Selenium-containing unsaturated polyesteramide and preparation method thereof

Abstract

The invention discloses selenium-containing unsaturated polyesteramide and a preparation method thereof, and the preparation method comprises the following steps: mixing and dissolving a diamine compound, propiolic acid ester and selenolactone in an organic solvent, and carrying out chemical reaction to obtain the selenium-containing unsaturated polyesteramide. A diamine compound, propiolic acid ester and selenolactone are used as raw materials, selenium-containing unsaturated polyesteramide is generated through click polymerization reaction of selenol and alkyne, the novel preparation method of selenium-containing unsaturated polyesteramide is developed, and the prepared polyesteramide is narrow in molecular weight distribution, controllable in structure and adjustable in degradation rate, and can be used for preparing selenium-containing unsaturated polyesteramide. Long-term stability is good, multiple responsiveness is achieved, and optical performance is good; the raw materials are wide in source, tedious substrate synthesis is avoided, the steps are simple, the reaction conditions are mild, the polymerization speed is high, and efficient large-scale production can be achieved; no catalyst is needed, no by-product is generated, and extra purification is not needed.

Description

Technical Field

[0001] The invention relates to the technical field of polymer synthesis, and in particular to a selenium-containing unsaturated polyester amide and a preparation method thereof. Background Art

[0002] Polyesteramide materials are a class of polymer materials with important application prospects. Their main molecular chains contain both ester bonds and amide bonds, which give them unique physical and chemical properties. In recent years, with the increasing demand for biodegradable materials and environmentally friendly materials, the research and application of polyesteramide materials has developed rapidly.

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

[0004] Although polyesteramide materials have many advantages, there are still some problems and challenges in practical applications. For example: (1) The synthesis method of polyester amide requires the use of expensive or difficult-to-obtain raw materials, which limits the possibility of large-scale production; (2) Polyester amide materials produce by-products during the polycondensation process, which not only increases the cost and complexity of subsequent purification, but also may affect the performance of the polymer; (3) Polymers prepared by traditional polycondensation methods usually have the problems of low molecular weight and wide molecular weight distribution, which limits their potential in high-performance applications; (4) The synthesis method has a slow reaction rate and requires a long time for polymerization, which affects production efficiency; (5) The synthesis method has many steps and requires high equipment conditions and manual operation, which increases production costs and operational difficulty; (6) The synthesis method uses toxic or corrosive raw materials and solvents, which poses potential pollution to the environment; (7) Although polyester amide has good biocompatibility, to achieve its application in the biomedical field, it is necessary to precisely control its degradation rate and mechanical properties, which is challenging in the synthesis process; (8) High refractive index polymers have shown 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 shading index of general organic polymers (usually 1.5-1.6) is relatively low, which usually requires the introduction of aromatic heterocycles into the polymer chain, but this also causes problems in transparency, solubility and processability of the material. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a method for preparing a selenium-containing unsaturated polyester amide. The method uses a diamine compound, propiolate and selenolactone 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 material sources are wide, the steps are simple, the reaction conditions are mild, the polymerization speed is fast, and efficient large-scale production can be achieved. The polymerization reaction does not require a catalyst, does not generate by-products, and does not require additional purification.

[0006] In order to solve the above technical problems, the present invention provides a method for preparing selenium-containing unsaturated polyester amide, comprising the following steps:

[0007] The diamine compound, propiolate and selenolactone are mixed and dissolved in an organic solvent to carry out a chemical reaction to obtain the selenium-containing unsaturated polyester amide;

[0008] 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);

[0009]

[0010]

[0011] Among them, R 1 Selected from (CH 2 CH 2 O) x or an alkyl group having 2 to 20 carbon atoms, x is an integer between 2 and 10; R 2 Selected from (CH 2 CH 2 O) y , an alkyl group having 2 to 20 carbon atoms or a carbocyclic group having 6 to 20 carbon atoms, y is an integer between 2 and 10; m is an integer selected from 1 to 3, and n is a positive integer.

