An ionic liquid / hy-drotope@cyclodextrin-derivatized cellulose bilayer sheet

Abstract

The application discloses an ionic liquid / eutectic solvent@cyclodextrin-derivative cellulose double-layer tablet and a preparation method thereof; the cyclodextrin is beta-cyclodextrin, the ionic liquid is 1-amine ethyl-3-methyl imidazole bromide, the eutectic solvent is composed of choline chloride as a hydrogen bond acceptor and acetic acid as a hydrogen bond donor, and derivative cellulose including ethyl cellulose is used as a diluent / binder. The application first prepares two kinds of inclusion compounds of ionic liquid@cyclodextrin and eutectic solvent@cyclodextrin through a saturated aqueous solution method, then uniformly mixes the two kinds of inclusion compounds with derivative cellulose respectively, and finally adopts a tablet pressing method to prepare a composite double-layer tablet. The preparation process is simple, the conditions are mild, the process is easy to popularize, and the process is suitable for large-scale production. The ionic liquid and the eutectic solvent are solidized by forming inclusion compounds with the cyclodextrin, and the state is stable. The obtained composite tablet has ideal hardness, different layers can play selective adsorption effects, and has ideal environmental friendliness and recycling properties.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite materials, especially to the field of composite materials composed of ionic liquids, deep eutectic solvents, cyclodextrins and derivatized cellulose; and specifically to the method for preparing double-layer tablets from the four objects. BACKGROUND

[0002] Cyclodextrin is an oligosaccharide compound, and its molecule is a hollow cylindrical three-dimensional ring structure. There are a large number of hydroxyl groups on the surface of the ring structure, so that the outside of the molecule has hydrophilicity, and the internal cavity exhibits hydrophobicity. By utilizing this characteristic, cyclodextrin has the ability to form host-guest inclusion compounds with a variety of different organic and inorganic guest molecules. β-cyclodextrin has become a widely used cyclodextrin product due to its moderate cavity size and easy separation and preparation, and β-cyclodextrin inclusion compounds have been widely used in the fields of medicine, food, environment, chemical analysis, separation technology, etc.

[0003] Ionic liquids are considered to be one of the potential green solvents in industry. Such solvents are of great concern due to their environmental-friendly characteristics and good physicochemical properties, such as strong stability, low vapor pressure, wide electrochemical window, good electrical conductivity, wide solubility range, and multiple functions. These advantages make them have obvious advantages over traditional organic solvents. Currently, various functional ionic liquids have been widely used in catalysis, separation, electrochemistry, nanomaterials, polymer science, biomass processing, and lubricants, and some processes have been operated on an industrial scale. In the field of separation, ionic liquids have been widely used for extracting / adsorbing objects such as gases, rare earth elements, active ingredients, harmful substances, and biological samples.

[0004] Deep eutectic solvents are mixtures formed by two or three components through intermolecular interactions, with a melting point lower than that of the monomer components. Due to its similarity to ionic liquids, it is called a kind of ionic liquid-like, which is a new type of green solvent. Deep eutectic solvents have the advantages of simple synthesis, strong designability, strong biocompatibility, low cost, and high atom utilization rate, and are widely used in the fields of energy, environmental protection, separation technology, etc. They have similar separation objects as ionic liquids, and the structure designability and performance adjustability of both determine that different green solvents can have selectivity for different target objects, but there is no report on the simultaneous use of both in the same separation process. In addition, if ionic liquids and deep eutectic solvents can be immobilized in a simple and effective way, it will be beneficial to their recovery and recycling, further reducing their consumption, loss and residue.

