阅读说明：本技术 一种二氧化碳基离子型聚脲及其制备方法与应用 (Carbon dioxide-based ionic polyurea and preparation method and application thereof ) 是由 欧旭 周莹杰 严锋 朱子鸣 于 2021-06-29 设计创作，主要内容包括：本发明涉及一种二氧化碳基离子型聚脲及其制备方法与应用。本发明通过以双胺功能化的离子液体和二氧化碳作为单体,在二氧化碳压力为0.1～20MPa和60～250℃下,聚合制成二氧化碳基离子型聚脲。本发明通过调控离子液体单体结构、阴离子类型等,赋予离子型聚脲丰富可调变的功能性。同时,聚合物骨架中大量的二氧化碳衍生极性官能团与丰富的阳离子基团,使得该离子型聚脲具有良好的离子传导率和生物抗菌性。这类二氧化碳基离子型聚脲的制备简单,绿色环保,不仅实现了二氧化碳的资源化利用,在柔性电子器件及生物医药领域具有潜在的应用前景。(The invention relates to carbon dioxide-based ionic polyurea and a preparation method and application thereof. The invention prepares the carbon dioxide-based ionic polyurea by taking diamine functionalized ionic liquid and carbon dioxide as monomers and polymerizing the monomers under the pressure of 0.1-20 MPa of the carbon dioxide and the temperature of 60-250 ℃. The ionic polyurea is endowed with rich and adjustable functionality by regulating and controlling the ionic liquid monomer structure, the anion type and the like. Meanwhile, a large amount of carbon dioxide derived polar functional groups and abundant cationic groups in the polymer skeleton enable the ionic polyurea to have good ionic conductivity and biological antibacterial property. The preparation of the carbon dioxide-based ionic polyurea is simple, green and environment-friendly, realizes resource utilization of carbon dioxide, and has potential application prospect in the fields of flexible electronic devices and biomedicine.)

1. The preparation method of the carbon dioxide-based ionic polyurea is characterized in that diamine functionalized ionic liquid and carbon dioxide are used as monomers to be polymerized to prepare the carbon dioxide-based ionic polyurea.

2. The method for preparing carbon dioxide-based ionic polyurea according to claim 1, wherein the cation in the diamine-functionalized ionic liquid is one or more selected from imidazole diamine ions, pyridine diamine ions and quaternary ammonium diamine ions,

wherein, the structure of the imidazole diamine ion is shown as follows:

the structure of the pyridine diamine ion is shown as follows:

the structure of quaternary ammonium diamine ions is shown as follows:

n in the structural formula represents the number of connecting C, n is a positive integer, and the selected range is 2-18.

3. The method for preparing carbon dioxide-based ionic polyurea according to claim 1, wherein the anion in the diamine-functionalized ionic liquid is selected from one or a mixture of chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion or bistrifluoromethylsulfonimide ion.

4. The method of claim 1, wherein the polymerization reaction is carried out in the presence of an organic or inorganic catalyst.

5. The method for preparing carbon dioxide-based ionic polyurea according to claim 4, wherein the organic catalyst is selected from one or more of 4-methyl choline oxide, triazabicyclo, diazabicyclo and triethylamine;

the inorganic catalyst is one or more selected from potassium carbonate, cesium carbonate, potassium hydroxide, cesium hydroxide monohydrate or potassium tert-butoxide.

6. The method for preparing carbon dioxide-based ionic polyurea of claim 4, wherein when the polymerization reaction is carried out in the presence of an organic catalyst or an inorganic catalyst, the molar content of the organic catalyst or the inorganic catalyst is 0 to 20 mol% but not 0 mol% of the diamine ionic liquid.

7. The method for preparing carbon dioxide-based ionic polyurea according to claim 1, wherein the polymerization conditions are as follows: reacting for 2-24 h under the pressure of 0.1-20 MPa of carbon dioxide and at the temperature of 60-250 ℃.

