Preparation method and application of dithioamino acid ester / polydithioamino acid ester compound

Abstract

The application discloses a preparation method and application of a dithio-carbamate compound / polypolydithio-carbamate compound. The dithio-carbamate compound / polypolydithio-carbamate compound is obtained by reacting an amine compound, an isonitrile compound, carbon disulfide and a mercaptan compound in an organic solvent in the presence of a base. The raw materials used in the application are all industrial raw materials, which can be directly purchased and have low cost, and can be produced in a large scale of gram grade. The polymerization operation is simple, the yield is high, the reaction condition is mild, no metal catalyst is needed, the reaction can be carried out at room temperature and in the air, and no toxic and harmful by-products are generated. The polypolydithio-carbamate compound obtained by the application also has excellent mechanical properties and luminescent properties, and can be applied to the fields of mechanical materials and optoelectronic devices, thereby promoting the further development of the polypolydithio-carbamate compound.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic chemistry, polymer chemistry and materials science, and particularly relates to a preparation method and application of a dithio carbamate compound / polyl dithio carbamate compound. BACKGROUND

[0002] Dithio carbamates and their derivatives have a wide range of biological activities and have become the focus of research in the chemical and pharmaceutical fields in recent years, and are widely used in the fields of pesticides and biological medicines. At present, although there are many synthesis methods, they all have certain defects. For example, dithio carbamates can be prepared by reacting amine with thiophosgene; or by reacting carbon disulfide with primary amine or secondary amine and halogenated alkane under the catalysis of sodium hydroxide or potassium hydroxide. However, thiophosgene is highly toxic and difficult to obtain, and the reaction environment is strongly alkaline, which limits the reaction substrates from containing groups sensitive to alkali. Therefore, it is extremely important to develop a new method for synthesizing dithio carbamates under mild conditions.

[0003] Polyl dithio carbamates have attracted much attention due to their excellent properties. Compared with other sulfur-containing polymers, they have more sulfur content, and the hydrogen bond of the dithio carbamate moiety is weaker, which brings polyl dithio carbamates the advantages of higher refractive index, strong metal coordination ability, lower glass transition temperature and excellent self-healing performance. However, the research on polyl dithio carbamates is still quite limited, which is due to the limitation of the synthesis method. At present, polyl dithio carbamates are basically prepared by diisothiocyanate and dithiol, as shown in formula (I). Due to the limited types of commercially available isothiocyanates and their high price, the synthesis is relatively difficult, and the diversity of monomers is severely limited, which seriously limits the development and further application of this type of polymers (J. Polym. Sci., Part A: Polym. Chem., 2010, 48, 845; Macromolecules 2019, 52, 6080.). Therefore, it is urgent to explore a new method for preparing polyl dithio carbamates and develop a more efficient and convenient polymerization system. Carbon disulfide is an important industrial raw material and is widely used in the fields of artificial fibers, glass paper, chemical industry, pesticides, dyes, oil refining, etc. However, these fields basically use carbon disulfide as a solvent or extractant, and rarely use its chemical properties to directly convert it into useful products to realize its high-value-added utilization. Using carbon disulfide and some commercial monomers to realize the low-cost and large-scale preparation of polyl dithio carbamates is expected to promote its further development.

[0004] SUMMARY

[0005] In order to solve the defects and deficiencies of the prior art, the primary purpose of the present application is to provide a preparation method of dithiocarbamate / polydithiocarbamate compounds. In a solvent, amine, isocyanide, carbon disulfide and mercaptan are reacted in the presence of a base, and after treatment, dithiocarbamate / polydithiocarbamate compounds are obtained. Compared with the existing method, the present application has great advantages, such as the use of raw materials which are all industrial raw materials and can be directly purchased and have low cost, large-scale production of grams can be carried out, simple polymerization operation, high yield, mild reaction conditions, no need for metal catalysts, reaction under the conditions of room temperature and air, and no toxic and harmful by-products are generated. On the other hand, the dithiocarbamate functional group has good dynamic covalent characteristics, which also brings potential self-repairing performance and degradable performance to the polymer, and is expected to be applied in the field of intelligent materials. The obtained series of polydithiocarbamate also has excellent self-repairing performance and luminescent performance, and can be applied in the fields of self-repairing and optoelectronic devices, promoting the further development of polydithiocarbamate compounds.

