Selenium-containing unsaturated polyester amides and methods for their preparation

Abstract

The application discloses a kind of selenium-containing unsaturated polyester amide and preparation method thereof, comprising the following steps: diamine compound, propargyl ester and selenium lactone are dissolved in organic solvent, chemical reaction is carried out, and the selenium-containing unsaturated polyester amide is obtained.The application uses diamine compound, propargyl ester and selenium lactone as raw material, generates selenium-containing unsaturated polyester amide by the click polymerization reaction of selenol and alkyne, develops a new type of selenium-containing unsaturated polyester amide preparation method, and the polyester amide obtained by preparation has narrow molecular weight distribution, controllable structure, adjustable degradation rate, good long-term stability, multiple responsiveness, good optical performance;Raw material source is extensive, avoids the cumbersome substrate synthesis, step is simple, reaction condition is mild, polymerization speed is fast, can realize efficient mass production;No catalyst is needed, no by-product is generated, and no additional purification is needed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer synthesis, and particularly relates to a selenium-containing unsaturated polyester amide and a preparation method thereof. BACKGROUND

[0002] Polyester amide materials are a class of high-molecular-weight materials with important application prospects. Their molecular main chains contain both ester bonds and amide bonds, which endow them with unique physical and chemical properties. In recent years, with the increasing demand for biodegradable materials and environmentally friendly materials, the research and application of polyester amide materials have developed rapidly.

[0003] Polyamide materials are widely used in various fields due to their excellent mechanical properties, wear resistance and chemical stability, including textiles, automobiles, electronics, packaging and other fields. In the field of medical materials, polyester amides are valued for their good biocompatibility and adjustable biodegradability, and are used in drug delivery systems, tissue engineering scaffolds, surgical sutures, etc.

[0004] Although polyester amide materials have many advantages, there are still some problems and challenges in practical application. For example: (1) the synthesis method of polyester amide needs to use expensive or difficult-to-obtain raw materials, which limits the possibility of large-scale production; (2) the by-products generated in the polycondensation process of polyester amide materials not only increase the cost and complexity of subsequent purification, but also may affect the performance of the polymer; (3) the polymer prepared by traditional polycondensation method usually has low molecular weight and wide molecular weight distribution, which limits its potential in high-performance applications; (4) the reaction rate of the synthesis method is slow, and the polymerization reaction needs to be carried out for a long time, affecting the production efficiency; (5) the synthesis method has many steps, and requires high equipment conditions and manual operation, increasing the production cost and operation difficulty; (6) the synthesis method uses toxic or corrosive raw materials and solvents, which may cause potential pollution to the environment; (7) although polyester amides have good biocompatibility, to realize their application in the biomedical field, it is necessary to accurately control their degradation rate and mechanical properties, which is challenging in the synthesis process; (8) high refractive index polymers have great application value in the field of optics, especially in the manufacture of advanced display devices, various lenses, optical waveguides and diffraction gratings. However, the light shielding index of general organic polymers is relatively low (generally 1.5-1.6), and the introduction of aromatic heterocyclic rings in the polymer chain is usually required, but it also leads to problems in transparency, solubility and processability of the material. SUMMARY

[0005] The present application aims at the deficiencies in the prior art, and provides a preparation method of selenium-containing unsaturated polyester amide, which uses a diamine compound, propynoate and selenium lactone as raw materials, and generates the selenium-containing unsaturated polyester amide through a click polymerization reaction of selenol and alkyne in a solvent.The product polyester amide has a narrow molecular weight distribution, a controllable structure, an adjustable degradation rate and good long-term stability; the raw materials are widely sourced, the steps are simple, the reaction conditions are mild, the polymerization speed is fast, efficient mass production can be realized, the polymerization reaction does not need a catalyst, no by-product is generated, and no additional purification is needed.

