Castor oil-based ionic liquid and preparation and application thereof

Abstract

The application discloses a castor oil-based ionic liquid and a preparation and application thereof. The castor oil-based ionic liquid is prepared by using castor oil and chloroethyl isocyanate as raw materials, heating and reacting in an organic solvent to prepare chloroethyl aminocarbonic acid castor oil ester in one step; then the chloroethyl aminocarbonic acid castor oil ester and a tertiary amine compound are mixed in the organic solvent, and heated and reacted under inert gas protection to obtain the castor oil-based ionic liquid in one step. The castor oil-based ionic liquid is a brand-new ionic liquid, has the characteristics of easy availability of raw materials, low price, renewability, simple preparation method, mild reaction condition, high atom economy, high yield, green environmental protection and excellent antibacterial performance, and is suitable for industrial popularization and application.

Description

TECHNICAL FIELD

[0001] The present application relates to an ionic liquid and its preparation and application, in particular a castor oil-based ionic liquid and its preparation and application. BACKGROUND

[0002] Ionic liquid, also known as room temperature molten salt, as the name implies, is a kind of molten salt which is in liquid state at room temperature. Ordinary salt needs to reach a certain temperature to change from solid to liquid, or be dissolved in water to be in liquid state at room temperature, while ionic liquid is different. Pure ionic liquid is in liquid state at room temperature.

[0003] The research direction of ionic liquid has developed from electrochemistry to organic synthesis, inorganic synthesis, and now has expanded to various chemical fields, and its types have also expanded from halide hydrochloride to imidazole, followed by pyridine, quaternary ammonium salt ionic liquid, etc. Today, various functional ionic liquids have also been explored. Ionic liquids have been widely used in new energy, synthesis processing, extraction separation, electrochemistry, nanomaterials, and functional materials, etc. The reason is that ionic liquids have outstanding physical and chemical properties, and are the most promising green and environmentally friendly reaction medium and ideal catalytic system.

[0004] At present, due to the overuse of antibiotics, bacterial drug resistance is increasing, and the threat of bacterial infection is increasing. At the same time, in order to alleviate the resource waste and environmental pollution caused by petrochemical energy polymers, and meet the requirements of green and sustainable development, the research and development of antibacterial bio-based medical materials has become an urgent need. The structure-adjustable ionic liquid antibacterial agent opens up a new direction for inhibiting the evolution of bacterial drug resistance. The cationic group of ionic liquid has electrostatic adsorption with the negative charge on the bacterial cell membrane, and then its hydrophobic long alkyl chain can pierce the phospholipid bilayer of the bacterial cell, thereby killing the bacteria.

[0005] Castor oil has three flexible long alkyl chains on the molecular chain, and each chain has a strong active hydroxyl group, which creates conditions for the preparation of ternary castor oil ionic liquid. At the same time, the carbon-carbon double bond structure on each chain can also be used for the preparation of cross-linked polymers through thiol-ene click chemistry with thiol monomers. The introduction of ammonium salt cationic group can greatly reduce the melting point and viscosity, improve the flowability, and enhance the antibacterial performance. Therefore, the castor oil-based ionic liquid prepared by using castor oil as the matrix is expected to become a flexible antibacterial material production raw material, and also can become a potential functional plasticizer substitute.

[0006] However, there are few reports on castor oil-based ionic liquids. Patent CN102776053A discloses a composite extreme pressure anti-wear agent containing A ionic liquid and B ionic liquid. The A ionic liquid is 1-(ethyl ricinoleate)-3-methyl imidazole tetrafluoroborate, which is prepared from ricinoleic acid. However, the use of the ionic liquid is mainly as an anti-wear agent, and the use and structure are relatively single. In order to expand the types of castor oil-based ionic liquids and increase their functions and uses, it is necessary to further explore and research castor oil-based ionic liquids.

[0007] Meanwhile, the preparation of the ricinoleic acid ionic liquid in the above-mentioned patent is by one-step method from ricinoleic acid and imidazole phosphate as raw materials. Although the process steps are less, the reaction needs to be carried out at high temperature and high pressure, and the reaction conditions are relatively harsh, which is not suitable for industrialization and popularization and application.