[0006] Another purpose of the present application is to provide the application of the above-mentioned polydithiocarbamate compounds.

[0007] The purpose of the present application is achieved by the following technical solutions.

[0008] A one-pot preparation method of dithiocarbamate / polydithiocarbamate compounds, characterized in that the polydithiocarbamate compounds include linear polydithiocarbamate compounds and hyperbranched / crosslinked polydithiocarbamate compounds.

[0009] (1) The preparation method of the linear polydithiocarbamate compounds includes the following steps:

[0010] The isocyanide compound and the diamine compound are mixed, an organic solvent is added, after dissolution, carbon disulfide, a binary mercaptan compound and a base are added, and the polymerization reaction is carried out under stirring to prepare the linear polydithiocarbamate compound.

[0011] (2) The preparation method of the hyperbranched / crosslinked polydithiocarbamate compound includes the following steps:

[0012] The isocyanide compound and the diamine compound are mixed, an organic solvent is added, after dissolution, carbon disulfide, a binary mercaptan compound and a base are added, and the polymerization reaction is carried out under stirring to prepare the linear polydithiocarbamate compound.

[0013] (3) The preparation method of the dithiocarbamate compound includes the following steps:

[0014] The dithio carbamate compound is prepared by mixing isonitrile compound and amine compound, adding organic solvent, dissolving, adding carbon disulfide, thiol compound and alkali, and stirring to react.

[0015] The structure of the diatomic amine compound is:

[0016] H2N-R 1 -NH2

[0017] The structure of the diatomic thiol compound is:

[0018] HS-R 2 -SH

[0019] The structure of the triatomic amine compound is:

[0020]

[0021] The structure of the monoatomic amine compound is:

[0022] R 5 -NH2

[0023] The structure of the monoatomic thiol compound is:

[0024] R 6 -SH

[0025] wherein, R 1 is an organic group, R 2 is an organic group, R 3 is an organic group, R 5 is an organic group, R 6 is an organic group.

[0026] Preferably, the R 1 is alkylene, alkyloxy or arylene, R 2 is alkylene, alkyloxy or arylene, R 3 is alkylene, alkyloxy or arylene, R 5 is alkyl, alkoxy or aryl, R 6 is alkyl, alkoxy or aryl.

[0027] Preferably, the structure of the linear polydithio carbamate compound is:

[0028]

[0029] The structure of the hyperbranched / crosslinked polydithio carbamate compound is:

[0030]

[0031] wherein, m, n, i are integers between 2 and 400;

[0032] The structure of the dithio carbamate compound is:

[0033]

[0034] Preferably, the molar ratio of the amino group of the diamine compound: the isonitrile functional group of the isonitrile compound: carbon disulfide: the mercapto group of the mercaptan compound in the method (1) is 1-1.2: 1-1.2: 1: 1-1.2;

[0035] Preferably, the concentration of the isonitrile compound in the organic solvent in the method (1) is 0.5-1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N dimethyl formamide;

[0036] Preferably, the molar ratio of the amino group of the triamine compound: the isonitrile functional group of the isonitrile compound: carbon disulfide: the mercapto group of the mercaptan compound in the method (2) is 1-1.2: 1-1.2: 1: 1-1.2;

[0037] Preferably, the concentration of the isonitrile compound in the organic solvent in the method (2) is 0.5-1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N dimethyl formamide;

[0038] Preferably, the molar ratio of the amino group of the amine compound: the isonitrile functional group of the isonitrile compound: carbon disulfide: the mercapto group of the mercaptan compound in the method (3) is 1-1.2: 1-1.2: 1: 1-1.2;

[0039] Preferably, the concentration of the isonitrile compound in the organic solvent in the method (3) is 0.5-1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N dimethyl formamide.

[0040] Preferably, the isonitrile compound is a monoisocyanide compound or a diisonitrile compound;

[0041] Preferably, the monoisocyanide compound is selected from any one of the following:

[0042]

[0043] wherein, i is an integer between 1 and 20;

[0044] Preferably, the diisocyanide compound is selected from any one of the following:

[0045]

[0046] wherein e, k are integers from 1 to 20.

