A polyamide-based thiourea compound and its preparation method and application

Abstract

The invention discloses a polyamide-based thiourea compound and a preparation method and application thereof. The invention comprises the following steps: mixing an isonitrile compound and a diamine compound, adding an organic solvent, dissolving and then adding carbon disulfide, stirring for the first time; then adding a dihydrazide compound, stirring for the second time to carry out a polymerization reaction, and obtaining the linear polyamide-based thiourea compound; mixing an isonitrile compound and a triamine compound, adding an organic solvent, dissolving and then adding carbon disulfide, stirring for the first time; then adding a dihydrazide compound, stirring for the second time to carry out a polymerization reaction, and obtaining the hyperbranched / cross-linked polyamide-based thiourea compound. The reaction operation of the invention is simple, can be carried out under the conditions of room temperature and air, has a high yield, and does not produce toxic and harmful byproducts; the obtained series of polyamide-based thioureas have better mechanical properties than ordinary polythioureas.

Description

Technical Field

[0001] The invention belongs to the technical fields of organic chemistry, polymer chemistry and materials science, and specifically relates to a polyamide-based thiourea compound and a preparation method and application thereof. Background Art

[0002] Polythiourea has attracted much attention due to its excellent properties, such as high refractive index, strong metal coordination ability, strong self-healing performance, excellent electrochemical properties and dielectric properties, etc. Compared with polyamide-based thiourea, each repeating unit has an additional amide group, which is very easy to form more heavy hydrogen bonds and supramolecular effects, etc., which will bring more other properties to the material. However, there are currently many studies on polythiourea (Nat. Commun. 2022, 13, 2633), while there is almost no research on polyamide-based thiourea. Based on this, we have developed a new method for preparing polyamide-based thiourea and developed an efficient and convenient polymerization system to achieve low-cost and large-scale preparation of polyamide-based thiourea, which is expected to promote its further development. Summary of the invention

[0003] In order to solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a polyamide-based thiourea compound.

[0004] Another object of the present invention is to provide a method for preparing the above-mentioned polyamide-thiourea compounds with different structures. In a solvent, an amine monomer, an isonitrile monomer, carbon disulfide and a hydrazide monomer are reacted, and polyamide-thiourea can be obtained by post-treatment. The present invention proposes for the first time a method for preparing a novel structural polymer, polyamide-thiourea, and has great advantages, such as the monomers used are all industrial raw materials, which can be directly purchased at low cost, and can also be mass-produced at the gram level; the reaction operation is simple, the conditions are mild, and it can be carried out at room temperature and air, the polymerization reaction yield is high, and no toxic or harmful by-products are produced; the obtained series of polyamide-thioureas also have excellent mechanical properties and luminescent properties, and can be applied to the fields of mechanical materials and optical materials, promoting the further development of polyamide-thiourea compounds.

[0005] Another object of the present invention is to provide applications of the polyamide-thiourea compounds.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A one-pot method for preparing polyamide-based thiourea compounds, wherein the polyamide-based thiourea compounds include linear polyamide-based thiourea compounds and hyperbranched / cross-linked polyamide-based thiourea compounds;

[0008] (1) The preparation method of the linear polyamide-based thiourea compound comprises the following steps:

[0009] An isonitrile compound and a diamine compound are mixed, an organic solvent is added, and carbon disulfide is added after dissolution, and stirred for the first time for reaction; a dihydrazide compound is then added, and stirred for the second time for polymerization reaction to obtain the linear polyamide-based thiourea compound;

[0010] (2) The preparation method of the hyperbranched / cross-linked polyamide-based thiourea compound comprises the following steps:

[0011] An isonitrile compound and a triamine compound are mixed, an organic solvent is added, and carbon disulfide is added after the mixture is dissolved, and the mixture is stirred for the first time for reaction; a dihydrazide compound is then added, and the mixture is stirred for the second time for polymerization reaction to obtain the hyperbranched / cross-linked polyamide-based thiourea compound;

[0012] The structural formula of the dihydrazide compound is:

[0013]

[0014] The structural formula of the diamine compound is:

[0015]

[0016] The structural formula of the triamine compound is:

[0017]

[0018] Among them, R 1 is an organic group, R 2 is an organic group, R 3 is an organic group, R 4 It is an organic group.