8. The method for preparing carbon dioxide-based ionic polyurea according to claim 1, comprising the following steps:

(1) selecting a proper organic solvent, and dissolving diamine-functionalized ionic liquid into a solution of 0.1-2 mol/L;

(2) adding an organic catalyst or an inorganic catalyst with the molar weight of 0-20 mol% of ionic liquid into the diamine ionic liquid solution prepared in the reaction step (1), and performing ultrasonic treatment to obtain a precursor solution which is uniformly mixed;

(3) and (3) injecting the precursor solution prepared in the reaction step (2) into a reaction kettle, purging with carbon dioxide to remove air, raising the temperature to 60-250 ℃, introducing 0.1-20 MPa of carbon dioxide, and reacting for 2-24 hours to obtain the carbon dioxide-based ionic polyurea.

9. A carbon dioxide-based ionic polyurea obtained on the basis of the preparation process according to any one of claims 1 to 8.

10. Use of the carbon dioxide-based ionic polyurea according to claim 9, wherein the carbon dioxide-based ionic polyurea is used as a functional material in the field of flexible electronics and/or biomedicine.

Technical Field

The invention belongs to the field of polymer synthesis, and particularly relates to carbon dioxide-based ionic polyurea and a preparation method and application thereof.

Background

From the viewpoint of environmental protection, carbon dioxide (CO)₂) Is the main component of the greenhouse effect and has serious influence on the ecological environment and the social development. From a green chemistry perspective, CO₂The carbon-based raw material is rich in reserves, low in price, non-toxic, renewable, green and environment-friendly. Over the last decades, CO has been developed₂Have been converted into a variety of high value-added chemical products such as methanol, urea, carbamic acid, cyclic carbonates, polycarbonates, polyurethanes, polyureas, and the like. At present, CO is mixed₂The polymer material with excellent conversion performance is CO₂One of the important routes for curing utilization. Among them, polyurea exhibits excellent wear resistance, oxidation resistance, corrosion resistance and thermal stability due to strong hydrogen bonding interaction between polymer chains thereof. The composite material has wide application in the fields of functional fibers, films, water-based coatings, thermoplastic plastics, thermoplastic elastomers, catalysts, templates, adsorbents and the like.

Compared with the traditional condensation polymerization method of isocyanate and diamine for preparing polyurea, CO₂The method directly used as a monomer polycondensation method avoids the use of toxic isocyanate, optimizes the operation and ensures that the whole synthesis path is more green and safer.

The ionic polymer has good potential application value in the fields of flexible electronic devices and biomedicine due to rich ionic groups in the polymer skeleton. However, at present, CO₂Ionic polyureas have been reported. Thus to CO₂The polyurea is subjected to ionization modification, so that the application value and the application range of the polyurea can be further widened.

Disclosure of Invention

The invention aims to provide a carbon dioxide-based ionic polyurea and a preparation method and application thereof.

The purpose of the invention can be realized by the following technical scheme:

the invention provides a preparation method of carbon dioxide-based ionic polyurea, which takes diamine functionalized ionic liquid and carbon dioxide as monomers to prepare the carbon dioxide-based ionic polyurea through polymerization.

In one embodiment of the invention, the cation in the diamine-functionalized ionic liquid is one or a mixture of more of imidazole diamine ions, pyridine diamine ions or quaternary ammonium diamine ions,

wherein, the structure of the imidazole diamine ion is shown as follows:

the structure of the pyridine diamine ion is shown as follows:

the structure of quaternary ammonium diamine ions is shown as follows:

n in the structural formula represents the number of connecting C, n is a positive integer, and the selected range is 2-18.

In one embodiment of the present invention, the anion in the diamine-functionalized ionic liquid is selected from one or a mixture of chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion or bistrifluoromethylsulfonimide ion.