[0047] Preferably, the isonitrile compound is selected from any one of the following:

[0048]

[0049] wherein R 4 represents an alkylene, alkyleneoxy or arylene group. Preferably, the monoamine compound is selected from any one of the following:

[0050]

[0051] wherein k is an integer from 1 to 20;

[0052] Preferably, the diamine compound is selected from any one of the following:

[0053]

[0054] wherein j, k are integers from 1 to 20;

[0055] Preferably, the triamine compound is selected from any one of the following:

[0056]

[0057] wherein h is an integer from 1 to 20.

[0058] Preferably, the base in the methods (1), (2) and (3) is one of triethylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and the amount of the base is 5% to 20% of the amount of substance of the amino group of the monoamine compound, the amino group of the diamine compound or the amino group of the triamine compound.

[0059] Preferably, the stirring speed in the methods (1), (2) and (3) is 300 to 600 rpm, and the reaction time is 2 to 24 h.

[0060] Preferably, after the reaction in the methods (1), (2) and (3) is completed, the reaction mother liquor is added to a precipitant for precipitation, and the precipitate is collected and dried to constant weight; the precipitant is a mixed solution of methanol or n-hexane / dichloromethane.

[0061] Preferably, the reaction in the methods (1), (2) and (3) is carried out at room temperature; the room temperature is 20 to 30°C.

[0062] Preferably, the methods (1), (2) and (3) are carried out under air conditions.

[0063] The polydithiocarbamate compound prepared by the preparation method has applications in mechanical materials and photoelectric materials.

[0064] Compared with the prior art, the polydithiocarbamate compound prepared by the preparation method has the following beneficial effects:

[0065] (1) The raw materials for the preparation method are easy to obtain, can be directly purchased commercially and are low in price; the polymerization conditions are mild, the process is simple and the polymerization efficiency is high.

[0066] (2) The preparation method does not require any catalyst, and the reaction can be carried out at room temperature under air conditions, and large-scale preparation of the product can be carried out.

[0067] (3) The preparation method has good universality and can be applied to various types of monomers.

[0068] (4) The polydithiocarbamate compound prepared by the preparation method has excellent mechanical properties, and is a non-traditional luminescent material, which has particularly outstanding properties compared with existing materials. BRIEF DESCRIPTION OF DRAWINGS

[0069] Figure 1 NMR hydrogen spectrum and NMR carbon spectrum of the polydithiocarbamate compound prepared for Example 1 of the present application in deuterated DMSO.

[0070] Figure 2 Thermogravimetric curve of the polydithiocarbamate compound prepared for Example 1 of the present application.

[0071] Figure 3 Mechanical property test diagram of the polydithiocarbamate P3 prepared for Example 3.

[0072] Figure 4 Self-repairing performance diagram of the polydithiocarbamate P3 prepared for Example 3.

[0073] Figure 5 Excitation diagram of the polydithiocarbamate P3 prepared for Example 3 in a solid state under 280-400 nm wavelength light.

[0074] Figure 6 NMR hydrogen spectrum and NMR carbon spectrum of the dithiocarbamate compound prepared for Example 5 of the present application in deuterated DMSO. DETAILED DESCRIPTION

[0075] The present application will be further described in detail below in combination with specific examples and drawings, but the embodiments of the present application are not limited thereto.

[0076] Example 1

[0077] A symmetrical polydithiocarbamate compound, whose structural formula is shown as P1:

[0078]

[0079] The polydithiocarbamate compound is prepared by direct one-pot reaction of amine, carbon disulfide, isocyanide and thiol, and the reaction equation is shown as formula (II):

[0080]

[0081] In the formula, the monomers used can be purchased from the market. 1a is 1,4-xylylenediamine, and 2 is carbon disulfide, both of which are purchased from Angene Chemical in the present example. 3 is p-toluenesulfonylmethyl isocyanide, which is purchased from Bid Pharmatech Co., Ltd. in the present example. 4a is 1,4-xylyl mercaptan, which is also purchased from Angene Chemical in the present example.

[0082] The preparation steps of the polydithiocarbamate compound are as follows:

[0083] In a 10-milliliter polymerization tube, monomer 1a (136 mg, 1 mmol) and 3 (390 mg, 2 mmol) were sequentially added, followed by 2 mL of dimethyl sulfoxide, and stirred at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol), 4a (170 mg, 1 mmol) and triethylamine (10 mg, 0.1 mmol) were added, and the stirring was continued at a speed of 500 rpm for 12 hours at room temperature. After the reaction was completed, the reaction mother liquor was added dropwise into methanol, and then left to stand, filtered and dried to obtain the polydithiocarbamate compound P1.