[0019] Preferably, R 1 is an alkylene group, an alkyleneoxy group or an arylene group, R 2 is an alkylene group or an arylene group, R 3 is an alkylene group or an arylene group, R 4 It is an alkylene group, an alkoxy group or an arylene group.

[0020] Preferably, in method (1), the molar ratio of the amino group of the diamine compound: the isonitrile functional group of the isonitrile compound: the carbon disulfide: the hydrazide group of the dihydrazide compound is 1-1.2: 1-1.2: 1: 1-1.2;

[0021] Preferably, the concentration of the isonitrile compound in the organic solvent in method (1) is 0.5 to 1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N-dimethylformamide;

[0022] Preferably, in method (2), the molar ratio of the amino group of the tertiary amine compound: the isonitrile functional group of the isonitrile compound: the carbon disulfide: the hydrazide group of the dihydrazide compound is 1-1.2: 1-1.2: 1: 1-1.2;

[0023] Preferably, in method (2), the concentration of the isonitrile compound in the organic solvent is 0.5 to 1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N-dimethylformamide.

[0024] Preferably, the isonitrile compound is a monoisocyanate compound or a diisocyanate compound;

[0025] Preferably, the dihydrazide compound is selected from any one of the following:

[0026]

[0027] Wherein p is an integer from 1 to 20.

[0028] Preferably, the isonitrile compound is selected from any one of the following:

[0029]

[0030] Among them, R 5 represents an alkylene group, an alkyleneoxy group or an aromatic group.

[0031] Preferably, the diamine compound is selected from any one of the following:

[0032]

[0033] Wherein, j and k are integers ranging from 1 to 20;

[0034] The triamine compound is selected from any one of the following:

[0035]

[0036] Here, h is an integer from 1 to 20.

[0037] Preferably, the rotation speed of the first stirring and the second stirring in method (1) is 300-600 rpm, the time of the first stirring is 1-5 h, and the time of the second stirring is 5-12 h;

[0038] Preferably, the rotation speed of the first stirring and the second stirring in method (2) is 300-600 rpm, the time of the first stirring is 1-5 h, and the time of the second stirring is 5-12 h.

[0039] Preferably, after the polymerization reaction in methods (1) and (2), the reaction mother liquor is added to a precipitant for precipitation, and the precipitate is collected and dried to a constant weight; the precipitant is methanol or a mixed solution of n-hexane / dichloromethane;

[0040] Preferably, the first stirring reaction and the second stirring polymerization reaction in methods (1) and (2) are both carried out at room temperature; the room temperature is 20 to 30° C.;

[0041] Preferably, methods (1) and (2) are carried out under air conditions.

[0042] A polyamide-based thiourea compound is prepared by the above preparation method.

[0043] Preferably, the polyamide-based thiourea compounds include linear polyamide-based thiourea compounds of Formula 1, Formula 2, Formula 3, and Formula 4 and hyperbranched / cross-linked polyamide-based thiourea compounds of Formula 5, Formula 6, Formula 7, and Formula 8;

[0044]

[0045]

[0046] Among them, m, n, and i are integers between 2 and 400.

[0047] The above-mentioned polyamide-based thiourea compounds are used as mechanical materials, self-repairing materials and optoelectronic materials.

[0048] Compared with the existing technology, the present invention has the following beneficial effects:

[0049] (1) The raw materials for the preparation method of the present invention are easily available and can be directly purchased commercially at a low price; the polymerization conditions are mild, the process is simple, and the polymerization efficiency is high.

[0050] (2) The preparation method of the present invention does not require any catalyst, the reaction can be carried out under room temperature and air conditions, and the product can be prepared on a large scale at the gram level.

[0051] (3) The preparation method of the present invention has good universality and can be applied to a variety of different types of monomers.

[0052] (4) The polyamide-based thiourea compounds prepared by the present invention have excellent self-healing properties and mechanical properties, and have particularly outstanding properties compared with existing materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 These are hydrogen nuclear magnetic resonance spectrum and carbon nuclear magnetic resonance spectrum of the polyamide-thiourea compound prepared in Example 1 of the present invention in deuterated DMSO.

[0054] Figure 2 This is a thermal gravimetric curve of the polyamide-based thiourea compound prepared in Example 1 of the present invention.