The structure of the triflate ion is shown below:

the structure of bis (trifluoromethyl) sulfonimide ion is shown as follows:

therefore, in one embodiment of the present invention, the diamine-functionalized ionic liquid is one or a mixture of imidazole diamine ionic liquid, pyridine diamine ionic liquid or quaternary ammonium diamine ionic liquid, a molecular structural formula of the diamine-functionalized ionic liquid is shown in fig. 1, a left side in fig. 1 is a cation type, a right side in fig. 1 is an anion type, X in a left side structure represents an anion, and may be selected from one or more of right side anions, n in the left side structure represents the number of connecting C, n is a positive integer, and a selected range is 2 to 18.

In one embodiment of the invention, the polymerization reaction takes place in the presence of an organic or inorganic catalyst.

In one embodiment of the invention, the organic catalyst is selected from one or more of 4-methyl choline oxide (MNO), Triazabicyclo (TBD), Diazabicyclo (DBU) or Triethylamine (TEA).

In one embodiment of the present invention, the inorganic catalyst is one or more selected from potassium carbonate, cesium carbonate, potassium hydroxide, cesium hydroxide monohydrate, or potassium tert-butoxide.

In one embodiment of the present invention, when the polymerization reaction is carried out in the presence of an organic catalyst or an inorganic catalyst, the organic catalyst or the inorganic catalyst is contained in an amount of 0 to 20 mol% but not 0 mol% based on the diamine ionic liquid.

The catalyst can also be omitted in the preparation of the carbon dioxide-based ionic polyurea.

In one embodiment of the present invention, the polymerization conditions are: reacting for 2-24 h under the pressure of 0.1-20 MPa of carbon dioxide and at the temperature of 60-250 ℃.

In one embodiment of the present invention, a method for preparing a carbon dioxide-based ionic polyurea includes the steps of:

(1) selecting a proper organic solvent, and dissolving diamine-functionalized ionic liquid into a solution of 0.1-2 mol/L;

(2) adding an organic catalyst or an inorganic catalyst with the molar weight of 0-20 mol% of ionic liquid into the diamine ionic liquid solution prepared in the reaction step (1), and performing ultrasonic treatment to obtain a precursor solution which is uniformly mixed;

(3) and (3) injecting the precursor solution prepared in the reaction step (2) into a reaction kettle, purging with carbon dioxide to remove air, raising the temperature to 60-250 ℃, introducing 0.1-20 MPa of carbon dioxide, and reacting for 2-24 hours to obtain the carbon dioxide-based ionic polyurea.

The invention also provides a carbon dioxide-based ionic polyurea obtained based on the preparation method. The carbon dioxide-based ionic polyurea has adjustable hydrophilicity and hydrophobicity; the carbon dioxide-based ionic polyurea realizes the solidification of carbon dioxide; the carbon dioxide-based ionic polyurea has better antibacterial property.

The invention also provides application of the carbon dioxide-based ionic polyurea obtained based on the preparation method, and the carbon dioxide-based ionic polyurea can be used as a functional material in the fields of flexible electronic devices and/or biomedicine.

The ionic polyurea is endowed with rich and adjustable functionality by regulating and controlling the ionic liquid monomer structure, the anion type and the like. Meanwhile, a large amount of carbon dioxide derived polar functional groups and abundant cationic groups in the polymer skeleton enable the ionic polyurea to have good ionic conductivity and biological antibacterial property. The preparation of the carbon dioxide-based ionic polyurea is simple, green and environment-friendly, realizes resource utilization of carbon dioxide, and has potential application prospect in the fields of flexible electronic devices and biomedicine.

Compared with the prior art, the invention has the following advantages:

(1) according to the carbon dioxide-based ionic polyurea prepared by the invention, carbon dioxide is used as a green monomer, so that the resource utilization of carbon dioxide is realized;

(2) compared with the traditional non-ionic polyurea, the carbon dioxide-based ionic polyurea prepared by the invention has the characteristics of an ionic polymer;

(3) the carbon dioxide-based ionic polyurea prepared by the method has better structure adjustability. When the anion/cation type of the ionic liquid is changed, the thermodynamic property, the mechanical property, the hydrophilic and hydrophobic property, the ionic conductivity and the antibacterial property of the carbon dioxide-based ionic polyurea can be regulated and controlled;

(4) the synthesis path of the carbon dioxide-based ionic polyurea abandons the use of toxic isocyanate, and the preparation method is simple, efficient, green and environment-friendly, conforms to the sustainable development concept, and has popularization and application values.