[0005] As one of the most polysaccharides in the world, cellulose is a natural degradable product without harm, and its different derivative products have been widely used as fine chemical auxiliaries. A series of derivatives represented by ethyl cellulose have very excellent adhesion and molding properties, as well as stable chemical properties and biocompatibility, so they are more and more applied in this technical field. SUMMARY

[0006] The purpose of the present application is to provide a preparation method of a double-layer tablet with ionic liquid, eutectic solvent and cyclodextrin as functional components. The method is simple in process, mild in conditions, easy to operate and promote. By forming inclusion compounds through simple saturated aqueous solution method and physically mixing with derivative cellulose, then pressing into composite tablets, the problems of high cost, difficulty in recycling, recovery difficulty and easy residue when they are used alone are greatly solved. The composite tablets have consistent and regular appearance, ideal hardness, and save storage space in volume. They are simple and flexible to use, easy to realize large-scale preparation and multiple use. The inclusion compounds formed by ionic liquid and eutectic solvent and cyclodextrin are stable, and the prepared composite tablets have ideal environmental friendliness and recycling property. The two sides of the composite tablets are different functional components, which can simultaneously exert their respective separation selectivity, realizing the effect of one tablet instead of two tablets.

[0007] Technical scheme: In order to achieve the above purpose, a double-layer tablet composed of ionic liquid, eutectic solvent, cyclodextrin and derivative cellulose and its preparation method are proposed.

[0008] An ionic liquid / eutectic solvent@cyclodextrin-derivative cellulose double-layer tablet is characterized in that cyclodextrin and ionic liquid / eutectic solvent are combined in the form of inclusion compounds, and then mixed with diluent / binder to prepare tablets. The specific preparation steps are as follows:

[0009] (1) Prepare a saturated cyclodextrin aqueous solution at 60℃, then add ionic liquid or eutectic solvent, stir at 60℃ for a certain time, then refrigerate at 4℃ for 24h; finally, filter and wash with deionized water for 3 times, and then vacuum dry to obtain two kinds of inclusion compounds of ionic liquid@cyclodextrin and eutectic solvent@cyclodextrin, respectively;

[0010] (2) Mix the two kinds of inclusion compounds in (1) with derivative cellulose respectively, grind thoroughly and pass through a 200 mesh sieve;

[0011] (3) Lay the sieved ionic liquid@cyclodextrin-derivative cellulose mixed powder on the bottom surface of the stainless steel tablet press mold, then lay the sieved eutectic solvent@cyclodextrin-derivative cellulose mixed powder on the upper layer, and then press to form the ionic liquid / eutectic solvent@cyclodextrin-derivative cellulose composite double-layer tablet.

[0012] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the ionic liquid / hydrothf is immobilized in the cyclodextrin cavity in the form of inclusion complex, and the preparation method used is saturated aqueous solution method.

[0013] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the cyclodextrin is β-cyclodextrin.

[0014] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the ionic liquid is 1-amine ethyl-3-methyl imidazole bromide, and the hydrothf is composed of choline chloride as a hydrogen bond acceptor and acetic acid as a hydrogen bond donor.

[0015] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the diluent / binder used is derived cellulose, including ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose.

[0016] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the molar ratio of ionic liquid / hydrothf to cyclodextrin in the preparation of inclusion complex is 1:1-5:1.

[0017] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the mass ratio (g / g) of ionic liquid / hydrothf @ cyclodextrin inclusion complex to diluent / binder is 0.025:0.125-0.125:0.025.

[0018] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the pressed composite tablet has a bilayer structure; one side is ionic liquid @ cyclodextrin-derived cellulose, and the other side is hydrothf @ cyclodextrin-derived cellulose.

[0019] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the tabletting pressure range is 5-15 MPa.