[0055] Figure 3 1 and 2 are the tensile curves of the polymer P3 film of Example 3 and the ordinary polythiourea of ​​Comparative Example 1.

[0056] Figure 4 This is the excitation diagram of the solid state polyamide thiourea P3 prepared in Example 3 at a wavelength of 280-400nm. DETAILED DESCRIPTION

[0057] The present invention is further described in detail below in conjunction with specific embodiments and drawings, but the embodiments of the present invention are not limited thereto.

[0058] Example 1

[0059] A polyamide-based thiourea compound, the structural formula of which is shown in P1:

[0060]

[0061] The polyamide-based thiourea compound is prepared by direct one-pot reaction of amine, isonitrile, carbon disulfide and hydrazide, and the reaction equation is as follows:

[0062]

[0063] Among them, all the monomers used can be purchased from the market. 1a is 1,8-octanediamine, 2 is carbon disulfide, both of which are purchased from Anaiji Chemical in this example. 3 is p-toluenesulfonylmethyl isocyanide, which is purchased from Bit Pharmaceutical Technology Co., Ltd. in this example. 4a is dihydrazide carbonate, which is also purchased from Anaiji Chemical in this example.

[0064] The polyamide-thiourea compound preparation steps are as follows:

[0065] In a 10 ml polymerization tube, monomers 1a (144 mg, 1 mmol) and 3 (390 mg, 2 mmol) were added in sequence, and then 4 mL of dimethyl sulfoxide was added and stirred at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol) was added and stirred at 500 rpm at room temperature for 3 hours, and then 4a (90 mg, 1 mmol) was added and stirred for 12 hours. After the reaction was completed, the reaction mother liquor was added dropwise to methanol, and then allowed to stand, filtered, and dried to obtain the polyamide thiourea compound P1.

[0066] The results of determination and analysis showed that the yield of the polyamide-based thiourea compound P1 was 91%, the weight average molecular weight was 6,000, and the molecular weight distribution was 1.20.

[0067] The H NMR spectrum of the polyamide-based thiourea compound is shown in Figure 1 The A in the graphene has a carbon NMR spectrum. Figure 1 B in Figure 1 The chemical shifts of 8.94, 8.52 and 7.95 ppm in A correspond to the characteristic peaks of hydrogen atoms on -NH of the polyamide-based thiourea compound. Figure 1 The chemical shift of 182.33 ppm in B corresponds to the characteristic peak of the carbon atom on the polyamide-based thiourea compound C=S. Figure 1 The chemical shift of 157.11 ppm in B corresponds to the characteristic peak of the carbon atom on C=O of the polyamide thiourea compound, so it can be determined that the polymer is a polyamide thiourea compound. Figure 2 : is the thermal weight loss curve of P1. It can be seen from the figure that the temperature corresponding to the weight loss of 5% is 205°C, indicating that the polyamide-based thiourea compound P1 has good thermal stability.

[0068] Example 2

[0069] A polyamide-based thiourea compound, the structural formula of which is shown in P2:

[0070]

[0071] The polyamide-based thiourea compound is prepared by direct one-pot reaction of amine, isonitrile, carbon disulfide and hydrazide, and the reaction equation is as shown in Formula (II):

[0072]

[0073] Among them, all the monomers used can be purchased from the market. 1a is 1,8-octanediamine, 2 is carbon disulfide, both of which are purchased from Anaiji Chemical in this example. 3 is p-toluenesulfonylmethyl isocyanide, which is purchased from Bit Pharmaceutical Technology Co., Ltd. in this example. 4b is thiocarbonic acid dihydrazide, which is also purchased from Anaiji Chemical in this example.

[0074] The polyamide-thiourea compound preparation steps are as follows:

[0075] In a 10 ml polymerization tube, monomers 1a (144 mg, 1 mmol) and 3 (390 mg, 2 mmol) were added in sequence, and then 4 mL of dimethyl sulfoxide was added and stirred at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol) was added and stirred at 500 rpm at room temperature for 3 hours, and then 4b (106 mg, 1 mmol) was added and stirred for 12 hours. After the reaction was completed, the reaction mother liquor was added dropwise into methanol, and then allowed to stand, filtered, and dried to obtain the polyamide thiourea compound P2.