[0006] To solve the above technical problems, the present application provides, in one aspect, a preparation method of selenium-containing unsaturated polyester amide, comprising the following steps:

[0007] The diamine compound, propynoate and selenium lactone are mixed and dissolved in an organic solvent to generate the selenium-containing unsaturated polyester amide through a chemical reaction;

[0008] The chemical reaction comprises: the diamine compound reacts with the selenium lactone to generate a compound of formula (1), and the compound of formula (1) reacts with the propynoate to generate a selenium-containing unsaturated polyester amide of formula (2);

[0009]

[0010]

[0011] wherein R 1 is selected from (CH2CH2O) x or an alkyl group with 2-20 carbon atoms, x is an integer between 2 and 10; R 2 is selected from (CH2CH2O) y , an alkyl group with 2-20 carbon atoms or a carbon ring-containing group with 6-20 carbon atoms, y is an integer between 2 and 10; m is selected from an integer between 1 and 3, and n is selected from a positive integer.

[0012] The present application uses a diamine compound, propynoate and selenium lactone as raw materials, and generates a selenium-containing unsaturated polyester amide through a click polymerization reaction of selenol and alkyne in a solvent, thereby developing a novel preparation method of selenium-containing unsaturated polyester amide; the product polyester amide has a narrow molecular weight distribution, a controllable structure, an adjustable degradation rate, good long-term stability, multiple responsiveness and good optical performance; the raw materials are widely sourced, the steps are simple, the reaction conditions are mild, the polymerization speed is fast, efficient mass production can be realized, the polymerization reaction does not need a catalyst, no by-product is generated, and no additional purification is needed.

[0013] Further, the molar ratio of the diamine compound, propynoate and selenium lactone is (1-1.2):(1-1.2):(2-2.4).

[0014] Furthermore, the concentration of the propynate is 0.5-2 mol / L, such as 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, etc., including but not limited to these.

[0015] Furthermore, the structural formula of the propynyl ester is:

[0016]

[0017] Among them, R 1 Selected from (CH2CH2O) x Or an alkyl group with 2-20 carbon atoms, where x is an integer between 2 and 10.

[0018] Furthermore, the structural formula of the diamine compound is as follows:

[0019]

[0020] Among them, R 2 Selected from (CH2CH2O) y Alkyl groups with 2-20 carbon atoms or carbon ring groups with 6-20 carbon atoms, where y is an integer between 2 and 10.

[0021] Furthermore, the selenolactone is selected from... One or more of them.

[0022] Furthermore, the temperature of the chemical reaction is 0-100℃, such as 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, and so on; the time is 0.5-10h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, and so on.

[0023] Furthermore, the chemical reaction is followed by steps of filtration and vacuum drying.

[0024] Furthermore, the organic solvent is selected from one or more of tetrahydrofuran, toluene, and hexafluoroisopropanol.

[0025] The second aspect of the present invention provides a selenium-containing unsaturated polyesteramide prepared by the preparation method described in the first aspect.

[0026] The beneficial effects of this invention are:

[0027] This invention develops a novel method for preparing selenium-containing unsaturated polyesteramide by using diamine compounds, propargyl esters, and selenolactones as raw materials and generating selenols and alkynes through click polymerization.

[0028] The polyester amide prepared by the method has a narrow molecular weight distribution, a controllable structure, an adjustable degradation rate, a good long-term stability, a multiple responsiveness and a good optical performance.

[0029] The raw material is widely available, the complicated substrate synthesis is avoided, the steps are simple, the reaction condition is mild, the polymerization speed is fast, and high-efficiency large-scale production can be realized.

