid inner ester, stir, react at 60°C for 6 h, filter to obtain white solid, which is a binuclear morpholine sulfonic acid inner salt, with a yield of 97%; the product structure is as follows:

[0100]

[0101] (4) Synthesis of binuclear morpholine sulfonic acid morpholine ethanesulfonic acid ionic liquid

[0102] Add binuclear sulfonic acid inner salt and morpholine ethanesulfonic acid (molar ratio 1:2.05) into a four-necked flask, stir at 60°C for 6 h, gradually form a homogeneous viscous liquid, which is a binuclear morpholine sulfonic acid morpholine ethanesulfonic acid ionic liquid, with a yield of 95.2%; the product structure is as follows:

[0103]

[0104] Binuclear morpholine intermediate (C 14 H 28 N2O4) NMR hydrogen spectrum: 1 H NMR (400 MHz, CDCl3)

[0105] δ (ppm) 3.79 (t, 8H, NCH CH2 O), 3.58 (t, 4H, O CH2CH2 O), 3.46 (t, 4H, NCH2 CH2 OC2H4O CH2 CH2N), 2.58 (t, 4H, N CH2 CH2OC2H4OCH2 CH2 N), 2.40 (t, 8H, N CH2 CH2O).

[0106] Binuclear morpholine intermediate (C 14 H 28 N2O4) NMR carbon spectrum: 13 C NMR (100 MHz, CDCl3)

[0107] δ(ppm)72.5, 70.3, 69.5, 57.8, 55.6.

[0108] binucleomorpholine intermediate (C 14 H 28 Elemental analysis of N2O4

[0109] Theoretical values ​​(%): C, 58.31; H, 9.79; N, 9.71.

[0110] Measured values ​​(%): C, 58.33; H, 9.77; N, 9.70.

[0111] Dinucleomorpholine sulfonate inner salt (C 20 H 40 N2O 10 S2) 1H NMR spectrum: 1 H NMR (400MHz, D2O)

[0112] δ(ppm) 3.89(t,4H,NCH2) CH2 OC2H4O CH2 CH2N), 3.85(t, 8H, NCH2) CH2 O), 3.60(t, 4H, O CH2CH2 O), 3.48(t, 4H, N CH2 CH2OC2H4OCH2 CH2 N), 3.42(t, 8H, N CH2 CH2O), 3.39(t, 4H, NCH2CH2 CH2 2SO3), 3.29(t, 4H, N CH2 CH2CH2SO3), 2.32(m, 4H, NCH2 CH2 CH2SO3).

[0113] Dinucleomorpholine sulfonate inner salt (C 20 H 40 N2O 10 Carbon NMR spectrum of S2 (100MHz, D2O)

[0114] δ(ppm)70.9, 67.9, 64.8, 63.6, 62.2, 61.8, 60.2, 18.5.

[0115] Dinucleomorpholine sulfonate inner salt (C 20 H 40 N2O 10 Elemental analysis of S2)

[0116] Theoretical values ​​(%): C, 45.10; H, 7.57; N, 5.26; S, 12.04.

[0117] Found (%): C, 45.12; H, 7.55; N, 5.24; S, 12.05.

[0118] Bimetallic morpholinium sulfonate morpholinium ethanesulfonate ionic liquid (C 20 H 42 N2O 10 S2.2C6H 12 NO4S) of the nuclear magnetic hydrogen spectrum: 1 H NMR (400 MHz, D2O)

[0119] δ (ppm) 8.50 (s, 2H, CH2SO3 H ), 3.81 (t, 4H, NCH2 CH2 O), 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), 2.51 (t, 8H, CH2 CH2 N), 2.46 (t, 4H, N CH2 CH2), 1.95 (m, 4H, CH2 CH2 CH2), 1.71 (m, 12H, NCH2 CH2 ), 1.68 (m, 8H, NCH2 CH2 ), 1.49 (m, 4H, CH2 CH2 CH2SO3).

[0120] Bimetallic morpholinium sulfonate morpholinium ethanesulfonate ionic liquid (C 20 H 42 N2O 10 S2.2C6H 12 NO4S) of the nuclear magnetic carbon spectrum (100 MHz, D2O) δ (ppm) 70.8, 67.9, 67.8, 60.3, 56.9, 55.4, 54.9, 51.9, 23.6, 24.0, 22.4, 19.5.