[0012] The invention uses diamine compounds, propiolate and selenolactone as raw materials, generates selenium-containing unsaturated polyester amide through click polymerization reaction of selenol and alkyne in a solvent, and develops a novel preparation method of selenium-containing unsaturated polyester amide; the prepared product polyester amide has narrow molecular weight distribution, controllable structure, adjustable degradation rate, good long-term stability, multiple responsiveness and good optical performance; the raw material sources are wide, and tedious substrate synthesis is avoided; the steps are simple, the reaction conditions are mild, the polymerization speed is fast, and efficient large-scale production can be realized; the polymerization reaction does not require a catalyst, no by-products are generated, and no additional purification is required.

[0013] Furthermore, the molar ratio of the diamine compound, propiolate and selenolactone is (1-1.2): (1-1.2): (2-2.4).

[0014] Further, the concentration of the propiolate 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] Further, the structural formula of the propiolate is:

[0016]

[0017] Among them, R 1 Selected from (CH 2 CH 2 O) x or an alkyl group having 2 to 20 carbon atoms, wherein x is an integer between 2 and 10.

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

[0019]

[0020] Among them, R 2 Selected from (CH 2 CH 2 O) y , an alkyl group having 2-20 carbon atoms or a carbocyclic group having 6-20 carbon atoms, and y is an integer between 2-10.

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

[0022] Furthermore, the temperature of the chemical reaction is 0-100°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, including but not limited to these; the time is 0.5-10h, for example, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, including but not limited to these.

[0023] Furthermore, the chemical reaction further includes the steps of filtering 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 selenium-containing unsaturated polyester amide prepared by the preparation method described in the first aspect.

[0026] Beneficial effects of the present invention:

[0027] The invention uses diamine compounds, propiolate and selenolactone as raw materials, generates selenium-containing unsaturated polyester amide through click polymerization reaction of selenol and alkyne, and develops a novel preparation method of selenium-containing unsaturated polyester amide.

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

[0029] The raw material sources of the invention are wide, and tedious substrate synthesis is avoided. The steps are simple, the reaction conditions are mild, the polymerization speed is fast, and efficient large-scale production can be achieved.

[0030] The polymerization reaction of the present invention does not require a catalyst, does not generate by-products, and does not require additional purification. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solution of the present invention, the drawings required for use in the embodiments are briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0032] Figure 1 and Figure 2 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 1;

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

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

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

[0036] Fig. 9 and Fig.10 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 5;

[0037] Fig.11 and Fig.12 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 6;

[0038] Fig.13 and Fig.14They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 7;

[0039] Fig.15 and Fig.16 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 8;

[0040] Fig.17 and Fig.18 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 9;

[0041] Fig.19 and Fig. 20 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 10;

[0042] Fig.21 and Fig. 22 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 11;

[0043] Fig.23 and Fig.24 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 12;

[0044] Fig.25 and Fig.26 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 13;

[0045] Fig. 27 and Fig.28 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 14;

[0046] Fig.29 and Fig.30 They are respectively the NMR spectrum and GPC test spectrum of the polymer prepared in Example 15;

[0047] Fig.31 It is a mechanical property test diagram of the polymer prepared in each embodiment;

[0048] Fig.32 is a comparison chart of the mechanical properties of the polymers prepared in Examples 9 and 15 and commercially available PLLA, PA6 and PCL;

[0049] Fig.33 It is the optical property test spectrum of the polymer prepared in Example 1 and Example 8. DETAILED DESCRIPTION

[0050] The technical solution of the present invention will be described clearly and completely below in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0051] In the embodiment of the present invention, the propiolic acid esters are ethylene glycol propiolate (1A), butylene glycol propiolate (1B), and hexanediol propiolate (1C), and their structural formulas are:

[0052]