[0084] According to the measurement and analysis, the yield of the polydithiocarbamate compound P1 is 99%, the weight average molecular weight is 16 600, and the molecular weight distribution is 1.36. The hydrogen spectrum of the nuclear magnetic resonance spectrum of the polydithiocarbamate compound is shown as A in Figure 1 , the carbon spectrum of the nuclear magnetic resonance spectrum is shown as B in Figure 1 , Figure 1 The chemical shift of 10.45 ppm in A in Figure 1 corresponds to the characteristic peak of the hydrogen atom on the polydithiocarbamate compound-NH, Figure 2 The chemical shift of 196.77 ppm in B in Figure 2 corresponds to the characteristic peak of the carbon atom on the polydithiocarbamate compound C=S, so it can be determined that the polymer is a polydithiocarbamate compound. In addition,

[0085] Example 2

[0086] A polydithiocarbamate compound, whose structural formula is shown as P2:

[0087]

[0088] The polydithiocarbamate compound is prepared by direct one-pot reaction of amine, carbon disulfide, isonitrile and thiol, and the reaction equation is shown as formula (three):

[0089]

[0090] Among them, the monomers used can be purchased from the market. 1a is 1,8-octanediamine, 2 is carbon disulfide, both of which are purchased from Angene Chemical in this example. 3 is p-toluenesulfonylmethyl isonitrile, which is purchased from Bid Pharmatech Co., Ltd. in this example. 4b is 1,8-octanethiol, which is also purchased from Angene Chemical in this example.

[0091] The preparation steps of the polydithiocarbamate compound are as follows:

[0092] In a 10-milliliter polymerization tube, monomer 1b (144 mg, 1 mmol) and 3 (390 mg, 2 mmol) were added in sequence, followed by 2 mL of dimethyl sulfoxide, and stirred at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol), 4b (178 mg, 1 mmol) and triethylamine (10 mg, 0.1 mmol) were added, and the stirring was continued at room temperature at a speed of 500 rpm for 12 hours. After the reaction was completed, the reaction mother liquor was added dropwise into methanol, and then left to stand, filtered and dried to obtain the polydithiocarbamate compound P2.

[0093] Determination and analysis showed that the yield of the polydithiocarbamate compound P2 was 93%, the weight average molecular weight was 18 300, and the molecular weight distribution was 1.66.

[0094] Example 3

[0095] A polydithiocarbamate compound, whose structural formula is shown as P3:

[0096]

[0097] The polydithiocarbamate compound is prepared by direct one-pot reaction of amine, carbon disulfide, isonitrile and thiol, and the reaction equation is shown as formula (four):

[0098]

[0099] The monomers used are commercially available. 1a is 1,4-benzenedimethanamine, 2 is carbon disulfide, both of which are commercially available from Angene Chemical. 3 is p-toluenesulfonylmethyl isocyanide, which is commercially available from Bide Pharmaceutical Technology Co., Ltd. in this example. 4b is 3,6-dioxa-1,8-octanedithiol, which is also commercially available from Angene Chemical in this example.

[0100] The preparation steps of the polydithiocarbamate compound are as follows:

[0101] In a 10-mL polymerization tube, monomer 1a (136 mg, 1 mmol) and 3 (390 mg, 2 mmol) were sequentially added, followed by 2 mL of dimethyl sulfoxide, stirring at room temperature. After the monomers were completely dissolved, carbon disulfide (152 mg, 2 mmol), 4b (182 mg, 1 mmol), and triethylamine (10 mg, 0.1 mmol) were added, and stirring was continued at room temperature at a speed 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 / dichloromethane, then left to stand, filtered, and dried to obtain the polydithiocarbamate compound P3.

[0102] Determination and analysis showed that the yield of the polydithiocarbamate compound P3 was 87%, the weight average molecular weight was 14 100, and the molecular weight distribution was 1.39.