[0008] Based on the above reasons, the researchers of the present application have modified and researched the structure, function and preparation method of castor oil-based ionic liquids. SUMMARY

[0009] In order to solve the above technical problems, the present application provides a castor oil-based ionic liquid and its preparation and application. The castor oil-based ionic liquid of the present application is a brand-new ionic liquid, which has the characteristics of easy-to-obtain raw materials, low price, renewability, simple preparation method, mild reaction conditions, high atom economy, high yield, green environmental protection and excellent antibacterial performance, and is suitable for industrialization and popularization and application.

[0010] The technical scheme of the present application is as follows:

[0011] A castor oil-based ionic liquid, whose chemical structural formula is shown as formula (I):

[0012]

[0013] In the formula, R' is an organic group containing a quaternary amine salt cation group.

[0014] As a preferred, the aforementioned castor oil-based ionic liquid, the R' is a pyridine quaternary ammonium salt organic group, an imidazole quaternary ammonium salt organic group or a tributylamine quaternary ammonium salt organic group.

[0015] A preparation method of the aforementioned castor oil-based ionic liquid, comprising the following steps:

[0016] (1) taking castor oil and chloroethyl isocyanate as raw materials, heating and reacting in an organic solvent to prepare chloroethyl aminomethylate castor oil ester by one-step method, and the structure is shown as formula (II);

[0017]

[0018] (2) mixing chloroethyl carbamic castor oil ester and tertiary amine compound in organic solvent, heating and reacting under inert gas protection to obtain said castor oil-based ionic liquid by one-step method.

[0019] As preferred, in the preparation method of the aforementioned castor oil-based ionic liquid, the molar ratio of castor oil to chloroethyl isocyanate in step (1) is 1:3-5; the organic solvent is one or a mixture of any number of dichloromethane, acetic acid, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide; the reaction temperature is 50-150℃, and the reaction time is 24-72h.

[0020] As preferred, in the preparation method of the aforementioned castor oil-based ionic liquid, the inert gas in step (2) is one of nitrogen, argon or helium; the molar ratio of chloroethyl carbamic castor oil ester to tertiary amine compound is 1:3-5; the organic solvent is one or a mixture of any number of acetonitrile, ethanol, acetone, tetrahydrofuran or 1,4-dioxane; the reaction temperature is 50-150℃, and the reaction time is 24-72h.

[0021] As preferred, in the preparation method of the aforementioned castor oil-based ionic liquid, the structure of the tertiary amine compound is as follows:

[0022]

[0023] A thermosetting sulfur-containing resin containing castor oil-based ionic liquid, which is prepared by thiol-ene click polymerization of the aforementioned castor oil-based ionic liquid and a bio-based aromatic carbonate-containing polymerizable polyene monomer represented by formula (III) with a thiol monomer;

[0024]

[0025] As preferred, in the aforementioned thermosetting sulfur-containing resin containing castor oil-based ionic liquid, the thiol monomer is one or a combination of any number of 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, bis(3-mercaptopropionic acid) ethylene glycol, trimethylolpropane tris(3-mercaptopropionate), tetra(3-mercaptoacetic acid) pentaerythritol ester or tetra(3-mercaptopropionic acid) pentaerythritol ester.

[0026] As preferred, the aforementioned thermosetting sulfur-containing resin containing the castor oil-based ionic liquid is prepared by the following method: first, melt the castor oil-based ionic liquid and the polymerizable polyene monomer at 100-120°C, then add the mercaptan monomer, and then add 1-3wt% of the photoinitiator 1173 or 2,2-dimethoxy-2-phenylacetophenone, stir uniformly, and then cure under a UV lamp for 10-45min, and then heat cure at 70-140°C for 0.5-12h.

[0027] As preferred, the aforementioned thermosetting sulfur-containing resin containing the castor oil-based ionic liquid, the molar ratio of the total amount of C=C double bonds in the castor oil-based ionic liquid and the polymerizable polyene monomer to the -SH functional groups in the mercaptan monomer is 1:1, and the mixing mass ratio of the castor oil-based ionic liquid and the polymerizable polyene monomer is any ratio, such as 2:8 or 1:9.

