Polyacyl dithiocarbamate compound as well as preparation method and application thereof

Abstract

The invention discloses a polyacyl dithiocarbamate compound as well as a preparation method and application thereof. The structural formulas of the polyacyl dithiocarbamate compounds are shown as a formula I, a formula II and a formula III, the preparation method comprises the following steps: mixing ammonium thiocyanate, a bilateral acyl chloride compound and a first organic solvent in a protective atmosphere, and then carrying out substitution reaction to obtain a mixed solution containing an intermediate product; the obtained mixed solution containing the intermediate product, a polythiol compound and a second organic solvent are mixed and then subjected to an addition reaction, and the polyacyl dithiocarbamate compound is obtained. The raw materials involved in the preparation method can be commercially purchased, the cost is low, the method is simple, the atom economy is high, and large-scale preparation can be carried out. And moreover, the synthesized polyacyl dithiocarbamate has good refraction property, metal ion adsorbability and degradability.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to a polyacyl dithiocarbamate compound, a preparation method thereof, and an application thereof. Background Art

[0002] Due to the advantages of high polarizability, strong metal ion coordination ability, high molar refraction, etc. of sulfur atoms. Introducing sulfur elements into polymers can endow polymer materials with different excellent properties and functions. Research shows that sulfur-containing polymers constructed by introducing sulfur atoms have high refractive index, strong metal ion adsorption ability, dielectric properties and self-healing properties. Therefore, such sulfur-containing functional polymers have broad application prospects in optoelectronic materials, high refractive index materials, and metal ion adsorption materials. Therefore, how to introduce sulfur atoms into polymers in a simple and green way is gradually attracting everyone's attention.

[0003] At present, the main methods for preparing sulfur-containing polymers include copolymerization of sulfur-containing monomers, ring-opening polymerization of sulfur-containing cyclic monomers, and multicomponent polymerization. Among them, multicomponent polymerization has been proven to be a powerful tool for preparing sulfur-containing polymers, with the advantages of high reaction efficiency, mild reaction conditions, simple operation, high atom economy, and diverse structures. In the prior art, most of the multicomponent polymerization of sulfur-containing polymers uses elemental sulfur and carbon disulfide as sulfur sources. Among them, elemental sulfur, as a by-product of the chemical industry, is rich in source, cheap and easy to obtain, and is commonly used in the preparation of polythioamides and polythioureas. However, elemental sulfur has serious side reactions and low reactivity in the reaction. Carbon disulfide is another sulfur-containing monomer with rich source and sustainability, and is also often used as a sulfur source for preparing sulfur-containing polymers. However, carbon disulfide usually has problems such as strong odor and toxicity. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a polyacyl dithiocarbamate compound, a preparation method thereof, and an application thereof.

[0005] In order to achieve the above invention purpose, the present invention provides the following technical solutions:

[0006] A polyacyl dithiocarbamate compound has a structure shown in Formula I or a structural unit shown in any one of Formula II and Formula III:

[0007]

[0008]

[0009] Among them, n is an integer from 2 to 2000;

[0010] R 1 Each independently is one of an aryl group, an alkyl group or an ether group;

[0011] R 2 、R 3 and R 4 are each independently an alkyl group, an ether group or an ester group.

[0012] Preferably, R 1 the aryl group is a diphenyl ether group, a substituted or unsubstituted benzophenone group, a meta-phenyl group, a para-phenyl group or a biphenyl group; the substituent in the substituted benzophenone group is a halogen, a straight-chain alkyl group having 1 to 80 carbon atoms, a branched-chain alkyl group having 3 to 80 carbon atoms, a cycloalkyl group having 3 to 80 carbon atoms or an aryl group having 6 to 80 carbon atoms;

[0013] R 1 the alkyl group is a straight-chain alkyl group, a branched-chain alkyl group or a cycloalkyl group having 1 to 80 carbon atoms;

[0014] R 1 the ether group is a straight-chain or branched-chain ether group having 1 to 80 carbon atoms;

[0015] R 2 the alkyl group is a straight-chain alkyl group, a branched-chain alkyl group or a cycloalkyl group having 1 to 80 carbon atoms;

[0016] R 2 the ether group is a straight-chain or branched-chain ether group having 1 to 80 carbon atoms;

[0017] R 2 the ester group is a straight-chain or branched-chain ester group having 3 to 80 carbon atoms;

[0018] R 3 the alkyl group is a branched-chain alkyl group or a cycloalkyl group having 1 to 80 carbon atoms;

[0019] R 3 the ether group is a branched-chain ether group or a cycloalkoxy group having 1 to 80 carbon atoms;

[0020] R 3 the ester group is a straight-chain or branched-chain ester group having 3 to 80 carbon atoms;

[0021] R 4 the alkyl group is a branched-chain alkyl group or a cycloalkyl group having 1 to 80 carbon atoms;

[0022] R 4 the ether group is a branched-chain ether group or a cycloalkoxy group having 1 to 80 carbon atoms;

[0023] R 4 the ester group is a straight-chain or branched-chain ester group having 3 to 80 carbon atoms.

[0024] Preferably, the polyacyl dithiocarbamate compound comprises any one of the following structural formulas:

[0025]

[0026] Among them, n is an integer from 2 to 2000; m is an integer from 1 to 20.