[0103] Example 4

[0104] A hyperbranched polydithiocarbamate compound, the structural formula of which is shown as P4:

[0105]

[0106] The polydithiocarbamate compound is prepared by direct one-pot reaction of an amine, carbon disulfide, an isocyanide, and a thiol, and the reaction equation is shown as formula (V):

[0107]

[0108] The monomers used are commercially available. 1c is tris(3-aminopropyl)amine, 2 is carbon disulfide, both of which are commercially available from Angene Chemical. 3 is p-toluenesulfonylmethyl isocyanide, which is commercially available from Bide Pharmaceutical Technology Co., Ltd. in this example. 4b is 3,6-dioxa-1,8-octanedithiol, which is also commercially available from Angene Chemical in this example.

[0109] The preparation steps of the polydithiocarbamate compound are as follows:

[0110] In a 10-mL polymerization tube, monomer 1c (125 mg, 0.66 mmol) and 3 (390 mg, 2 mmol) were sequentially added, followed by 2 mL of dimethyl sulfoxide, stirring at room temperature, and then adding carbon disulfide (152 mg, 2 mmol), 4b (182 mg, 1 mmol), and triethylamine (10 mg, 0.1 mmol) after the monomers were completely dissolved. The stirring was continued at a rate of 500 rpm for 12 hours at room temperature. After the reaction was completed, the reaction mother liquor was added dropwise into a mixed solution of n-hexane / dichloromethane, and then left to stand, filtered, and dried to obtain the hyperbranched polydithioaminothiocarbamate compound P4.

[0111] According to the measured analysis, the yield of the hyperbranched polydithioaminothiocarbamate compound P5 was 95%, the weight average molecular weight was 23 100, and the molecular weight distribution was 1.59.

[0112] Example 5

[0113] A thioaminothiocarbamate compound, the structural formula of which is shown as 5a:

[0114]

[0115] The thioaminothiocarbamate compound is prepared by a direct one-pot reaction of an amine, carbon disulfide, an isocyanide, and a thiol, and the reaction equation is shown as formula (I):

[0116]

[0117] Among them, the monomers used can be purchased from the market. 1d is benzylamine, 2 is carbon disulfide, and 4c is dodecanethiol, which are purchased from Angene Chemical in this example. 3 is p-toluenesulfonylmethyl isocyanide, which is purchased from Bide Pharmaceutical Technology Co., Ltd. in this example.

[0118] The preparation steps of the thioaminothiocarbamate compound are as follows:

[0119] In a 10-mL polymerization tube, monomer 1d (107 mg, 1 mmol) and 3 (195 mg, 1 mmol) were sequentially added, followed by 2 mL of dimethyl sulfoxide, stirring at room temperature, and then adding carbon disulfide (76 mg, 1 mmol), 4c (202 mg, 1 mmol), and TBD (7 mg, 0.05 mmol) after the monomers were completely dissolved. The stirring was continued at a rate of 500 rpm for 5 hours at room temperature. After the reaction was completed, ethyl acetate and water were added, and then the organic phase was separated by extraction with ethyl acetate for several times, dried, filtered, concentrated under reduced pressure, separated by column chromatography, and then concentrated under reduced pressure and dried to obtain the thioaminothiocarbamate compound 5a (the proton nuclear magnetic resonance spectrum is shown as A in FIG. 5, and the carbon nuclear magnetic resonance spectrum is shown as B in FIG. 5). Figure 6 Figure 6 ​​

[0120] Example 6

[0121] A dithio-carbamate compound, the structural formula of which is shown as 5b:

[0122]

[0123] The dithio-carbamate compound is prepared by direct one-pot reaction of amine, carbon disulfide, isonitrile and thiol, and the reaction equation is shown as formula (II):

[0124]

[0125] Among them, the monomers used can be purchased from the market. 1d is benzylamine, 2 is carbon disulfide, and 4d is 2-ethylhexyl thiol, which are purchased from Angene Chemical in this example. 3 is p-toluenesulfonylmethyl isonitrile, which is purchased from Bide Pharmaceutical Technology Co., Ltd. in this example.