[0028] A polylactic acid material containing a castor oil-based ionic liquid is prepared by the following method:

[0029] (1) Dry the polylactic acid raw material in a constant temperature drying oven at 60-80°C for 24-48h;

[0030] (2) Mix the dried polylactic acid obtained in step (1) and the castor oil-based ionic liquid of claim 1 or 2 in a ratio of phr:phr=100:5-30, and mix uniformly;

[0031] (3) Add the mixture of step (2) to an extruder, and melt blend in the extruder at 130-185°C;

[0032] (4) Add the blend obtained in step (3) to an injection molding machine, and injection mold at 160-185°C.

[0033] Advantages of the present application:

[0034] 1. The raw material of the ionic liquid of the present application is selected from bio-based castor oil, which is first reacted with chloroethyl isocyanate to prepare chloroethyl carbamate castor oil ester, and then reacted with a nitrogen-containing compound with a specific structure to prepare a castor oil ionic liquid containing carbon-carbon double bonds and quaternary ammonium salt cation groups by one-pot method. The raw material is easy to obtain, low in price, renewable, simple in preparation method, mild in reaction conditions, high in atomic economy, high in yield, green and environmentally friendly, and excellent in antibacterial performance, which is suitable for industrialization and popularization and application.

[0035] 2、The carboxylate structure is contained in the castor oil-based ionic liquid of the application, when the castor oil-based ionic liquid is used to prepare a thermosetting polymer, a degradable thermosetting polymer can be obtained. When the castor oil-based ionic liquid is mixed with polylactic acid, a polylactic acid material containing the castor oil-based ionic liquid can be prepared. The polylactic acid material not only has excellent antibacterial performance, but also achieves the purpose of toughening modification of polylactic acid. The polylactic acid material containing the castor oil-based ionic liquid has better toughness.

[0036] 3, The castor oil-based ionic liquid and the bio-based aromatic carbonate-containing polymerizable polyene monomer are used to prepare a thermosetting resin, the rigid chain segment is introduced, and a series of cross-linked network structure controllable and performance adjustable castor oil-based sulfur-containing cross-linked thermosetting resin is prepared through sulfur-based-alkene click chemistry and a multi-functional thiol monomer. The flexible resin has high cross-linking degree, good light transmittance, good mechanical properties and adjustable glass transition temperature. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the castor oil-based methyl imidazole ionic liquid monomer prepared in Example 1 of the application.

[0038] Figure 2 The nuclear magnetic resonance carbon spectrum of the castor oil-based methyl imidazole ionic liquid monomer prepared in Example 1 of the application.

[0039] Figure 3 The nuclear magnetic resonance hydrogen spectrum of the castor oil-based vinyl imidazole ionic liquid monomer prepared in Example 4 of the application.

[0040] Figure 4 The nuclear magnetic resonance carbon spectrum of the castor oil-based vinyl imidazole ionic liquid monomer prepared in Example 4 of the application.

[0041] Figure 5 The nuclear magnetic resonance hydrogen spectrum of the castor oil-based allyl imidazole ionic liquid monomer prepared in Example 7 of the application.

[0042] Figure 6 The nuclear magnetic resonance carbon spectrum of the castor oil-based allyl imidazole ionic liquid monomer prepared in Example 7 of the application.

[0043] Figure 7 The tensile test of the thermosetting sulfur-containing resin prepared in Example 10 of the application.

[0044] Figure 8 The antibacterial test of the thermosetting sulfur-containing resin prepared in Example 10 of the application.

[0045] Figure 9 The tensile test of the polylactic acid material prepared in Example 13 of the application.

[0046] Figure 10Antibacterial test of the polylactic acid material prepared for Example 13 of the present application. DETAILED DESCRIPTION

[0047] The present application is further described below in conjunction with examples, but is not limited to the basis of the examples.

[0048] Embodiments of the present application

[0049] Example 1

[0050]

[0051] A single-necked flask was charged with castor oil (140.7 g), chloroethyl isocyanate (57.1 g), and 250 mL of dichloromethane was added to dissolve, and refluxed at 80°C for 72 hours. After the reaction was completed, purification by distillation was performed to obtain chloroethyl carbamic acid castor oil ester with a yield of 97.6%.