[0030] The polymerization reaction does not need a catalyst, does not generate a byproduct, and does not need additional purification. BRIEF DESCRIPTION OF DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the present application, the drawings needed in the examples will be briefly introduced below. Obviously, the drawings described below are only the embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0032] Figure 1 and Figure 2 are the nuclear magnetic spectrum and GPC test spectrum of the polymer prepared in Example 1, respectively;

[0033] Figure 3 and Figure 4 are the nuclear magnetic spectrum and GPC test spectrum of the polymer prepared in Example 2, respectively;

[0034] Figure 5 and Figure 6 are the nuclear magnetic spectrum and GPC test spectrum of the polymer prepared in Example 3, respectively;

[0035] Figure 7 and Figure 8 are the nuclear magnetic spectrum and GPC test spectrum of the polymer prepared in Example 4, respectively;

[0036] Figure 9 and Figure 10 are the nuclear magnetic spectrum and GPC test spectrum of the polymer prepared in Example 5, respectively;

[0037] Figure 11 and Figure 12 are the nuclear magnetic spectrum and GPC test spectrum of the polymer prepared in Example 6, respectively;

[0038] Figure 13 and Figure 14 are the nuclear magnetic spectrum and GPC test spectrum of the polymer prepared in Example 7, respectively;

[0039] Figure 15 and Figure 16 are the nuclear magnetic spectrum and GPC test spectrum of the polymer prepared in Example 8, respectively;

[0040] Figure 17 and Figure 18 are the NMR and GPC test spectra of the polymer prepared in Example 9, respectively;

[0041] Figure 19 and Figure 20 are the NMR and GPC test spectra of the polymer prepared in Example 10, respectively;

[0042] Figure 21 and Figure 22 are the NMR and GPC test spectra of the polymer prepared in Example 11, respectively;

[0043] Figure 23 and Figure 24 are the NMR and GPC test spectra of the polymer prepared in Example 12, respectively;

[0044] Figure 25 and Figure 26 are the NMR and GPC test spectra of the polymer prepared in Example 13, respectively;

[0045] Figure 27 and Figure 28 are the NMR and GPC test spectra of the polymer prepared in Example 14, respectively;

[0046] Figure 29 and Figure 30 are the NMR and GPC test spectra of the polymer prepared in Example 15, respectively;

[0047] Figure 31 are the mechanical property test spectra of the polymers prepared in the respective examples;

[0048] Figure 32 are the mechanical property comparison spectra of the polymers prepared in Example 9 and Example 15 with commercially available PLLA, PA6 and PCL, respectively;

[0049] Figure 33 are the optical property test spectra of the polymers prepared in Example 1 and Example 8, respectively. DETAILED DESCRIPTION

[0050] The technical solutions of the present application will be described clearly and completely below in conjunction with the specific embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0051] The propiolate in the embodiment of the present application is respectively propiolate ethylene glycol ester (1A), propiolate butanediol ester (1B), and propiolate hexanediol ester (1C), and the structural formulas thereof are respectively:

[0052]

[0053] The diamine compound in the embodiment of the present application is respectively hexanediamine (2A), decanediamine (2B), 4,4'-diaminodicyclohexyl methane (2C), 1,8-diamino-3,6-dioxaoctane (2D), and 4,7,10-trio-1,13-tridecanediamine (2E), and the structural formulas thereof are respectively:

[0054]

[0055] The five-membered selenium lactone is used in the embodiment of the present application, and the structural formula thereof is

[0056] Embodiment 1

[0057] The propiolate ethylene glycol ester (1A), hexanediamine (2A), and five-membered selenium lactone are mixed and dissolved in a round-bottom flask by using hexafluoroisopropanol as a solvent, wherein the concentration of the propiolate ethylene glycol ester is 1 mol / L, and the reaction is carried out at room temperature for 3 hours, and the polymer is precipitated. The solvent is removed by filtration, and vacuum drying is performed to obtain the selenium-containing unsaturated polyester amide polymer (1A2A), and the nuclear magnetic resonance spectrum thereof is shown in Figure 1 The polymer is subjected to GPC test, and the result is shown in Figure 2 The weight average molecular weight of the polymer obtained in the embodiment is 35.3 kg / mol, and the molecular weight distribution is 1.4.