[0053] In the embodiment of the present invention, the diamine compounds are hexamethylenediamine (2A), decanediamine (2B), 4,4'-diaminodicyclohexylmethane (2C), 1,8-diamino-3,6-dioxaoctane (2D), and 4,7,10-trioxo-1,13-tridecanediamine (2E), and their structural formulas are:

[0054]

[0055] In the embodiment of the present invention, a five-membered selenolactone is used, and its structural formula is

[0056] Example 1

[0057] The three raw materials of propiolic acid glycol ester (1A), hexamethylenediamine (2A), and penta-selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and a polymer precipitated. The solvent was removed by filtration, and vacuum drying was performed to prepare a selenium-containing unsaturated polyester amide polymer (1A2A), and its NMR spectrum was as follows: Figure 1 The polymer was subjected to GPC test, and the results were as follows Figure 2 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 35.3 kg / mol, the molecular weight distribution is 1.4, and the molecular weight distribution is narrow.

[0058] Example 2

[0059] The three raw materials of propiolic acid butanediol ester (1B), hexamethylenediamine (2A), and penta-selenolide were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid ethylene glycol ester was 1 mol / L, reacted at room temperature for 3 hours, and a polymer precipitated. The solvent was removed by filtration, and vacuum drying was performed to prepare a selenium-containing unsaturated polyester amide polymer (1B2A), and its NMR spectrum was as follows: Figure 3The polymer was subjected to GPC test, and the results were as follows Figure 4 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 59.0 kg / mol, and the molecular weight distribution is 1.7.

[0060] Example 3

[0061] The three raw materials of hexanediol propiolate (1C), hexanediamine (2A), and penta-selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of ethylene glycol propiolate was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and a polymer precipitated. The solvent was removed by filtration, and vacuum drying was performed to prepare a selenium-containing unsaturated polyester amide polymer (1C2A), and its NMR spectrum was as follows: Figure 5 The polymer was subjected to GPC test, and the results were as follows Figure 6 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 38.0 kg / mol, and the molecular weight distribution is 1.4.

[0062] Example 4

[0063] The three raw materials of propiolic acid glycol ester (1A), decanediamine (2B), and penta-selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and a polymer precipitated. The solvent was removed by filtration, and vacuum drying was performed to prepare a selenium-containing unsaturated polyester amide polymer (1A2B), and its NMR spectrum was as follows: Figure 7 The polymer was subjected to GPC test, and the results were as follows Figure 8 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 37.4 kg / mol, and the molecular weight distribution is 1.3.

[0064] Example 5

[0065] The three raw materials of propiolic acid butanediol ester (1B), decanediamine (2B), and penta-selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid ethylene glycol ester was 1 mol / L, reacted at room temperature for 3 hours, and a polymer precipitated. The solvent was removed by filtration, and vacuum drying was performed to prepare a selenium-containing unsaturated polyester amide polymer (1B2B), and its NMR spectrum was as follows Fig. 9 The polymer was subjected to GPC test, and the results were as follows Fig.10 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 36.8 kg / mol, and the molecular weight distribution is 1.3.

[0066] Example 6

[0067] The three raw materials of hexanediol propiolate (1C), decanediamine (2B), and penta-selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of ethylene glycol propiolate was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and a polymer precipitated. The solvent was removed by filtration, and vacuum drying was performed to prepare a selenium-containing unsaturated polyester amide polymer (1C2B), and its NMR spectrum was as follows: Fig.11 The polymer was subjected to GPC test, and the results were as follows Fig.12 As shown, the test results show 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] The three raw materials of propiolic acid glycol ester (1A), 4,4'-diaminodicyclohexylmethane (2C), and five-membered selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated. The solvent was removed by filtration and vacuum drying to prepare the selenium-containing unsaturated polyester amide polymer (1A2C), and its nuclear magnetic resonance spectrum is shown as follows Fig.13 The polymer was subjected to GPC test, and the results were as follows Fig.14 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 25.7 kg / mol, and the molecular weight distribution is 2.6.