[0126] The preparation steps of the dithio-carbamate compound are as follows:

[0127] In a 10-milliliter polymerization tube, monomer 1d (107 mg, 1 mmol) and 3 (195 mg, 1 mmol) were added in sequence, followed by 2 mL of dimethyl sulfoxide, and stirring at room temperature. After the monomers were completely dissolved, carbon disulfide (76 mg, 1 mmol), 4d (146 mg, 1 mmol) and TBD (7 mg, 0.05 mmol) were added, and stirring was continued at room temperature at a speed of 500 rpm for 5 hours. After the reaction was completed, ethyl acetate and water were added, and the organic phase was extracted with ethyl acetate several times, dried, filtered, and concentrated under reduced pressure. After column chromatography separation and concentration under reduced pressure, the dithio-carbamate compound 5b was obtained after drying.

[0128] Example 7

[0129] A dithio-carbamate compound, the structural formula of which is shown as 5c:

[0130]

[0131] The dithio-carbamate compound is prepared by direct one-pot reaction of amine, carbon disulfide, isonitrile and thiol, and the reaction equation is shown as formula (III):

[0132]

[0133] Among them, the monomers used can be purchased from the market. 1e is p-methoxybenzylamine, 2 is carbon disulfide, and 4c is dodecanethiol, which are purchased from Angene Chemical in this example. 3 is p-toluenesulfonylmethyl isonitrile, which is purchased from Bide Pharmaceutical Technology Co., Ltd. in this example.

[0134] The preparation steps of the dithiocarbamate compound are as follows:

[0135] Monomers 1e (137 mg, 1 mmol) and 3 (195 mg, 1 mmol) were added sequentially to a 10 mL polymerization tube, followed by 2 mL of dimethyl sulfoxide. The mixture was stirred at room temperature until the monomers were completely dissolved. Then, carbon disulfide (76 mg, 1 mmol), 4c (146 mg, 1 mmol), and TBD (7 mg, 0.05 mmol) were added, and the mixture was stirred at 500 rpm for 5 hours at room temperature. After the reaction was completed, ethyl acetate and water were added, and the mixture was extracted multiple times with ethyl acetate. The organic phases were combined, dried, filtered, and the filtrate was concentrated under reduced pressure. After separation by column chromatography, the filtrate was concentrated under reduced pressure and dried to obtain the dithiocarbamate compound 5c.

[0136] Mechanical properties of polymers

[0137] Taking the linear polydithiocarbamate P3 prepared in Example 3 as an example, the obtained polymer was subjected to a tensile test, and the results are as follows: Figure 3 The stress can reach about 2 MPa, indicating that this type of polymer has good mechanical properties.

[0138] self-healing properties of polymers

[0139] Self-healing materials can repair damage spontaneously or under external stimuli, greatly extending the service life of materials and improving their safety and stability. The series of polymers prepared in this invention exhibit excellent self-healing properties.

[0140] Taking the linear polydithiocarbamate P3 prepared in Example 3 as an example, a rigid rectangular sheet (2*1*0.2 cm) is obtained by heating it at 120°C for 3 hours using a mold and then cooling it to room temperature. After cutting this sheet, pressing the two cut surfaces together at room temperature for 30 seconds can repair it into a complete piece. The repaired sheet can withstand a weight of 1 kg without breaking (e.g., ...). Figure 4 This demonstrates the excellent self-healing properties of this type of polymer.

[0141] Non-traditional luminescent properties of polymers

[0142] All polymers prepared in this invention exhibit luminescent properties. For example, the linear polydithiocarbamate P3 prepared in Example 3, in both solution and solid states (… Figure 5 When excited by light with a wavelength of 280-400nm, it emits blue fluorescence, making it a novel type of non-traditional luminescent material.

[0143] The above embodiments of the present application are merely used for clearly illustrating the present application, but not for limiting the present application. Based on the above description, any modification, equivalent replacement and improvement made by those skilled in the art should be included in the protection scope of the present application.