[0121] Bimetallic morpholinium sulfonate morpholinium ethanesulfonate ionic liquid (C 20 H 42 N2O 10 S2.2C6H 12 NO4S) of the elemental analysis

[0122] Theoretical value (%): C, 41.63; H, 7.21; N, 6.07; S, 13.89.

[0123] Found (%): C, 41.61; H, 7.23; N, 6.09; S, 13.87.

[0124] Example 4

[0125] (1) Dibromo triethylene glycol

[0126] In a 250 mL four-necked flask, add acetonitrile 100 mL, add 0.1 mol triethylene glycol and 0.2 mol phosphorus tribromide, stir, reflux for 12 h, filter to obtain white solid, dibromo triethylene glycol, yield 96%; the product structure is as follows:

[0127]

[0128] (2) Binuclear morpholine intermediate

[0129] In a 250 mL four-necked flask, add acetonitrile 100 mL, add 0.1 mol morpholine and 0.05 mol dibromo triethylene glycol, stir, reflux for 12 h, filter to obtain white solid, binuclear morpholine intermediate, yield 98%; the product structure is as follows:

[0130]

[0131] (3) Binuclear morpholine sulfonic acid inner salt

[0132] In a 250 mL four-necked flask, add cyclohexane 100 mL, add 0.1 mol binuclear morpholine intermediate and 0.2 mol 1,4-butane sulfonic acid inner ester, stir, react at 60°C for 6 h, filter to obtain white solid, binuclear morpholine sulfonic acid inner salt, yield 97%; the product structure is as follows:

[0133]

[0134] (4) Synthesis of binuclear morpholine sulfonic acid morpholine propanesulfonic acid ionic liquid

[0135] Add binuclear morpholine sulfonic acid inner salt and morpholine propanesulfonic acid (molar ratio 1:2.05) to a four-necked flask, stir at 60°C for 6 h, gradually form a homogeneous viscous liquid, which is binuclear morpholine sulfonic acid morpholine propanesulfonic acid ionic liquid, yield 95%; the product structure is as follows:

[0136]

[0137] The nuclear magnetic hydrogen spectrum of binuclear morpholine sulfonic acid inner salt (C 22 H 44 N2O 10 S2) is as follows: 1 H NMR (400 MHz, D2O)

[0138] δ (ppm) 3.87 (t, 4H, NCH2 CH2 OC2H4O CH2 CH2N), 3.83 (t, 8H, NCH2 CH2 O), 3.60 (t, 4H, O CH2CH2 O), 3.47 (t, 4H, N CH2 CH2OC2H4OCH2 CH2 2N), 3.41 (t, 8H, N CH2 CH2O), 3.37 (t, 4H, NCH2CH2CH2 CH2 SO3), 3.29 (t, 4H, N CH2 CH2CH2CH2SO3), 1.90 (m, 4H, NCH2CH2 CH2 CH2SO3), 1.55 (m, 4H, NCH2 CH2 CH2CH2SO3).

[0139] Nuclear magnetic carbon spectrum (100 MHz, D2O) of the dinuclear morpholinium sulfonate inner salt (C 22 H 44 N2O 10 S2) of the dinuclear morpholinium sulfonate inner salt (C

[0140] δ (ppm) 69.9, 67.9, 64.8, 63.6, 62.2, 61.8, 60.2, 26.3, 18.5

[0141] Elemental analysis of the dinuclear morpholinium sulfonate inner salt (C 22 H 44 N2O 10 S2) of the dinuclear morpholinium sulfonate inner salt (C

[0142] Theoretical values (%): C, 47.12; H, 7.91 ; N, 5.00; S, 11.44.

[0143] Found (%): C, 47.14; H, 7.90; N, 5.02; S, 11.42.

[0144] Nuclear magnetic hydrogen spectrum of the dinuclear morpholinium sulfonate morpholinium propanesulfonate ionic liquid (C 22 H 46 N2O 10 S2.2C7H 14 NO4S) of the dinuclear morpholinium sulfonate inner salt (C 1 H NMR (400 MHz, D2O)

[0145] δ (ppm) 8.50 (s, 2H, CH2SO3 H ), 3.81 (t, 4H, NCH2 CH2 O), 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), 2.51(t, 8H, CH2 CH2 N), 2.46(t, 4H, N CH2 CH2), 1.95(m, 4H, CH2) CH2 CH2), 1.71(m, 12H, NCH2) CH2 ),1.68(m,8H,NCH2 CH2 ),1.49(m,4H,CH2 CH2 CH2SO3).