[0058] Embodiment 2

[0059] The propiolate butanediol ester (1B), hexanediamine (2A), and five-membered selenium lactone are mixed and dissolved in a round-bottom flask by using hexafluoroisopropanol as a solvent, wherein the concentration of the propiolate ethylene glycol ester is 1 mol / L, and the reaction is carried out at room temperature for 3 hours, and the polymer is precipitated. The solvent is removed by filtration, and vacuum drying is performed to obtain the selenium-containing unsaturated polyester amide polymer (1B2A), and the nuclear magnetic resonance spectrum thereof is shown in Figure 3 The polymer is subjected to GPC test, and the result is shown in Figure 4 The weight average molecular weight of the polymer obtained in the embodiment is 59.0 kg / mol, and the molecular weight distribution is 1.7.

[0060] Embodiment 3

[0061] The propiolyl hexanediol ester (1C), hexanediamine (2A), and five-membered selenium lactone were mixed and dissolved in a round-bottom flask with hexafluoroisopropanol as the solvent, with a propiolyl glycol ester concentration of 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated out. The solvent was removed by filtration, and vacuum drying yielded the selenium-containing unsaturated polyester amide polymer (1C2A), whose nuclear magnetic resonance spectrum is shown in FIG. 1C2A. Figure 5 The polymer was tested by GPC, and the results are shown in FIG. 2A2A. Figure 6 The polymer obtained in this example had a weight average molecular weight of 38.0 kg / mol and a molecular weight distribution of 1.4.

[0062] Example 4

[0063] The propiolyl glycol ester (1A), decanediamine (2B), and five-membered selenium lactone were mixed and dissolved in a round-bottom flask with hexafluoroisopropanol as the solvent, with a propiolyl glycol ester concentration of 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated out. The solvent was removed by filtration, and vacuum drying yielded the selenium-containing unsaturated polyester amide polymer (1A2B), whose nuclear magnetic resonance spectrum is shown in FIG. 1A2B. Figure 7 The polymer was tested by GPC, and the results are shown in FIG. 2A2A. Figure 8 The polymer obtained in this example had a weight average molecular weight of 37.4 kg / mol and a molecular weight distribution of 1.3.

[0064] Example 5

[0065] The propiolyl glycol ester (1A), decanediamine (2B), and five-membered selenium lactone were mixed and dissolved in a round-bottom flask with hexafluoroisopropanol as the solvent, with a propiolyl glycol ester concentration of 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated out. The solvent was removed by filtration, and vacuum drying yielded the selenium-containing unsaturated polyester amide polymer (1A2B), whose nuclear magnetic resonance spectrum is shown in FIG. 1A2B. Figure 9 The polymer was tested by GPC, and the results are shown in FIG. 2A2A. Figure 10 The polymer obtained in this example had a weight average molecular weight of 37.4 kg / mol and a molecular weight distribution of 1.3.

[0066] Example 6

[0067] hexyne acid glycol ester (1C), decanediamine (2B), five selenium lactone three raw materials are fed in a round bottom flask with a molar ratio of 1:1:2, dissolved in hexafluoroisopropanol as the solvent, wherein the concentration of propargyl acid glycol ester is 1 mol / L, and the reaction is carried out at room temperature for 3 hours, and the polymer precipitates. The solvent is removed by filtration, and vacuum drying can prepare selenium-containing unsaturated polyester amide polymer (1C2B), and its nuclear magnetic resonance spectrum is shown in Figure 11 The polymer is tested by GPC, and the results are shown in Figure 12 The test shows that the weight average molecular weight of the polymer obtained in this example is 37.2 kg / mol, and the molecular weight distribution is 1.6.