[0052] Then, a three-necked flask was charged with chloroethyl carbamic acid castor oil ester (100.0 g), N-methyl imidazole (40.0 g), and 200 mL of acetonitrile was added, and refluxed at 85°C for 24 hours under a nitrogen atmosphere. After the reaction, solvent washing, filtration, and purification by distillation were performed to obtain castor oil-based methyl imidazole ionic liquid with a yield of 95.2%.

[0053] Example 2

[0054] A single-necked flask was charged with castor oil and chloroethyl isocyanate at a molar ratio of 1:5, and 250 mL of N,N-dimethylacetamide was added to dissolve, and refluxed at 150°C for 24 hours. After the reaction was completed, purification by distillation was performed to obtain chloroethyl carbamic acid castor oil ester.

[0055] Then, a three-necked flask was charged with chloroethyl carbamic acid castor oil ester and N-methyl imidazole at a molar ratio of 1:5, and 200 mL of tetrahydrofuran was added, and refluxed at 150°C for 24 hours under a helium atmosphere. After the reaction, solvent washing, filtration, and purification by distillation were performed to obtain castor oil-based methyl imidazole ionic liquid.

[0056] Example 3

[0057] A single-necked flask was charged with castor oil and chloroethyl isocyanate at a molar ratio of 1:3, and 250 mL of ethanol was added to dissolve, and refluxed at 50°C for 72 hours. After the reaction was completed, purification by distillation was performed to obtain chloroethyl carbamic acid castor oil ester.

[0058] Then, a three-necked flask was charged with chloroethyl carbamic acid castor oil ester and N-methyl imidazole at a molar ratio of 1:3, and 200 mL of acetone was added, and refluxed at 50°C for 72 hours under an argon atmosphere. After the reaction, solvent washing, filtration, and purification by distillation were performed to obtain castor oil-based methyl imidazole ionic liquid.

[0059] Example 4

[0060]

[0061] Into a single-necked flask, castor oil (140.7 g) and chloroethyl isocyanate (57.1 g) were added, and 250 mL of dichloromethane was added to dissolve the mixture. The reaction was carried out at 80°C for 72 hours. After the reaction, purification by distillation was carried out to obtain chloroethyl carbamic acid castor oil ester at a yield of 97.6%.

[0062] Into a three-necked flask, chloroethyl carbamic acid castor oil ester (100.0 g) and N-vinylimidazole (40.0 g) were added, and 200 mL of acetonitrile was added to dissolve the mixture. The reaction was carried out at 85°C for 24 hours under a nitrogen atmosphere. After the reaction, purification by solvent washing, filtration, and distillation was carried out to obtain castor oil-based vinyl imidazole ionic liquid at a yield of 99.5%.

[0063] Example 5

[0064] Into a single-necked flask, castor oil and chloroethyl isocyanate were added at a molar ratio of 1:5, and 250 mL of N,N-dimethylacetamide was added to dissolve the mixture. The reaction was carried out at 150°C for 24 hours. After the reaction, purification by distillation was carried out to obtain chloroethyl carbamic acid castor oil ester.

[0065] Into a three-necked flask, chloroethyl carbamic acid castor oil ester and N-vinylimidazole were added at a molar ratio of 1:5, and 200 mL of tetrahydrofuran was added to dissolve the mixture. The reaction was carried out at 150°C for 24 hours under a helium atmosphere. After the reaction, purification by solvent washing, filtration, and distillation was carried out to obtain castor oil-based vinyl imidazole ionic liquid.

[0066] Example 6

[0067] Into a single-necked flask, castor oil and chloroethyl isocyanate were added at a molar ratio of 1:3, and 250 mL of ethanol was added to dissolve the mixture. The reaction was carried out at 50°C for 72 hours. After the reaction, purification by distillation was carried out to obtain chloroethyl carbamic acid castor oil ester.

[0068] Into a three-necked flask, chloroethyl carbamic acid castor oil ester and N-vinylimidazole were added at a molar ratio of 1:3, and 200 mL of acetone was added to dissolve the mixture. The reaction was carried out at 50°C for 72 hours under an argon atmosphere. After the reaction, purification by solvent washing, filtration, and distillation was carried out to obtain castor oil-based vinyl imidazole ionic liquid.