[0020] The ionic liquid / hydrothf @ cyclodextrin-derived cellulose bilayer tablet of the above-mentioned one, its feature lies in that the pressing time range is 5-60 min. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The infrared spectra of the two inclusion complexes of ionic liquid @ β-cyclodextrin and hydrothf @ β-cyclodextrin;

[0022] Figure 2(a) Appearance of bilayer sheets with ionic liquid / eutectic solvent@β-cyclodextrin-ethyl cellulose and (b) appearance of bilayer sheets with pigment mixed with ionic liquid@β-cyclodextrin-ethyl cellulose layer (pigment added to the upper layer to observe the boundary between the two layers);

[0023] Figure 3 Scanning electron microscope (SEM) images of cross sections of ionic liquid / eutectic solvent@β-cyclodextrin-ethyl cellulose bilayer sheets (a: ionic liquid@β-cyclodextrin-ethyl cellulose layer, b: eutectic solvent@β-cyclodextrin-ethyl cellulose layer);

[0024] Figure 4 The effects of (a) the amount of ethyl cellulose and (b) the tableting pressure on the hardness of the bilayer tablets;

[0025] Figure 5 The effect of the amount of ethyl cellulose on the hardness of (a) ionic liquid@β-cyclodextrin monolayer sheets and (b) eutectic solvent@β-cyclodextrin monolayer sheets. Detailed Implementation

[0026] The following is a detailed description of the present invention. While specific embodiments of the invention have been shown, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the invention and to fully convey its scope to those skilled in the art.

[0027] This specification and claims do not distinguish components by differences in terminology, but rather by differences in function. The terms "comprising" or "including" used in this application are open-ended and should be interpreted as "including but not limited to." The embodiments described later in the specification are preferred embodiments of the invention and are intended to convey the general principles of the specification, not to limit the scope of the invention.

[0028] Example 1

[0029] (1) Prepare a saturated β-cyclodextrin aqueous solution at 60℃, then add an ionic liquid with a molar ratio of 1:1 to β-cyclodextrin, stir thoroughly at 60℃ for 2 hours, then refrigerate at 4℃ for 24 hours, finally filter and wash three times with deionized water, and then vacuum dry to obtain the ionic liquid@β-cyclodextrin inclusion complex; similarly, prepare a saturated β-cyclodextrin aqueous solution at 60℃, then add a eutectic solvent with a molar ratio of 1:1 to β-cyclodextrin, stir thoroughly at 60℃ for 2 hours, then refrigerate at 4℃ for 24 hours, finally filter and wash three times with deionized water, and then vacuum dry to obtain the eutectic solvent@β-cyclodextrin inclusion complex;

[0030] (2) The ionic liquid@β-cyclodextrin inclusion compound was mixed with ethyl cellulose at a mass ratio (g / g) of 0.025:0.125, and the eutectic solvent@β-cyclodextrin inclusion compound was mixed with ethyl cellulose at a mass ratio (g / g) of 0.025:0.125. After being fully ground and passed through a 200-mesh sieve, the mixture was uniformly mixed.

[0031] (3) The sieved ionic liquid@β-cyclodextrin-ethyl cellulose mixed powder was laid on the bottom surface of a stainless steel tablet press mold, and the sieved eutectic solvent@β-cyclodextrin-ethyl cellulose mixed powder was laid on the upper layer. After being pressed at a pressure of 15 MPa for 30 min, ionic liquid / eutectic solvent@β-cyclodextrin-ethyl cellulose double-layer tablets were obtained.

[0032] Example 2

[0033] (1) A saturated β-cyclodextrin aqueous solution at 60°C was prepared, and ionic liquid was added at a molar ratio of 2:1 with respect to β-cyclodextrin. After being fully stirred at 60°C for 6 h, the solution was refrigerated at 4°C for 24 h. After being filtered and washed with deionized water three times, the ionic liquid@β-cyclodextrin inclusion compound was obtained after vacuum drying. Similarly, a saturated β-cyclodextrin aqueous solution at 60°C was prepared, and eutectic solvent was added at a molar ratio of 3:1 with respect to β-cyclodextrin. After being fully stirred at 60°C for 4 h, the solution was refrigerated at 4°C for 24 h. After being filtered and washed with deionized water three times, the eutectic solvent@β-cyclodextrin inclusion compound was obtained after vacuum drying.