Drawings

FIG. 1 is a schematic diagram of the structure of a diamine-functionalized ionic liquid.

FIG. 2 is a hydrogen spectrum a and a carbon spectrum b of the carbon dioxide-based ionic polyurea prepared in example 1.

FIG. 3 is an infrared spectrum of the carbon dioxide-based ionic polyurea prepared in example 2.

FIG. 4 is a polymer film obtained by casting the carbon dioxide-based ionic polyurea prepared in example 2.

FIG. 5 shows the antibacterial properties of the carbon dioxide-based ionic polyurea prepared in example 1. Wherein (a) is a control group and (b) is an experimental group.

Detailed Description

The invention is described in detail below with reference to the figures and specific embodiments. It should be noted that the examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention. Further, it will be appreciated that those skilled in the art, upon reading the teachings of the present invention, may make insubstantial modifications and adaptations to the invention described above, and that such equivalents are within the scope of the claims appended hereto.

Example 1

0.87g of pyridine type diamine ionic liquid (1,1 '-bis (aminopropyl) -4, 4' -bipyridine bromide salt) was dissolved in 7mL of N, N-dimethylacetamide, and 20 mole fraction of triethylamine as an ionic liquid was added. Injecting the precursor solution into a reaction kettle, purging with carbon dioxide for 5min to remove oxygen, heating to 200 deg.C, and introducing 10MPa CO₂Stirring and reacting for 24 hours, washing the solid precipitate with ethyl acetate for multiple times and drying to obtain CO₂And (3) ionic polyurea.

FIG. 2 shows the above-mentioned pyridine type CO₂Corresponding characteristic peaks of the ion-based polyurea nuclear magnetic hydrogen spectrum and carbon spectrum prove that the pyridine type CO is successfully prepared₂And (3) ionic polyurea.

FIG. 5 shows the above-mentioned pyridine type CO₂The ion-based polyurea was tested for antibacterial properties. In particular to CO₂The ionic polyurea was prepared as a 1mg/mL PBS solution with 5 wt% dimethyl sulfoxide added as a co-solvent to improve solubility. The bacterial suspension was dropped into the prepared sample solution and incubated at 37 ℃ for 4 hours, and then 10. mu.L of the bacterial suspension was taken out, dropped onto an agar plate, and spread uniformly. After incubation in an incubator at 37 ℃ for 12h, the number of surviving bacterial colonies was recorded. Each set of tests was repeated 3 times and the antibacterial rate was calculated. Wherein a is a control group experiment, b is experimental group data, and bacterium E represents Escherichia coli.

The experimental result shows that the pyridine type CO₂The ion-based polyurea has good antibacterial activity to colibacillus and has potential application prospect in the field of biological medicine materials.

Example 2

0.50g of imidazole type diamine ionic liquid (1, 3-bis (aminoethyl) -2-methylimidazolium bromide) was dissolved in 7mL of N, N-dimethylacetamide, and 20 mole fraction of DBU as the ionic liquid was added. Injecting the precursor solution into a reaction kettle, purging with carbon dioxide for 5min to remove oxygen, heating to 200 deg.C, and introducing 10MPa CO₂Stirring and reacting for 24 hours, washing the solid precipitate with ethyl acetate for multiple times and drying to obtain CO₂And (3) ionic polyurea.

FIG. 3 shows the imidazole type CO₂The ion-based polyurea infrared spectrogram and the corresponding characteristic peak prove that the imidazole type CO is successfully prepared₂And (3) ionic polyurea.