[0068] Example 7

[0069] hexyne acid glycol ester (1C), decanediamine (2B), five selenium lactone three raw materials are fed in a round bottom flask with a molar ratio of 1:1:2, dissolved in hexafluoroisopropanol as the solvent, wherein the concentration of propargyl acid glycol ester is 1 mol / L, and the reaction is carried out at room temperature for 3 hours, and the polymer precipitates. The solvent is removed by filtration, and vacuum drying can prepare selenium-containing unsaturated polyester amide polymer (1C2B), and its nuclear magnetic resonance spectrum is shown in Figure 13 The polymer is tested by GPC, and the results are shown in Figure 14 The test shows that the weight average molecular weight of the polymer obtained in this example is 37.2 kg / mol, and the molecular weight distribution is 1.6.

[0070] Example 8

[0071] hexyne acid glycol ester (1C), decanediamine (2B), five selenium lactone three raw materials are fed in a round bottom flask with a molar ratio of 1:1:2, dissolved in hexafluoroisopropanol as the solvent, wherein the concentration of propargyl acid glycol ester is 1 mol / L, and the reaction is carried out at room temperature for 3 hours, and the polymer precipitates. The solvent is removed by filtration, and vacuum drying can prepare selenium-containing unsaturated polyester amide polymer (1C2B), and its nuclear magnetic resonance spectrum is shown in Figure 15 The polymer is tested by GPC, and the results are shown in Figure 16 The test shows that the weight average molecular weight of the polymer obtained in this example is 37.2 kg / mol, and the molecular weight distribution is 1.6.

[0072] Example 9

[0073] Hexyne diol ester propiolate (1C), 4,4'-diamino dicyclohexyl methane (2C), and five-membered selenium lactone were mixed and dissolved in a round-bottom flask with hexafluoroisopropanol as the solvent, with a molar ratio of 1:1:2, and a propiolate ethylene glycol ester concentration of 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated out. The solvent was removed by filtration, and vacuum drying was performed to obtain the selenium-containing unsaturated polyester amide polymer (1C2C), the nuclear magnetic resonance spectrum of which is shown in Figure 17 . The polymer was tested by GPC, and the results are shown in Figure 18 . The weight average molecular weight of the polymer obtained in this example was 16.4 kg / mol, and the molecular weight distribution was 2.4.

[0074] Example 10

[0075] Hexyne diol ester propiolate (1C), 4,4'-diamino dicyclohexyl methane (2C), and five-membered selenium lactone were mixed and dissolved in a round-bottom flask with hexafluoroisopropanol as the solvent, with a molar ratio of 1:1:2, and a propiolate ethylene glycol ester concentration of 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated out. The solvent was removed by filtration, and vacuum drying was performed to obtain the selenium-containing unsaturated polyester amide polymer (1C2C), the nuclear magnetic resonance spectrum of which is shown in Figure 19 . The polymer was tested by GPC, and the results are shown in Figure 20 . The weight average molecular weight of the polymer obtained in this example was 16.4 kg / mol, and the molecular weight distribution was 2.4.

[0076] Example 11

[0077] Hexyne diol ester propiolate (1C), 4,4'-diamino dicyclohexyl methane (2C), and five-membered selenium lactone were mixed and dissolved in a round-bottom flask with hexafluoroisopropanol as the solvent, with a molar ratio of 1:1:2, and a propiolate ethylene glycol ester concentration of 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated out. The solvent was removed by filtration, and vacuum drying was performed to obtain the selenium-containing unsaturated polyester amide polymer (1C2C), the nuclear magnetic resonance spectrum of which is shown in Figure 21 . The polymer was tested by GPC, and the results are shown in Figure 22 . The weight average molecular weight of the polymer obtained in this example was 16.4 kg / mol, and the molecular weight distribution was 2.4.

[0078] Example 12

[0079] hexyne acid glycol ester (1C), 1,8-diamino-3,6-dioxaoctane (2D), and five-membered selenium lactone in a molar ratio of 1:1:2, and the mixture was dissolved in hexafluoroisopropanol as a solvent. The concentration of the propynic acid ethylene glycol ester was 1 mol / L, and the reaction was carried out at room temperature for 3 hours. The polymer was precipitated. The solvent was removed by filtration, and vacuum drying was performed to obtain the selenium-containing unsaturated polyester amide polymer (1C2D). The nuclear magnetic resonance spectrum thereof is shown in Figure 23 The polymer was subjected to GPC testing, and the results are shown in Figure 24 The weight average molecular weight of the polymer obtained in this example was 45.9 kg / mol, and the molecular weight distribution was 3.7.