[0034] (2) The ionic liquid@β-cyclodextrin inclusion compound was mixed with methyl cellulose at a mass ratio (g / g) of 0.05:0.1, and the eutectic solvent@β-cyclodextrin inclusion compound was mixed with methyl cellulose at a mass ratio (g / g) of 0.05:0.1. After being fully ground and passed through a 200-mesh sieve, the mixture was uniformly mixed.

[0035] (3) The sieved ionic liquid@β-cyclodextrin-methyl cellulose mixed powder was laid on the bottom surface of a stainless steel tablet press mold, and the sieved eutectic solvent@β-cyclodextrin-methyl cellulose mixed powder was laid on the upper layer. After being pressed at a pressure of 5 MPa for 60 min, ionic liquid / eutectic solvent@β-cyclodextrin-methyl cellulose double-layer tablets were obtained.

[0036] Example 3

[0037] (1) Preparation of saturated β-cyclodextrin aqueous solution at 60℃, then add ionic liquid with a molar ratio of 4:1 to β-cyclodextrin, fully stir at 60℃ for 2h, then refrigerate at 4℃ for 24h, finally vacuum drying after suction filtration and washing with deionized water for 3 times, to obtain ionic liquid @ β-cyclodextrin inclusion complex; similarly, prepare saturated β-cyclodextrin aqueous solution at 60℃, then add deep eutectic solvent with a molar ratio of 5:1 to β-cyclodextrin, fully stir at 60℃ for 4h, then refrigerate at 4℃ for 24h, finally vacuum drying after suction filtration and washing with deionized water for 3 times, to obtain deep eutectic solvent @ β-cyclodextrin inclusion complex;

[0038] (2) Mix the ionic liquid @ β-cyclodextrin inclusion complex with a mass ratio (g / g) of 0.075:0.75 with carboxymethyl cellulose, and mix the deep eutectic solvent @ β-cyclodextrin inclusion complex with a mass ratio (g / g) of 0.025:0.125 with carboxymethyl cellulose, fully grind and pass through a 200 mesh sieve;

[0039] (3) Spread the sieved ionic liquid @ β-cyclodextrin-carboxymethyl cellulose mixed powder on the bottom surface of the stainless steel tablet press mold, then spread the sieved deep eutectic solvent @ β-cyclodextrin-carboxymethyl cellulose mixed powder on the upper layer, press at a pressure of 15MPa for 30min, to obtain ionic liquid / deep eutectic solvent @ β-cyclodextrin-carboxymethyl cellulose double-layer tablets.

[0040] Example 4

[0041] (1) Preparation of saturated β-cyclodextrin aqueous solution at 60℃, then add ionic liquid with a molar ratio of 3:1 to β-cyclodextrin, fully stir at 60℃ for 6h, then refrigerate at 4℃ for 24h, finally vacuum drying after suction filtration and washing with deionized water for 3 times, to obtain ionic liquid @ β-cyclodextrin inclusion complex; similarly, prepare saturated β-cyclodextrin aqueous solution at 60℃, then add deep eutectic solvent with a molar ratio of 3:1 to β-cyclodextrin, fully stir at 60℃ for 6h, then refrigerate at 4℃ for 24h, finally vacuum drying after suction filtration and washing with deionized water for 3 times, to obtain deep eutectic solvent @ β-cyclodextrin inclusion complex;

[0042] (2) Mix the ionic liquid @ β-cyclodextrin inclusion complex with a mass ratio (g / g) of 0.1:0.05 with hydroxypropyl cellulose, and mix the deep eutectic solvent @ β-cyclodextrin inclusion complex with a mass ratio (g / g) of 0.1:0.05 with hydroxypropyl cellulose, fully grind and pass through a 200 mesh sieve;

[0043] (3) The sieved ionic liquid@β-cyclodextrin-hydroxypropyl cellulose mixed powder is laid on the bottom surface of a stainless steel tablet press mold, and the sieved eutectic solvent@β-cyclodextrin-hydroxypropyl cellulose mixed powder is laid on the upper layer, and a ionic liquid / eutectic solvent@β-cyclodextrin-hydroxypropyl cellulose double-layer tablet is prepared under a pressure of 10 MPa for 45 min.