[0076] According to the measurement and analysis, the yield of the final product polyamide-based thiourea compound P2 is 88%, the weight average molecular weight is 8100, and the molecular weight distribution is 1.24.

[0077] Example 3

[0078] A polyamide-based thiourea compound, the structural formula of which is shown in P3:

[0079]

[0080] The polyamide-based thiourea compound is prepared by direct one-pot reaction of amine, isonitrile, carbon disulfide and hydrazide, and the reaction equation is as shown in Formula (III):

[0081]

[0082] Among them, all the monomers used can be purchased from the market. 1b is 1,2-bis(2-aminoethoxy)ethane, 2 is carbon disulfide, both of which are purchased from Anaiji Chemical in this example. 3 is p-toluenesulfonylmethyl isocyanide, which is purchased from Bit Pharmaceutical Technology Co., Ltd. in this example. 4c is adipic acid hydrazide, which is also purchased from Anaiji Chemical in this example.

[0083] The polyamide-thiourea compound preparation steps are as follows:

[0084] In a 10 ml polymerization tube, monomers 1b (148 mg, 1 mmol) and 3 (390 mg, 2 mmol) were added in sequence, and then 4 mL of dimethyl sulfoxide was added and stirred at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol) was added and stirred at 500 rpm at room temperature for 3 hours, and then 4c (174 mg, 1 mmol) was added and continued to stir for 12 hours. After the reaction was completed, the reaction mother liquor was added dropwise into methanol, and then allowed to stand, filtered, and dried to obtain the polyamide thiourea compound P3.

[0085] According to the measurement and analysis, the yield of the final product polyamide-based thiourea compound P3 is 98%, the weight average molecular weight is 22200, and the molecular weight distribution is 1.36.

[0086] Example 4

[0087] A polyamide-based thiourea compound, the structural formula of which is shown in P4:

[0088]

[0089] The polyamide-based thiourea compound is prepared by direct one-pot reaction of amine, isonitrile, carbon disulfide and hydrazide, and the reaction equation is as shown in Formula (IV):

[0090]

[0091] Among them, all the monomers used can be purchased from the market. 1a is 1,8-octanediamine, 2 is carbon disulfide, both of which are purchased from Anaiji Chemical in this example. 3 is p-toluenesulfonylmethyl isocyanide, which is purchased from Bit Pharmaceutical Technology Co., Ltd. in this example. 4d is 4,4-oxybisbenzenesulfonylhydrazide, which is also purchased from Anaiji Chemical in this example.

[0092] The polyamide-thiourea compound preparation steps are as follows:

[0093] In a 10 ml polymerization tube, monomers 1a (144 mg, 1 mmol) and 3 (390 mg, 2 mmol) were added in sequence, and then 4 mL of dimethyl sulfoxide was added and stirred at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol) was added and stirred at 500 rpm at room temperature for 3 hours, and then 4d (358 mg, 1 mmol) was added and stirred for 12 hours. After the reaction was completed, the reaction mother liquor was added dropwise to methanol, and then allowed to stand, filtered, and dried to obtain the polyamide thiourea compound P4.

[0094] According to the measurement and analysis, the yield of the final product polyamide-based thiourea compound P4 is 94%, the weight average molecular weight is 10,000, and the molecular weight distribution is 1.22.

[0095] Example 5

[0096] A hyperbranched / cross-linked polyamide-based thiourea compound, the structural formula of which is shown in P5:

[0097]

[0098] The hyperbranched polyamide-based thiourea compound is prepared by direct one-pot reaction of amine, isonitrile, carbon disulfide and hydrazide, and the reaction equation is as shown in Formula (V):

[0099]

[0100] Among them, all the monomers used can be purchased from the market. 1b is tris (3-aminopropyl) amine, 2 is carbon disulfide, both of which are purchased from Anaiji Chemical in this example. 3 is p-toluenesulfonylmethyl isocyanide, which is purchased from Bit Pharmaceutical Technology Co., Ltd. in this example. 4c is adipic acid hydrazide, which is also purchased from Anaiji Chemical in this example.