FIG. 4 shows imidazole type CO₂An ionic polyurea film. Specifically, 0.10g of imidazole type CO₂Dissolving base ion type polyurea in 0.5mL dimethyl sulfoxide to obtain 0.2g/mL solution, spraying on clean glass plate, placing in 80 deg.C oven for 24 hr, and removing solvent to obtain imidazole type CO₂Radical ionPolyurea-type films.

The experimental result shows that the imidazole type CO₂The ionic polyurea has good film forming property and excellent machinability, and has potential application prospect in the field of polyurea coating.

Example 3

0.50g of imidazole type diamine ionic liquid (1, 3-bis (aminoethyl) -2-methylimidazolium tetrafluoroborate) was dissolved in 7mL of N, N-dimethylacetamide, and 20 mole fraction of DBU was added as the ionic liquid. Injecting the precursor solution into a reaction kettle, purging with carbon dioxide for 5min to remove oxygen, heating to 200 deg.C, and introducing 10MPa CO₂Stirring and reacting for 24 hours, washing the solid precipitate with ethyl acetate for multiple times and drying to obtain CO₂And (3) ionic polyurea.

Example 4

0.50g of imidazole type diamine ionic liquid (1, 3-bis (aminoethyl) -2-methylimidazolium bromide) was dissolved in 7mL of N, N-dimethylacetamide. Injecting the precursor solution into a reaction kettle, purging with carbon dioxide for 5min to remove oxygen, heating to 200 deg.C, and introducing 10MPa CO₂Stirring and reacting for 12h, washing the solid precipitate with ethyl acetate for multiple times and drying to obtain CO₂And (3) ionic polyurea.

Example 5

0.10g of imidazole type diamine ionic liquid (1, 3-bis (aminoethyl) -2-methylimidazolium bromide) was dissolved in 7mL of N, N-dimethylacetamide, and 20 mole fraction of DBU as the ionic liquid was added. Injecting the precursor solution into a reaction kettle, purging with carbon dioxide for 5min to remove oxygen, heating to 200 deg.C, and introducing 10MPa CO₂Stirring and reacting for 24 hours, washing the solid precipitate with ethyl acetate for multiple times and drying to obtain CO₂And (3) ionic polyurea.

Example 6

0.50g of imidazole type diamine ionic liquid (1, 3-bis (aminoethyl) -2-methylimidazolium bromide) was dissolved in 7mL of N, N-dimethylacetamide, and 20 mole fraction of DBU as the ionic liquid was added. Injecting the precursor solution into a reaction kettle, purging with carbon dioxide for 5min to remove oxygen, heating to 100 deg.C, and introducing 10MPa CO₂Stirring for reaction for 24h, and reacting with acetic acidWashing the ester for multiple times, precipitating and drying to obtain CO₂And (3) ionic polyurea.

Example 7

0.50g of imidazole type diamine ionic liquid (1, 3-bis (aminoethyl) -2-methylimidazolium bromide) was dissolved in 7mL of N, N-dimethylacetamide, and 20 mole fraction of DBU as the ionic liquid was added. Injecting the precursor solution into a reaction kettle, purging with carbon dioxide for 5min to remove oxygen, heating to 200 deg.C, and introducing 4MPa CO₂Stirring and reacting for 24 hours, washing the solid precipitate with ethyl acetate for multiple times and drying to obtain CO₂And (3) ionic polyurea.

Example 8 0.50g of imidazole-type diamine ionic liquid (1, 3-bis (aminoethyl) -2-methylimidazolium bromide) was dissolved in 7mL of N, N-dimethylacetamide and 20 mole fraction of DBU was added as ionic liquid. Injecting the precursor solution into a reaction kettle, purging with carbon dioxide for 5min to remove oxygen, heating to 200 deg.C, and introducing 10MPa CO₂Stirring and reacting for 12h, washing the solid precipitate with ethyl acetate for multiple times and drying to obtain CO₂And (3) ionic polyurea.

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.