[0044] Example 5

[0045] (1) A saturated β-cyclodextrin aqueous solution at 60°C is prepared, and an ionic liquid is added at a molar ratio of 2:1 with respect to β-cyclodextrin, and stirred sufficiently at 60°C for 4 h, then refrigerated at 4°C for 24 h, and finally vacuum dried after suction filtration and washing with deionized water for 3 times, to obtain an ionic liquid@β-cyclodextrin inclusion compound; similarly, a saturated β-cyclodextrin aqueous solution at 60°C is prepared, and a eutectic solvent is added at a molar ratio of 5:1 with respect to β-cyclodextrin, and stirred sufficiently at 60°C for 2 h, then refrigerated at 4°C for 24 h, and finally vacuum dried after suction filtration and washing with deionized water for 3 times, to obtain a eutectic solvent@β-cyclodextrin inclusion compound;

[0046] (2) The ionic liquid@β-cyclodextrin inclusion compound is mixed uniformly with ethyl cellulose at a mass ratio (g / g) of 0.125:0.025, and the eutectic solvent@β-cyclodextrin inclusion compound is mixed uniformly with ethyl cellulose at a mass ratio (g / g) of 0.075:0.075, and ground sufficiently and sieved through a 200-mesh sieve;

[0047] (3) The sieved ionic liquid@β-cyclodextrin-ethyl cellulose mixed powder is laid on the bottom surface of a stainless steel tablet press mold, and the sieved eutectic solvent@β-cyclodextrin-ethyl cellulose mixed powder is laid on the upper layer, and a ionic liquid / eutectic solvent@β-cyclodextrin-ethyl cellulose double-layer tablet is prepared under a pressure of 10 MPa for 30 min.

[0048] Example 6

[0049] (1) A saturated β-cyclodextrin aqueous solution at 60°C is prepared, and an ionic liquid is added at a molar ratio of 4:1 with respect to β-cyclodextrin, and stirred sufficiently at 60°C for 2 h, then refrigerated at 4°C for 24 h, and finally vacuum dried after suction filtration and washing with deionized water for 3 times, to obtain an ionic liquid@β-cyclodextrin inclusion compound; similarly, a saturated β-cyclodextrin aqueous solution at 60°C is prepared, and a eutectic solvent is added at a molar ratio of 1:1 with respect to β-cyclodextrin, and stirred sufficiently at 60°C for 6 h, then refrigerated at 4°C for 24 h, and finally vacuum dried after suction filtration and washing with deionized water for 3 times, to obtain a eutectic solvent@β-cyclodextrin inclusion compound;

[0050] (2) The ionic liquid@β-cyclodextrin inclusion complex was mixed with methyl cellulose at a mass ratio (g / g) of 0.1:0.05, and the deep eutectic solvent@β-cyclodextrin inclusion complex was mixed with methyl cellulose at a mass ratio (g / g) of 0.05:0.1, and then they were ground thoroughly and passed through a 200-mesh sieve;

[0051] (3) The sieved ionic liquid@β-cyclodextrin-methyl cellulose mixed powder was laid on the bottom surface of a stainless steel tablet press mold, and then the sieved deep eutectic solvent@β-cyclodextrin-methyl cellulose mixed powder was laid on the upper layer, and then a double-layer tablet of ionic liquid / deep eutectic solvent@β-cyclodextrin-methyl cellulose was prepared by pressing under a pressure of 5 MPa for 45 min.