[0101] The polyamide-thiourea compound preparation steps are as follows:

[0102] In a 10 ml polymerization tube, monomers 1c (125 mg, 0.67 mmol) and 3 (390 mg, 2 mmol) were added in sequence, and then 4 mL of dimethyl sulfoxide was added and stirred at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol) was added and stirred at 500 rpm at room temperature for 3 hours, and then 4c (174 mg, 1 mmol) was added and stirred for 12 hours. After the reaction was completed, the reaction mother liquor was added dropwise to methanol, and then allowed to stand, filtered, and dried to obtain the polyamide thiourea compound P5.

[0103] According to the determination and analysis, the yield of the final product polyamide-based thiourea compound P5 is 95%, the weight average molecular weight is 18300, and the molecular weight distribution is 1.32.

[0104] Comparative Example 1

[0105]

[0106] In a 10 ml polymerization tube, monomers 1d (136 mg, 1 mmol), 1b (148 mg, 1 mmol), and 3 (390 mg, 2 mmol) were added in sequence, and then 4 mL of dimethyl sulfoxide was added, and stirred at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol) was added, and stirring continued at room temperature at a rate of 500 rpm for 12 hours. After the reaction was completed, the reaction mother liquor was added dropwise to a mixed solution of n-hexane and dichloromethane, and then allowed to stand, filtered, and dried to obtain the polythiourea compound P6. After measurement and analysis, the yield of the final product polyamide-based thiourea compound P6 was 92%, the weight average molecular weight was 203 00, and the molecular weight distribution was 1.52.

[0107] Self-healing properties of polymers

[0108] The series of polymers prepared by the invention have excellent self-repairing properties and mechanical properties.

[0109] Take the polyamide-based thiourea P3 prepared in Example 3 as an example. A hard rectangular sheet (2*1*0.2 cm) was obtained by heating the mold at 120°C for 3 hours and cooling to room temperature. After the sheet was cut, the two sections were repaired at 70°C for 3 minutes to repair it into a complete piece. The repaired sheet can withstand a weight of 1 kg without breaking, which reflects the excellent self-healing properties of this type of polymer.

[0110] Mechanical properties of polymers

[0111] The series of polymers prepared by the invention have excellent mechanical properties.

[0112] Take the polyamide thiourea P3 prepared in Example 3 as an example. The polymer P3 is dissolved in DMF, and a film is scraped by a film scraper. After drying in a vacuum oven, a transparent film of P3 is obtained. The film is subjected to a tensile test, and its stress is as high as 14.7 Mpa ( Figure 3 ), compared with the common polythiourea compound in comparative example 1, the stress is greatly improved, showing more excellent mechanical properties.

[0113] Luminescent properties of polymers

[0114] The series of polymers prepared by the present invention all have luminescent properties. For example, the polyamide-based thiourea P3 prepared in Example 3 has a solution and a solid state ( Figure 4 )When excited by light with a wavelength of 280-400nm, it will emit blue fluorescence and is a new type of non-traditional luminescent material.

[0115] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for preparing polyamide-based thiourea compounds in one pot, characterized in that: The polyamide-thiourea compounds include linear polyamide-thiourea compounds and hyperbranched / cross-linked polyamide-thiourea compounds; (1) The preparation method of the linear polyamide-based thiourea compound comprises the following steps: Under air conditions, an isonitrile compound and a diamine compound are mixed, an organic solvent is added, and carbon disulfide is added after dissolution, and a first stirring reaction is performed; a dihydrazide compound is then added, and a second stirring polymerization reaction is performed to obtain the linear polyamide-based thiourea compound; the first stirring reaction and the second stirring polymerization reaction are both performed at room temperature; the first stirring time is 1 to 5 hours, and the second stirring time is 5 to 12 hours; (2) The preparation method of the hyperbranched / cross-linked polyamide-based thiourea compound comprises the following steps: Under air conditions, isonitrile compounds and triamine compounds are mixed, an organic solvent is added, carbon disulfide is added after dissolution, and a first stirring reaction is performed; a dihydrazide compound is then added, and a second stirring polymerization reaction is performed to obtain the hyperbranched / cross-linked polyamide-based thiourea compound; the first stirring reaction and the second stirring polymerization reaction are both performed at room temperature; the first stirring time is 1 to 5 hours, and the second stirring time is 5 to 12 hours; The isonitrile compound is a monoisocyanate compound or a diisocyanate compound; The structural formula of the dihydrazide compound is: The structural formula of the diamine compound is: The structural formula of the triamine compound is: Among them, R 1 is an alkylene group, an alkyleneoxy group or an arylene group, R 2 is an alkylene group or an arylene group, R 3 is an alkylene group or an arylene group, R 4 It is an alkylene group, an alkoxyene group or an arylene group.