[0069] Example 7

[0070]

[0071] A three-necked flask was charged with castor oil (100.0 g), chloroethyl isocyanate (40.0 g), and 200 mL of acetonitrile. The reaction was carried out under a nitrogen atmosphere at 85°C for 24 hours. After the reaction, the solvent was washed, filtered, and distilled to obtain castor oil-based allyl imidazole ionic liquid with a yield of 99.8%.

[0072] A three-necked flask was charged with castor oil (100.0 g), chloroethyl isocyanate (40.0 g), and 200 mL of acetonitrile. The reaction was carried out under a nitrogen atmosphere at 85°C for 24 hours. After the reaction, the solvent was washed, filtered, and distilled to obtain castor oil-based allyl imidazole ionic liquid with a yield of 99.8%.

[0073] Example 8

[0074] A single-necked flask was charged with castor oil (100.0 g) and chloroethyl isocyanate (40.0 g) at a molar ratio of 1:5, and 250 mL of N,N-dimethylacetamide was added for dissolution. The reaction was carried out under reflux at 150°C for 24 hours. After the reaction, distillation was performed to obtain chloroethyl carbamic acid castor oil ester.

[0075] A three-necked flask was charged with castor oil (100.0 g), chloroethyl isocyanate (40.0 g), and 200 mL of acetonitrile. The reaction was carried out under a nitrogen atmosphere at 85°C for 24 hours. After the reaction, the solvent was washed, filtered, and distilled to obtain castor oil-based allyl imidazole ionic liquid with a yield of 99.8%.

[0076] Example 9

[0077] A single-necked flask was charged with castor oil (100.0 g) and chloroethyl isocyanate (40.0 g) at a molar ratio of 1:5, and 250 mL of N,N-dimethylacetamide was added for dissolution. The reaction was carried out under reflux at 150°C for 24 hours. After the reaction, distillation was performed to obtain chloroethyl carbamic acid castor oil ester.

[0078] A three-necked flask was charged with castor oil (100.0 g), chloroethyl isocyanate (40.0 g), and 200 mL of acetonitrile. The reaction was carried out under a nitrogen atmosphere at 85°C for 24 hours. After the reaction, the solvent was washed, filtered, and distilled to obtain castor oil-based allyl imidazole ionic liquid with a yield of 99.8%.

[0079] Example 10

[0080] Step: Castor oil-based methyl imidazole ionic liquid monomer of Example 1 and bio-based aromatic carbonate-structured polymerizable polyene monomer were completely melted at 110°C, and a multifunctional thiol monomer and 1.5 wt% of 2,2-dimethoxy-2-phenylacetophenone were added and stirred uniformly. The mixture was poured into a glass culture dish, and then crosslinked under a UV lamp with a wavelength of 365 nm for 15 min, followed by thermal curing in an oven at 80°C for 12 hours to obtain a transparent film.

[0081] The resin is named as Pa i b m -nSH, wherein P represents the antibacterial resin polymer, a represents the castor oil-based methyl imidazole ionic liquid, i represents the addition amount (unit g) of the castor oil-based methyl imidazole ionic liquid, b represents the bio-based aromatic carbonate-structure-containing polymerizable polyene monomer, m represents the addition amount (unit g) thereof, n is the number of functionality of the thiol monomer, and SH represents the thiol. The thermal properties of the obtained thermosetting resin are shown in Table 1, the mechanical properties are shown in Table 2, and the antibacterial properties are shown in Table 3.

[0082] Table 1 Thermal properties of the thermosetting resin prepared in Example 10

[0083]

[0084] Table 2 Mechanical properties of the thermosetting resin prepared in Example 10

[0085] Number Tensile strength (MPa) Elongation at break (%) Pa1b9-3SH 0.6±0.1 490.9±9.6 Pa1b9-3.5SH 0.7±0.01 354.3±8.0 Pa1b9-4SH 9.42±0.71 279.9±24.8

[0086] Table 3 Antibacterial properties of the thermosetting resin prepared in Example 10

[0087] Number E. coli (%) S. aureus (%) Pa1b9-3SH 88.0±3.2 98.8±0.2 Pa1b9-3.5SH 99.9±0.0 98.6±0.4 Pa1b9-4SH 99.9±0.0 98.2±0.4

[0088] Example 11

[0089] Step: The castor oil-based methyl imidazole ionic liquid monomer and the bio-based aromatic carbonate-structure-containing polymerizable polyene monomer of Example 1 were completely melted at 100°C, and a multi-functionality thiol monomer and 1wt% of 2,2-dimethoxy-2-phenylacetophenone were added and stirred uniformly, the molar ratio of the total amount of C=C double bonds in the castor oil-based ionic liquid and the polymerizable polyene monomer to the -SH functional groups in the thiol monomer was 1:1, the mixture was poured into a glass culture dish, then crosslinked under a UV lamp with a wavelength of 365nm for 10min, and then heat cured in an oven at 70°C for 10 hours to obtain a transparent film.