[0052] Example 7

[0053] (1) A saturated β-cyclodextrin aqueous solution at 60°C was prepared, and then ionic liquid was added at a molar ratio of 2:1 with respect to β-cyclodextrin, and then the mixture was stirred thoroughly at 60°C for 4 h, and then it was refrigerated at 4°C for 24 h, and then it was vacuum-dried after being filtered and washed with deionized water for 3 times, to obtain an ionic liquid@β-cyclodextrin inclusion complex; similarly, a saturated β-cyclodextrin aqueous solution at 60°C was prepared, and then deep eutectic solvent was added at a molar ratio of 4:1 with respect to β-cyclodextrin, and then the mixture was stirred thoroughly at 60°C for 2 h, and then it was refrigerated at 4°C for 24 h, and then it was vacuum-dried after being filtered and washed with deionized water for 3 times, to obtain a deep eutectic solvent@β-cyclodextrin inclusion complex;

[0054] (2) The ionic liquid@β-cyclodextrin inclusion complex was mixed with carboxymethyl cellulose at a mass ratio (g / g) of 0.075:0.075, and the deep eutectic solvent@β-cyclodextrin inclusion complex was mixed with carboxymethyl cellulose at a mass ratio (g / g) of 0.125:0.025, and then they were ground thoroughly and passed through a 200-mesh sieve;

[0055] (3) The sieved ionic liquid@β-cyclodextrin-carboxymethyl cellulose mixed powder was laid on the bottom surface of a stainless steel tablet press mold, and then the sieved deep eutectic solvent@β-cyclodextrin-carboxymethyl cellulose mixed powder was laid on the upper layer, and then a double-layer tablet of ionic liquid / deep eutectic solvent@β-cyclodextrin-carboxymethyl cellulose was prepared by pressing under a pressure of 15 MPa for 60 min.

[0056] Example 8

[0057] (1) Preparation of saturated β-cyclodextrin aqueous solution at 60℃, then add ionic liquid with a molar ratio of 2:1 to β-cyclodextrin, fully stir at 60℃ for 6h, then refrigerate at 4℃ for 24h, finally vacuum dry after suction filtration and washing with deionized water for 3 times, to obtain ionic liquid@β-cyclodextrin inclusion complex; similarly, preparation of saturated β-cyclodextrin aqueous solution at 60℃, then add deep eutectic solvent with a molar ratio of 2:1 to β-cyclodextrin, fully stir at 60℃ for 4h, then refrigerate at 4℃ for 24h, finally vacuum dry after suction filtration and washing with deionized water for 3 times, to obtain deep eutectic solvent@β-cyclodextrin inclusion complex;

[0058] (2) Mix ionic liquid@β-cyclodextrin inclusion complex with a mass ratio (g / g) of 0.025:0.125 with hydroxypropyl cellulose, mix deep eutectic solvent@β-cyclodextrin inclusion complex with a mass ratio (g / g) of 0.125:0.025 with hydroxypropyl cellulose, fully grind and pass through a 200 mesh sieve;

[0059] (3) Spread the sieved ionic liquid@β-cyclodextrin-hydroxypropyl cellulose mixed powder on the bottom surface of the stainless steel tablet press mold, then spread the sieved deep eutectic solvent@β-cyclodextrin-hydroxypropyl cellulose mixed powder on the upper layer, press at a pressure of 10MPa for 15min, to obtain ionic liquid / deep eutectic solvent@β-cyclodextrin-hydroxypropyl cellulose double-layer tablets.

[0060] Example 9

[0061] (1) Preparation of saturated β-cyclodextrin aqueous solution at 60℃, then add ionic liquid with a molar ratio of 5:1 to β-cyclodextrin, fully stir at 60℃ for 2h, then refrigerate at 4℃ for 24h, finally vacuum dry after suction filtration and washing with deionized water for 3 times, to obtain ionic liquid@β-cyclodextrin inclusion complex; similarly, preparation of saturated β-cyclodextrin aqueous solution at 60℃, then add deep eutectic solvent with a molar ratio of 5:1 to β-cyclodextrin, fully stir at 60℃ for 2h, then refrigerate at 4℃ for 24h, finally vacuum dry after suction filtration and washing with deionized water for 3 times, to obtain deep eutectic solvent@β-cyclodextrin inclusion complex;