2. A method for preparing polyamide-based thiourea compounds in one pot, characterized in that: The polyamide-thiourea compounds include linear polyamide-thiourea compounds and hyperbranched / cross-linked polyamide-thiourea compounds; (1) The preparation method of the linear polyamide-based thiourea compound comprises the following steps: Under air conditions, an isonitrile compound and a diamine compound are mixed, an organic solvent is added, and carbon disulfide is added after dissolution, and a first stirring reaction is performed; a dihydrazide compound is then added, and a second stirring polymerization reaction is performed to obtain the linear polyamide-based thiourea compound; the first stirring reaction and the second stirring polymerization reaction are both performed at room temperature; the first stirring time is 1 to 5 hours, and the second stirring time is 5 to 12 hours; (2) The preparation method of the hyperbranched / cross-linked polyamide-based thiourea compound comprises the following steps: Under air conditions, isonitrile compounds and triamine compounds are mixed, an organic solvent is added, carbon disulfide is added after dissolution, and a first stirring reaction is performed; a dihydrazide compound is then added, and a second stirring polymerization reaction is performed to obtain the hyperbranched / cross-linked polyamide-based thiourea compound; the first stirring reaction and the second stirring polymerization reaction are both performed at room temperature; the first stirring time is 1 to 5 hours, and the second stirring time is 5 to 12 hours; The isonitrile compound is a monoisocyanate compound or a diisocyanate compound; The dihydrazide compound is selected from any one of the following: Where p is an integer from 1 to 20; The diamine compound is selected from any one of the following: Wherein, j and k are integers ranging from 1 to 20; The triamine compound is selected from any one of the following: Here, h is an integer from 1 to 20.

3. The method for preparing polyamidothiourea compounds in one pot according to claim 1 or 2, characterized in that: The isonitrile compound is selected from any one of the following: Among them, R 5 represents an alkylene group, an alkyleneoxy group or an aromatic group.

4. The method for preparing polyamidothiourea compounds in one pot according to claim 1 or 2, characterized in that: Method (1) The molar ratio of the amino group of the diamine compound: the isonitrile functional group of the isonitrile compound: the carbon disulfide: the hydrazide group of the dihydrazide compound is 1-1.2: 1-1.2: 1: 1-1.2; Method (1) The concentration of the isonitrile compound in the organic solvent is 0.5 to 1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N-dimethylformamide; Method (2) The molar ratio of the amino group of the ternary amine compound: the isonitrile functional group of the isonitrile compound: the carbon disulfide: the hydrazide group of the dihydrazide compound is 1-1.2: 1-1.2: 1: 1-1.2; In method (2), the concentration of the isonitrile compound in the organic solvent is 0.5 to 1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N-dimethylformamide.

5. The method for preparing polyamidothiourea compounds in one pot according to claim 1 or 2, characterized in that: The rotation speed of the first stirring and the second stirring in method (1) is 300-600 rpm; The rotation speed of the first stirring and the second stirring in method (2) is 300-600 rpm.

6. The one-pot method for preparing polyamidothiourea compounds according to claim 1 or 2, characterized in that: After the polymerization reaction in methods (1) and (2), the reaction mother liquor is added to a precipitant for precipitation, and the precipitate is collected and dried to a constant weight; the precipitant is methanol or a mixed solution of n-hexane / dichloromethane; The room temperature in methods (1) and (2) is 20 to 30°C.

7. A polyamide-thiourea compound, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 6.

8. The polyamidothiourea compound according to claim 7, characterized in that: The polyamide-based thiourea compounds include linear polyamide-based thiourea compounds of formula 1, formula 2, formula 3, and formula 4, and hyperbranched / cross-linked polyamide-based thiourea compounds of formula 5, formula 6, formula 7, and formula 8; Among them, m, n, and i are integers between 2 and 400.

9. Use of the polyamide thiourea compound according to any one of claims 7 to 8 as a mechanical material and a photoelectric material.

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