[0146] Binonomorpholine sulfonic acid propanesulfonic acid ionic liquid (C 22 H 46 N2O 10 S2.2C7H 14 The carbon NMR spectra of NO4S (100MHz, D2O) δ (ppm) are 67.9, 67.8, 60.3, 56.9, 56.5, 55.4, 54.9, 51.9, 23.6, 24.0, 22.4, 21.7, 19.5.

[0147] Binonomorpholine sulfonic acid propanesulfonic acid ionic liquid (C 22 H 46 N2O 10 S2.2C7H 14 Elemental analysis of NO4S

[0148] Theoretical values ​​(%): C, 44.15; H, 7.62; N, 5.72; S, 13.10.

[0149] Measured values ​​(%): C, 44.13; H, 7.64; N, 5.70; S, 13.11.

[0150] The acidity of the multifunctional binuclear morpholine ionic liquids was calculated using the Hammett acidity method. Multifunctional binuclear morpholine ionic liquids were prepared using different glycols, alkyl sulfonates, and sulfonic acid derivatives; their yields and Hammett acidities are summarized in Table 1.

[0151] Table 1 Examples of the preparation of multifunctional binuclear morpholine ionic liquids

[0152] CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 92.6 3.62 CH2 CH2 CH2 CH2 90.5 3.97 CH2 CH2 CH2 CH2 92.0 4.15 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 89.8 4.37

Claims

1. A multifunctional binuclear morpholine ionic liquid and its preparation method, characterized in that: The structural formula of the multifunctional binuclear morpholine ionic liquid is as follows: The preparation method of the multifunctional binuclear morpholine 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 binucleomorpholine intermediate Using morpholine and dibromo(chloro)glycol as raw materials, a binuclear morpholine intermediate was synthesized by reacting in an organic solvent at 80℃-120℃ for 12-24h. (3) Preparation of binucleomorpholine sulfonate inner salt Using a dinuclear morpholine intermediate and an alkyl sulfonate lactone as raw materials, the dinuclear morpholine sulfonate inner salt was synthesized by reacting in an organic solvent at 40℃-60℃ for 6-12 h. (4) Preparation of multifunctional binuclear morpholine ionic liquids Multifunctional binuclear morpholine ionic liquids were prepared by reacting binuclear morpholine sulfonic acid inner salt and sulfonic acid derivatives at 60℃-80℃ for 6-8 hours.

2. The multifunctional binuclear morpholine 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, or octaethylene glycol; the dibromo(chloro)glycol is one of dibromo(chloro)diethylene glycol, dibromo(chloro)triethylene glycol, dibromo(chloro)tetraethylene glycol, dibromo(chloro)pentane glycol, dibromo(chloro)hexaethylene glycol, dibromo(chloro)heptaethylene glycol, or dibromo(chloro)octaethylene glycol; the organic solvent is one of acetonitrile, n-hexane, cyclohexane, xylene, toluene, or 1,4-dioxane; the molar ratio of the glycol to phosphorus trichloride or phosphorus tribromide is 1:(1.95-2.05).

3. The multifunctional binuclear morpholine ionic liquid and its preparation method according to claim 1, characterized in that: The organic solvent in step (2) is one of methanol, ethanol, isopropanol, acetonitrile, n-hexane, cyclohexane, xylene, toluene, or 1,4-dioxane; the molar ratio of morpholine to dibromo(chloro)glycol is 1:(1.95-2.05).

4. The multifunctional binuclear morpholine ionic liquid and its preparation method according to claim 1, characterized in that: The 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 dinuclear morpholine intermediate to the alkyl sulfonate lactone is 1:(1.95-2.10).

5. The multifunctional binuclear morpholine 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 acid, pyrrolopropanesulfonic acid, pyrrolobutanesulfonic 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, cyclohexylaminopropanesulfonic acid; the molar ratio of the dinuclear morpholine sulfonic acid inner salt to the sulfonic acid derivative is 1:(1.95-2.1).

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