[0062] (2) Mix ionic liquid@β-cyclodextrin inclusion complex with a mass ratio (g / g) of 0.075:0.075 with ethyl cellulose, mix deep eutectic solvent@β-cyclodextrin inclusion complex with a mass ratio (g / g) of 0.075:0.075 with ethyl cellulose, fully grind and pass through a 200 mesh sieve;

[0063] (3) The sieved ionic liquid@β-cyclodextrin-ethyl cellulose mixed powder is laid on the bottom surface of a stainless steel tablet press mold, and the sieved eutectic solvent@β-cyclodextrin-ethyl cellulose mixed powder is laid on the upper layer, and then pressed under a pressure of 15 MPa for 15 min to obtain ionic liquid / eutectic solvent@β-cyclodextrin-ethyl cellulose double-layer tablets;

[0064] (4) A mixed solution of 10 mL of lead ions and basic red with a concentration of 1 mg / mL is prepared, the double-layer tablets in (3) are added to the solution, and then placed on a shaker with a rotation speed of 300 rpm for adsorption experiment, until the solution color no longer changes, the adsorption is completed. The ionic liquid@β-cyclodextrin layer selectively adsorbs lead ions with an adsorption capacity of 88.7 mg / g, and the eutectic solvent@β-cyclodextrin layer selectively adsorbs basic red with an adsorption capacity of 60.8 mg / g.

[0065] The infrared spectra of the ionic liquid@β-cyclodextrin and eutectic solvent@β-cyclodextrin prepared in Example 9 are tested, and the results are shown in Figures Figure 1 The infrared test results are briefly analyzed as follows: the strong peaks at 3433 cm -1 , 2929 cm -1 , and 1026 cm -1 in the spectrum of ionic liquid@β-cyclodextrin and the strong peaks at 3370 cm -1 , 2923 cm -1 , and 1028 cm -1 in the spectrum of eutectic solvent@β-cyclodextrin are respectively O-H stretching vibration peaks, C-H stretching vibration peaks, and C-O stretching vibration peaks in β-cyclodextrin; the absorption peak near 1570 cm -1 in the spectrum of ionic liquid@β-cyclodextrin is generated by N-H bending vibration, indicating that the ionic liquid has been successfully immobilized; the absorption peak at 1708 cm -1 in the spectrum of eutectic solvent@β-cyclodextrin is generated by C=O stretching vibration, indicating that the eutectic solvent has been successfully immobilized.

[0066] The ionic liquid / eutectic solvent@β-cyclodextrin-ethyl cellulose double-layer tablets prepared in Example 9 are directly observed, dyed and observed, and observed by scanning electron microscope, and the results are shown in Figures Figure 2 (a), (b), and Figures Figure 3 (a), (b).

[0067] Maintaining a total bilayer tablet mass of 0.3 g and a single layer mass of 0.15 g, 0.15–0.05 g of ionic liquid@β-cyclodextrin inclusion complex and eutectic solvent@β-cyclodextrin inclusion complex were mixed thoroughly with 0–0.1 g of ethyl cellulose, ground completely, and passed through a 200-mesh sieve. The tablets were then pressed at 15 MPa for 15 min to investigate the effect of different diluent dosages on tablet hardness. Simultaneously, 0.075 g of ionic liquid@β-cyclodextrin inclusion complex and 0.75 g of eutectic solvent@β-cyclodextrin inclusion complex were mixed thoroughly with 0.075 g of ethyl cellulose, ground completely, and passed through a 200-mesh sieve. The tablets were then pressed at 5–15 MPa for 15 min to investigate the effect of different tableting pressures on tablet hardness. The results are shown in the appendix. Figure 4 (a) and 4(b).