[0070] Example 8

[0071] The three raw materials of propiolic acid butanediol ester (1B), 4,4'-diaminodicyclohexylmethane (2C), and five-membered selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid ethylene glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated. The solvent was removed by filtration and vacuum drying to prepare a selenium-containing unsaturated polyester amide polymer (1B2C), and its nuclear magnetic resonance spectrum is shown as follows Fig.15 The polymer was subjected to GPC test, and the results were as follows Fig.16 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 21.2 kg / mol, and the molecular weight distribution is 2.4.

[0072] Example 9

[0073] The three raw materials of propiolic acid hexanediol ester (1C), 4,4'-diaminodicyclohexylmethane (2C), and five-membered selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid ethylene glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated. The solvent was removed by filtration and vacuum drying to prepare a selenium-containing unsaturated polyester amide polymer (1C2C), and its nuclear magnetic resonance spectrum is shown as follows Fig.17 The polymer was subjected to GPC test, and the results were as follows Fig.18 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 16.4 kg / mol, and the molecular weight distribution is 2.4.

[0074] Example 10

[0075] The three raw materials of propiolic acid glycol ester (1A), 1,8-diamino-3,6-dioxaoctane (2D), and penta-selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated. The solvent was removed by filtration, and vacuum drying was performed to prepare a selenium-containing unsaturated polyester amide polymer (1A2D), and its NMR spectrum was as follows: Fig.19 The polymer was subjected to GPC test, and the results were as follows Fig. 20 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 29.4 kg / mol, and the molecular weight distribution is 2.4.

[0076] Embodiment 11

[0077] The three raw materials of propiolic acid butanediol ester (1B), 1,8-diamino-3,6-dioxaoctane (2D), and penta-selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid ethylene glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated. The solvent was removed by filtration, and the selenium-containing unsaturated polyester amide polymer (1B2D) was prepared by vacuum drying. Its NMR spectrum is shown as follows Fig.21 The polymer was subjected to GPC test, and the results were as follows Fig. 22 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 34.7 kg / mol, and the molecular weight distribution is 2.2.

[0078] Example 12

[0079] The three raw materials of propiolic acid hexanediol ester (1C), 1,8-diamino-3,6-dioxaoctane (2D), and penta-selenolactone were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid ethylene glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated. The solvent was removed by filtration and vacuum drying to prepare the selenium-containing unsaturated polyester amide polymer (1C2D), and its NMR spectrum was as follows: Fig.23 The polymer was subjected to GPC test, and the results were as follows Fig.24 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 45.9 kg / mol, and the molecular weight distribution is 3.7.

[0080] Example 13

[0081] The three raw materials of propiolic acid glycol ester (1A), 4,7,10-trioxy-1,13-tridecanediamine (2E), and penta-selenolide were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated. The solvent was removed by filtration, and vacuum drying was performed to prepare a selenium-containing unsaturated polyester amide polymer (1A2E), and its NMR spectrum was as follows Fig.25 The polymer was subjected to GPC test, and the results were as follows Fig.26 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 37.3 kg / mol, and the molecular weight distribution is 1.7.

[0082] Embodiment 14

[0083] The three raw materials of propiolic acid butanediol ester (1B), 4,7,10-trioxy-1,13-tridecanediamine (2E), and penta-selenolide were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid ethylene glycol ester was 1 mol / L, reacted at room temperature for 3 hours, and a polymer precipitated. The solvent was removed by filtration and vacuum drying to prepare a selenium-containing unsaturated polyester amide polymer (1B2E), and its nuclear magnetic resonance spectrum is shown as follows Fig. 27 The polymer was subjected to GPC test, and the results were as follows Fig.28 As shown, the test results show that the weight average molecular weight of the polymer obtained in this example is 47.1 kg / mol, and the molecular weight distribution is 3.2.