Claims

1. A method for one-pot preparation of dithiocarbamic acid compounds / polydithiocarbamic acid compounds, characterized by, The polydithiocarbamate compound includes linear polydithiocarbamate compound and hyperbranched / crosslinked polydithiocarbamate compound; (1) the preparation method of the linear polydithiocarbamate compound includes the following steps: The isonitrile compound and the diamine compound are mixed, an organic solvent is added, after dissolution, carbon disulfide, a binary mercaptan compound and a base are added, and stirring is carried out to carry out polymerization reaction, thereby obtaining the linear polydithiocarbamate compound; (2) the preparation method of the hyperbranched / crosslinked polydithiocarbamate compound includes the following steps: The isonitrile compound and the diamine compound are mixed, an organic solvent is added, after dissolution, carbon disulfide, a binary mercaptan compound and a base are added, and stirring is carried out to carry out polymerization reaction, thereby obtaining the linear polydithiocarbamate compound; (3) the preparation method of the polydithiocarbamate compound includes the following steps: The isonitrile compound and the diamine compound are mixed, an organic solvent is added, after dissolution, carbon disulfide, a binary mercaptan compound and a base are added, and stirring is carried out to carry out polymerization reaction, thereby obtaining the linear polydithiocarbamate compound; The structure formula of the binary amine compound is: The structure formula of the binary mercaptan compound is: The structure formula of the ternary amine compound is: The structure formula of the monovalent amine compound is: The structure formula of the monovalent mercaptan compound is: wherein R 1 is an organic group, R 2 is an organic group, R 3 is an organic group, R 5 is an organic group, R 6 is an organic group.

2. The method of claim 1, wherein, R 1 is alkylene, alkylenoxy or arylene, R 2 is alkylene, alkylenoxy or arylene, R 3 is alkylene, alkylenoxy or arylene, R 5 is alkyl, alkoxy or aryl, R 6 is alkyl, alkoxy or aryl.

3. The method of claim 1, wherein, The structure formula of the linear polydithiocarbamate compound is: Formula 1 Wherein, n is an integer between 2 and 400; The structure formula of the polydithiocarbamate compound is: Formula 3 Formula 4 Formula 5.

4. The method of claim 1, wherein, In method (1), the molar ratio of the amino group of the binary amine compound, the isonitrile functional group of the isonitrile compound, carbon disulfide and the mercapto group of the binary mercaptan compound is 1-1.2:1-1.2:1:1-1.2; In method (1), the concentration of the isonitrile compound in the organic solvent is 0.5-1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N-dimethylformamide; In method (2), the molar ratio of the amino group of the ternary amine compound, the isonitrile functional group of the isonitrile compound, carbon disulfide and the mercapto group of the binary mercaptan 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 0.5-1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N-dimethylformamide; In method (3), the molar ratio of the amino group of the amine compound, the isonitrile functional group of the isonitrile compound, carbon disulfide and the mercapto group of the mercaptan compound is 1-1.2:1-1.2:1:1-1.2; In method (3), the concentration of the isonitrile compound in the organic solvent is 0.5-1 mol / L, and the organic solvent is dimethyl sulfoxide or N,N-dimethylformamide.

5. The method of claim 1, wherein, The isonitrile compound is a monovalent isonitrile compound or a binary isonitrile compound; The monohydric thiol compound is selected from any one of the following: wherein i is an integer from 1 to 20; The dihydric thiol compound is selected from any one of the following: wherein e, k are integers from 1 to 20.

6. The method of claim 1, wherein, The isonitrile compound is selected from any one of the following: wherein R 4 represents an alkylene, alkyleneoxy or arylene group.

7. The method of claim 1, wherein, The monohydric amine compound is selected from any one of the following: wherein k is an integer from 1 to 20; The dihydric amine compound is selected from any one of the following: wherein j, k are integers from 1 to 20; The trihydric amine compound is selected from any one of the following: wherein h is an integer from 1 to 20.

8. The method of claim 1, wherein, The base in the methods (1), (2) and (3) is one of triethylamine, triethylenediamine and 1,8-diazabicyclo[5.4.0]undec-7-ene, and the amount of the base is 5% to 20% of the amount of substance of the amino group of the monohydric amine compound, the amino group of the dihydric amine compound or the amino group of the trihydric amine compound.

9. The method of claim 1, wherein, The stirring speed in the methods (1), (2) and (3) is 300 to 600 rpm, and the reaction time is 2 to 24 h. After the reaction in the methods (1), (2) and (3) is completed, the reaction mother liquor is added to a precipitant for precipitation, and the precipitate is collected and dried to constant weight; the precipitant is a mixture of methanol or n-hexane / dichloromethane. The reaction in the methods (1), (2) and (3) is carried out at room temperature; the room temperature is 20 to 30℃. The methods (1), (2) and (3) are carried out under air condition.

10. The application of the polydithiocarbamic compound prepared by the method in any one of claims 1 to 9 in mechanical materials and optoelectronic materials.

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