[0068] To conduct a comparison, keeping the total mass of the monolayer tablets at 0.15 g, 0.15–0.025 g of ionic liquid@β-cyclodextrin inclusion complex or eutectic solvent@β-cyclodextrin inclusion complex were mixed evenly with 0–0.125 g of ethyl cellulose, thoroughly ground, and passed through a 200-mesh sieve. Subsequently, the tablets were compressed at 15 MPa for 15 min to obtain two types of monolayer tablets. The effect of different diluent dosages on tablet hardness was investigated, and the results are shown in the appendix. Figure 5 (a) and 5(b). It can be seen that the bilayer sheet has higher hardness with the same amount of diluent.

Claims

1. An ionic liquid / deep eutectic solvent @ cyclodextrin-derivatized cellulose double-layer tablet, characterized in that the cyclodextrin and the ionic liquid / deep eutectic solvent are combined in the form of an inclusion complex and then tabletted with derivatized cellulose as a diluent / binder, the specific preparation steps being as follows: (1) a saturated aqueous solution of cyclodextrin at 60℃ is prepared, and then ionic liquid or deep eutectic solvent is added, and the mixture is stirred thoroughly at 60℃ for a certain period of time, and then stored at 4℃ for 24 h; finally, the mixture is suction filtered and washed with deionized water three times, and then vacuum dried, to obtain two kinds of inclusion complexes, ionic liquid @ cyclodextrin and deep eutectic solvent @ cyclodextrin, respectively; (2) the two kinds of inclusion complexes in (1) are mixed with derivatized cellulose respectively, and then ground thoroughly and passed through a 200-mesh sieve; (3) the sieved ionic liquid @ cyclodextrin-derivatized cellulose mixed powder is laid flat on the bottom surface of a stainless steel tabletting die, and then the sieved deep eutectic solvent @ cyclodextrin-derivatized cellulose mixed powder is laid flat on the upper layer, and then pressure-formed to obtain ionic liquid / deep eutectic solvent @ cyclodextrin-derivatized cellulose composite double-layer tablets. The ionic liquid / deep eutectic solvent is immobilized in the cavity of the cyclodextrin in the form of an inclusion complex, and the preparation method used is the saturated aqueous solution method. The cyclodextrin is β-cyclodextrin. The ionic liquid is 1-aminomethyl-3-methylimidazolium bromide, and the deep eutectic solvent is composed of choline chloride as a hydrogen bond acceptor and acetic acid as a hydrogen bond donor.

2. The ionic liquid / hy-dro-tro-pes@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, characterized by, The diluent / binder used is derivatized cellulose, including ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose.

3. The ionic liquid / hy-drotemic solvent@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, characterized by, In the preparation of the inclusion complex, the molar ratio of ionic liquid / deep eutectic solvent to cyclodextrin is 1:1 to 5:

1.

4. The ionic liquid / hy-dro-tro-pes@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, characterized by, The mass ratio of ionic liquid / deep eutectic solvent @ cyclodextrin inclusion complex to diluent / binder is 0.025 g:0.125 g to 0.125 g:0.025 g.

5. The ionic liquid / hy-dro-tro-pes@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, characterized by, The compressed composite tablet has a double-layer structure; one side is ionic liquid @ cyclodextrin-derivatized cellulose, and the other side is deep eutectic solvent @ cyclodextrin-derivatized cellulose.

6. The ionic liquid / hy-dro-tro-pes@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, wherein The tabletting pressure ranges from 5 to 15 MPa.

7. The ionic liquid / hy-drotemic solvent@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, characterized by, The tabletting time ranges from 5 to 60 min.

8. The ionic liquid / hy-drotemic solvent@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, characterized by, ​ 9. The ionic liquid / hy-dro-tro-pes@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, characterized by, ​ 10. The ionic liquid / hy-dro-tro-pes@cyclodextrin-derivatized cellulose bilayer tablet according to claim 1, characterized by, ​

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