[0084] Embodiment 15

[0085] The three raw materials of propiolic acid hexanediol ester (1C), 4,7,10-trioxy-1,13-tridecanediamine (2E), and penta-selenolide were added in a molar ratio of 1:1:2, added to a round-bottom flask, and mixed and dissolved with hexafluoroisopropanol as a solvent, wherein the concentration of propiolic acid ethylene glycol ester was 1 mol / L. The reaction was carried out at room temperature for 3 hours, and the polymer precipitated. The solvent was removed by filtration and vacuum drying to prepare a selenium-containing unsaturated polyester amide polymer (1C2E), and its nuclear magnetic resonance spectrum was as follows Fig.29 The polymer was subjected to GPC test, and the results were as follows Fig.30 As shown, the test results show 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 Case

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

[0088] Table 1

[0089]

[0090]

[0091] High refractive index polymers have shown 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 shading index of general organic polymers (generally 1.5-1.6) is relatively low, and aromatic heterocycles are usually introduced into the polymer chain, which also leads to problems in transparency, solubility and processability of the material. The present invention is based on the molar refractive index [R] value (11.17cm 3 ·mol-1 ), a high refractive index material without aromatic heterocycles was prepared. The polymer (1A2A) obtained in Example 1, the polymer (1B2C) obtained in Example 8, and the polymer (1B2D) obtained in Example 11 were tested for optical properties. The refractive index test results are as follows: Fig.33 It can be seen that the polymer has excellent optical properties, wherein the light shielding index of the polymer (1A2A) obtained in Example 1 is as high as 1.7660.

[0092] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing selenium-containing unsaturated polyester amide, characterized in that: The steps include: The diamine compound, propiolate and selenolactone are mixed and dissolved in an organic solvent to carry out 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); Among them, R 1 Selected from (CH2CH2O) x or an alkyl group having 2 to 20 carbon atoms, x is an integer between 2 and 10; R 2 Selected from (CH2CH2O) y , an alkyl group having 2 to 20 carbon atoms or a carbocyclic group having 6 to 20 carbon atoms, y is an integer between 2 and 10; m is an integer selected from 1 to 3, and n is a positive integer.

2. The method for preparing the selenium-containing unsaturated polyester amide according to claim 1, characterized in that: The molar ratio of the diamine compound, propiolate and selenolactone is (1-1.2): (1-1.2): (2-2.4).

3. The method for preparing the selenium-containing unsaturated polyester amide according to claim 2, characterized in that: The concentration of the propiolate is 0.5-2 mol / L.

4. The method for preparing the selenium-containing unsaturated polyester amide according to claim 1, characterized in that: The structural formula of the propiolate is: Among them, R 1 Selected from (CH2CH2O) x or an alkyl group having 2 to 20 carbon atoms, wherein x is an integer between 2 and 10.

5. The method for preparing the selenium-containing unsaturated polyester amide according to claim 1, characterized in that: The structural formula of the diamine compound is: Among them, R 2 Selected from (CH2CH2O) y , an alkyl group having 2-20 carbon atoms or a carbocyclic group having 6-20 carbon atoms, and y is an integer between 2-10.

6. The method for preparing the selenium-containing unsaturated polyester amide according to claim 1, characterized in that: The selenolactone is selected from One or more of the .

7. The method for preparing the selenium-containing unsaturated polyester amide according to claim 1, characterized in that: The temperature of the chemical reaction is 0-100°C and the time is 0.5-10h.

8. The method for preparing the selenium-containing unsaturated polyester amide according to claim 1, characterized in that: The method further comprises the steps of filtering and vacuum drying after the chemical reaction.

9. The method for preparing the selenium-containing unsaturated polyester amide according to claim 1, characterized in that: The organic solvent is selected from one or more of tetrahydrofuran, toluene and hexafluoroisopropanol.

10. A selenium-containing unsaturated polyester amide prepared by the preparation method according to any one of claims 1 to 9.

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