[0080] Example 13

[0081] hexyne acid glycol ester (1C), 1,8-diamino-3,6-dioxaoctane (2D), and five-membered selenium lactone in a molar ratio of 1:1:2, and the mixture was dissolved in hexafluoroisopropanol as a solvent. The concentration of the propynic acid ethylene glycol ester was 1 mol / L, and the reaction was carried out at room temperature for 3 hours. The polymer was precipitated. The solvent was removed by filtration, and vacuum drying was performed to obtain the selenium-containing unsaturated polyester amide polymer (1C2D). The nuclear magnetic resonance spectrum thereof is shown in Figure 25 The polymer was subjected to GPC testing, and the results are shown in Figure 26 The weight average molecular weight of the polymer obtained in this example was 45.9 kg / mol, and the molecular weight distribution was 3.7.

[0082] Example 14

[0083] hexyne acid glycol ester (1C), 1,8-diamino-3,6-dioxaoctane (2D), and five-membered selenium lactone in a molar ratio of 1:1:2, and the mixture was dissolved in hexafluoroisopropanol as a solvent. The concentration of the propynic acid ethylene glycol ester was 1 mol / L, and the reaction was carried out at room temperature for 3 hours. The polymer was precipitated. The solvent was removed by filtration, and vacuum drying was performed to obtain the selenium-containing unsaturated polyester amide polymer (1C2D). The nuclear magnetic resonance spectrum thereof is shown in Figure 27 The polymer was subjected to GPC testing, and the results are shown in Figure 28 The weight average molecular weight of the polymer obtained in this example was 45.9 kg / mol, and the molecular weight distribution was 3.7.

[0084] Example 15

[0085] The three raw materials of hexyne diol propiolate (1C), 4,7,10-trioxa-1,13-tridecanediamine (2E), and pentaselenolactone are fed into a round-bottom flask in a molar ratio of 1:1:2, dissolved and mixed in hexafluoroisopropanol, wherein the concentration of ethylene glycol propiolate is 1 mol / L, and the reaction is carried out at room temperature for 3 hours, and the polymer precipitates. The solvent is removed by filtration, and vacuum drying is performed to obtain the selenium-containing unsaturated polyester amide polymer (1C2E), the nuclear magnetic resonance spectrum of which is shown in Figure 29 The polymer is subjected to GPC testing, and the results are shown in Figure 30 The test shows that the weight average molecular weight of the polymer obtained in this example is 37.6 kg / mol, and the molecular weight distribution is 2.6.

[0086] Test Example

[0087] The polymer prepared in each example is placed in an iron mold by hot pressing into a film, heated to 160-200°C, and hot pressed at a pressure of 10 MPa for 1 h to obtain a 0.5 mm thick film, which is cut into a dumbbell shape for mechanical tensile testing, and the results are shown in Figure 31 The mechanical properties and glass transition temperature and melting point of the polymer obtained in each example are shown in Table 1. As can be seen from Figure 31 and Table 1, the selenium-containing unsaturated polyester amide material of the present application exhibits a wide range of thermal and mechanical performance characteristics, and has diversified mechanical properties. This proves that the polymerization method of the present application can prepare materials with different properties by changing the structure of the monomer through one-pot two-step synthesis technology. In addition, the polymer (1C2C) prepared in Example 9, the polymer (1C2E) prepared in Example 15, and commercially available PLLA (poly-L-lactic acid), PA6 (polyamide 6), and PCL (polycaprolactone) are compared in terms of mechanical properties, and the results are shown in Figure 32 It can be seen that the mechanical properties of the selenium-containing unsaturated polyester amide material synthesized by the present application are better than those of the commonly used commercial polymers.