[0090] Example 12

[0091] Step: The castor oil-based methyl imidazole ionic liquid monomer and the bio-based aromatic carbonate-structure-containing polymerizable polyene monomer of Example 1 were completely melted at 120°C, and a multi-functionality thiol monomer and 3wt% of a photoinitiator 1173 were added and stirred uniformly, the molar ratio of the total amount of C=C double bonds in the castor oil-based ionic liquid and the polymerizable polyene monomer to the -SH functional groups in the thiol monomer was 1:1, the mixture was poured into a glass culture dish, then crosslinked under a UV lamp with a wavelength of 365nm for 45min, and then heat cured in an oven at 140°C for 0.5 hours to obtain a transparent film.

[0092] Example 13

[0093] Table 4 Formulation table of antibacterial polylactic acid material

[0094] Sample PLA / phr Ionic liquid / phr PLA 100 0 PLA / 5CAIL 100 5 PLA / 10CAIL 100 10 PLA / 15CAIL 100 15 PLA / 20CAIL 100 20

[0095] The PLA granules were dried in a constant temperature drying oven at 70℃ for 36 hours. Then, castor oil-based allyl imidazole ionic liquid (CAIL for short) and PLA were weighed according to the proportions in Table 4, mixed uniformly, and then mixed in a micro twin-screw extruder (three-stage temperature of 150, 160 and 170℃), and then injection molded in a micro injection molding machine (heating temperature of 170℃ and mold temperature of 45℃) to prepare the antibacterial polylactic acid material.

[0096] Example 14

[0097] The PLA granules were dried in a constant temperature drying oven at 80℃ for 24 hours. Then, PLA and castor oil-based methyl imidazole ionic liquid were weighed according to a certain proportion (100:30, phr:phr), mixed uniformly, and then mixed in a micro twin-screw extruder (three-stage temperature of 155, 165 and 175℃), and then injection molded in a micro injection molding machine (heating temperature of 175℃ and mold temperature of 45℃) to prepare the antibacterial polylactic acid material.

[0098] Example 15

[0099] The PLA granules were dried in a constant temperature drying oven at 70℃ for 36 hours. Then, PLA and castor oil-based vinyl imidazole ionic liquid were weighed according to a certain proportion (100:20, phr:phr), mixed uniformly, and then mixed in a micro twin-screw extruder (three-stage temperature of 145, 160 and 175℃), and then injection molded in a micro injection molding machine (heating temperature of 175℃ and mold temperature of 45℃) to prepare the antibacterial polylactic acid material.

[0100] Example 16

[0101] The PLA granules were dried in a constant temperature drying oven at 60℃ for 48 hours. Then, PLA and castor oil-based pyridine ionic liquid were weighed according to a certain proportion (100:5, phr:phr), mixed uniformly, and then mixed in a micro twin-screw extruder (three-stage temperature of 145, 155 and 165℃), and then injection molded in a micro injection molding machine (heating temperature of 165℃ and mold temperature of 45℃) to prepare the antibacterial polylactic acid material.

[0102] The thermal performance, mechanical performance and antibacterial performance test results of the polylactic acid antibacterial material prepared in Example 13 are shown in Tables 5-7, respectively.

[0103] Table 5 Thermal properties of the antibacterial polylactic acid material prepared in Example 13

[0104]

[0105]

[0106] Table 6 Mechanical properties of the antibacterial polylactic acid material prepared in Example 13

[0107] Number Tensile strength (MPa) Elongation at break (%) PLA 64.0±0.3 8.9±0.7 PLA / 5CAIL 54.7±0.1 10.6±0.1 PLA / 10CAIL 37.3±1.3 14.1±0.5 PLA / 15CAIL 34.3±0.7 16.5±0.6 PLA / 20CAIL 27.0±3.0 26.6±1.1

[0108] Table 7 Antibacterial properties of the antibacterial polylactic acid material prepared in Example 13

[0109] Number E. coli (%) S. aureus (%) PLA / 5CAIL 81.0±0.5 98.3±0.1 PLA / 10CAIL 88.5±0.9 98.8±0.1 PLA / 15CAIL 97.1±1.2 99.3±0.1 PLA / 20CAIL 98.2±0.1 99.7±0.1

[0110] The above merely describes the preferred embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, according to the technical scheme and inventive concept of the present application, should be covered within the protection scope of the present application.

Claims

1. A castor oil-based ionic liquid, characterized in that, Its chemical structural formula is shown in formula (I): Formula (I); Where R' is , or One of them.

2. A method for preparing a castor oil-based ionic liquid according to claim 1, characterized in that, Includes the following steps: (1) Using castor oil and chloroethyl isocyanate as raw materials, the reaction is carried out in an organic solvent by heating to prepare chloroethyl carbamate castor oil ester in one step, the structure of which is shown in formula (II). Equation (II); (2) The castor oil-based ionic liquid is prepared by mixing chloroethyl carbamate castor oil ester and tertiary amine compound in an organic solvent and heating under inert gas protection. The structure of the tertiary amine compound is as follows: , or .

3. The method for preparing the castor oil-based ionic liquid according to claim 2, characterized in that: In step (1), the molar ratio of castor oil to chloroethyl isocyanate is 1:3-5; the organic solvent is one or a mixture of any of the following: dichloromethane, acetic acid, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide; the reaction temperature is 50-150℃ and the reaction time is 24-72h.

4. The method for preparing the castor oil-based ionic liquid according to claim 2, characterized in that: The inert gas in step (2) is one of nitrogen, argon or helium; the molar ratio of chloroethylcarbamate castor oil ester to tertiary amine compound is 1:3-5; the organic solvent is one or a mixture of several of acetonitrile, ethanol, acetone, tetrahydrofuran or 1,4-dioxane; the reaction temperature is 50-150℃ and the reaction time is 24-72h.

5. A thermosetting sulfur-containing resin containing castor oil-based ionic liquid, characterized in that: The product is prepared by mercapto-olefin click polymerization of the castor oil-based ionic liquid of claim 1 and the bio-based aromatic carbonate-containing polymerizable polyolefin monomer shown in formula (III) with a thiol monomer. Equation (III); The specific preparation method is as follows: First, melt the castor oil-based ionic liquid and polymerizable polyolefin monomer at 100-120℃, then add the thiol monomer, and then add 1-3wt% of photoinitiator 1173 or 2,2-dimethoxy-2-phenylacetophenone. After stirring evenly, cure under ultraviolet light for 10-45 minutes, and then heat cure at 70-140℃ for 0.5-12 hours to obtain the final product.

6. The thermosetting sulfur-containing resin containing castor oil-based ionic liquid according to claim 5, characterized in that: The thiol monomer is one or any combination of 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, bis(3-mercaptopropionic acid) ethylene glycol, trimethylolpropane tri(3-mercaptopropionic acid) tri(3-mercaptopropionic acid) pentaerythritol ester or pentaerythritol tetra(3-mercaptopropionic acid) pentaerythritol ester.

7. The thermosetting sulfur-containing resin containing castor oil-based ionic liquid according to claim 5, characterized in that: The molar ratio of the total C=C double bonds in the castor oil-based ionic liquid and polymerizable polyolefin monomer to the -SH functional groups in the thiol monomer is 1:

1.

8. A polylactic acid material containing a castor oil-based ionic liquid, characterized in that, Prepared by the following method: (1) Dry the polylactic acid raw material in a constant temperature drying oven at 60-80℃ for 24-48 hours; (2) The dried polylactic acid obtained in step (1) and the castor oil-based ionic liquid of claim 1 are mixed in a ratio of phr: phr = 100: 5-30 and then mixed evenly. (3) Add the mixture from step (2) into an extruder and melt-blend it in the extruder at 130-185°C; (4) Add the blend obtained in step (3) into the injection molding machine and injection mold it at 160-185℃.

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