[0088] Table 1

[0089]

[0090]

[0091] High refractive index polymers have great application value in the field of optics, especially in the manufacture of advanced display devices, various lenses, optical waveguides, and diffraction gratings. However, the refractive index of general organic polymers is relatively low (generally 1.5-1.6), and it is necessary to introduce aromatic heterocycles into the polymer chain, which leads to problems in transparency, solubility, and processability. The present application is based on the molar refractivity [R] value (11.17 cm 3 ·mol-1 ), high refractive index materials without aromatic heterocycle were prepared. The polymers (1A2A) obtained in Example 1, the polymers (1B2C) obtained in Example 8 and the polymers (1B2D) obtained in Example 11 were subjected to optical performance test, and the refractive index test results are shown in Table 1. Figure 33 As can be seen, the polymers have excellent optical performance, wherein the light shielding index of the polymer (1A2A) obtained in Example 1 is as high as 1.7660.

[0092] The above detailed description of the present application is made in combination with the specific embodiments and exemplary examples, but these descriptions cannot be understood as limiting the present application. Those skilled in the art understand that various equivalent substitutions, modifications or improvements can be made to the technical solutions and embodiments of the present application without departing from the spirit and scope of the present application, and these all fall within the scope of the present application. The protection scope of the present application is subject to the appended claims.

Claims

1. A process for the preparation of a selenium-containing unsaturated polyester amide, characterized in that, The method comprises the following steps: The diamine compound, propiolate and selenolactone are mixed and dissolved in an organic solvent to perform a chemical reaction to obtain the selenium-containing unsaturated polyester amide; The chemical reaction comprises: the diamine compound reacts with selenolactone to generate a compound of formula (1), and the compound of formula (1) reacts with propiolate to generate a selenium-containing unsaturated polyester amide of formula (2). wherein R 1 is selected from (CH2CH20) x or an alkyl group having 2 to 20 carbon atoms, x is an integer between 2 and 10; R 2 is selected from (CH2CH20) y , an alkyl group having 2 to 20 carbon atoms or a carbon ring containing group having 6 to 20 carbon atoms, y is an integer between 2 and 10; m is selected from an integer between 1 and 3, n is selected from a positive integer; The molar ratio of the diamine compound, propiolate and selenolactone is (1-1.2):(1-1.2):(2-2.4).

2. The process for the production of a selenium-containing unsaturated polyester amide according to claim 1, characterized in that, The concentration of the propiolate is 0.5-2 mol / L.

3. The method of making a selenium-containing unsaturated polyester amide according to claim 1, wherein, The structural formula of the propiolate is: wherein R 1 selected from (CH2CH20) x or an alkyl group having 2 to 20 carbon atoms, and x is an integer between 2 and 10.

4. The method of making a selenium-containing unsaturated polyester amide according to claim 1, wherein, The structural formula of the diamine compound is: wherein R 2 is selected from (CH2CH20) y , an alkyl group having 2 to 20 carbon atoms or a carbon ring-containing group having 6 to 20 carbon atoms, and y is an integer between 2 and 10.

5. The method of making a selenium-containing unsaturated polyester amide according to claim 1, wherein, The selenium lactone is selected from one or several of the group consisting of 6. The method of making a selenium-containing unsaturated polyester amide according to claim 1, wherein, The temperature of the chemical reaction is 0-100℃, and the time is 0.5-10 h.

7. The method of making a selenium-containing unsaturated polyester amide according to claim 1, wherein, The chemical reaction further comprises the steps of filtering and vacuum drying.

8. The process for producing a selenium-containing unsaturated polyester amide according to claim 1, characterized by, The organic solvent is selected from one or more of tetrahydrofuran, toluene and hexafluoroisopropanol. 9.A selenium-containing unsaturated polyester amide prepared by the preparation method of any one of claims 1-8.

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