[0027] The preparation method of the above-mentioned polyacyl dithiocarbamate compounds includes the following steps:

[0028] (1) In a protective atmosphere, ammonium thiocyanate, a dibilateral acyl chloride compound, and a first organic solvent are mixed and then subjected to a substitution reaction to obtain a mixed solution containing an intermediate product;

[0029] (2) The mixed solution containing the intermediate product obtained in step (1), a polyvalent thiol compound, and a second organic solvent are mixed and then subjected to an addition reaction to obtain the polyacyl dithiocarbamate compound;

[0030] Among them, when the dibilateral acyl chloride compound is and the polyvalent thiol compound is HS-R 2 -SH, the compound of formula I is prepared, and the R 1 is one of aryl, alkyl or ether group, and the R 2 is alkyl, ether group or ester group;

[0031] When the dibilateral acyl chloride compound is and the polyvalent thiol compound is , the compound of formula II is prepared, and the R 3 is alkyl, ether group or ester group;

[0032] When the dibilateral acyl chloride compound is and the polyvalent thiol compound is , the compound of formula III is prepared, and the R 4 is alkyl, ether group or ester group.

[0033] Preferably, the dibilateral acyl chloride compound is at least one of the following structures:

[0034]

[0035] Among them, in formula IV, R 5 is alkyl or ether group;

[0036] The molar ratio of ammonium thiocyanate to the dibilateral acyl chloride compound is 1 to 12: 1 to 4.

[0037] Preferably, the polyvalent thiol compound is at least one of the following structural formulas:

[0038]

[0039] Among them, in formula V, R6 is an alkyl group or an ether group;

[0040] The molar ratio of the polyhydric thiol compound to ammonium thiocyanate is 1-2:1-16.

[0041] Preferably, the temperature of the substitution reaction in step (1) is 0-100 °C, and the time of the substitution reaction is 10-120 min;

[0042] The temperature of the addition reaction in step (2) is 0-130 °C, and the time of the addition reaction is 1-72 h;

[0043] The protective atmosphere in step (1) contains one of nitrogen and argon;

[0044] The addition reaction in step (2) is carried out in an air atmosphere or a protective atmosphere;

[0045] The dosage ratio of the first organic solvent to ammonium thiocyanate is 1.0 mL:1-10 mmol;

[0046] The dosage ratio of ammonium thiocyanate to the second organic solvent is 0.5-10 mmol:1.5 mL;

[0047] The first organic solvent and the second organic solvent each independently contain one or more of chloroform, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, toluene, acetonitrile, dichloromethane, 1,2-dichloroethane, acetone and tetrahydrofuran.

[0048] More preferably, the addition reaction in step (2) is carried out in an air atmosphere or a protective atmosphere containing one of nitrogen and argon.

[0049] Application of the above polyacyl dithiocarbamate compound or the polyacyl dithiocarbamate compound prepared by the above preparation method as a refractive index material or as a metal ion adsorption material.

[0050] The above polyacyl dithiocarbamate compound or the polyacyl dithiocarbamate compound prepared by the above preparation method has the application of degradation and recycling.

[0051] The polyacyl dithiocarbamate prepared in the present invention contains an acyl dithiocarbamate group in its structure. When used as a refractive index material, it has a higher refractive index and a higher Abbe number compared with general sulfur-containing polymers. When used as a metal ion adsorption material, it has good metal ion adsorption performance. Compared with general sulfur-containing polymers, it can be directly degraded into another polymer through diamine.

[0052] The polymerization method used in this invention is multi-component tandem polymerization. Using ammonium thiocyanate as the sulfur source monomer, it can generate polyacyl dithiocarbamate with a well-defined structure with high added value.

[0053] Advantages of this invention:

[0054] (1) The preparation method provided by this invention uses ammonium thiocyanate as the sulfur source monomer to react with bilateral acyl chloride compounds and polyvalent thiol compounds to prepare polyacyl dithiocarbamate compounds. The reaction raw materials used in this process are easily available, can be directly purchased commercially, are inexpensive, and the reaction conditions are mild and the process is simple. It can prepare polyacyl dithiocarbamate with a well-defined structure with high added value.

[0055] (2) The second-step reaction in the preparation method of this invention can be carried out under air conditions and can be prepared on a large scale in grams.

[0056] (3) The preparation method of this invention has good universality. Using this method, various monomers can be made into polymers with different structures. Description of the drawings

[0057] Figure 1 Comparative diagrams of 1H NMR and 13C NMR spectra of the polyacyl dithiocarbamate compound prepared in Example 4, the acyl dithiocarbamate model small molecule, and 1,10-hexanedithiol in deuterated tetrahydrofuran; among them, A is the 1H NMR spectrum of 1,10-decanedithiol in deuterated tetrahydrofuran, B is the 1H NMR spectrum of the acyl dithiocarbamate small molecule in deuterated tetrahydrofuran, C is the 1H NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 4 in deuterated tetrahydrofuran; D is the 13C NMR spectrum of 1,10-decanedithiol in deuterated tetrahydrofuran, E is the comparative diagram of the 13C NMR spectrum of the acyl thiocarbamate model small molecule in deuterated tetrahydrofuran, and F is the 13C NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 4 in deuterated tetrahydrofuran.

[0058] Figure 2 Infrared absorption spectra of the polyacyl dithiocarbamate compound prepared in Example 1 and the acyl dithiocarbamate model small molecule; among them, A is the infrared absorption spectrum of the acyl dithiocarbamate model small molecule, and B is the infrared absorption spectrum of the polyacyl dithiocarbamate compound prepared in Example 1.

[0059] Figure 3 1H NMR and 13C NMR spectra of the polyacyl dithiocarbamate compounds prepared in Examples 1 to 6 in deuterated tetrahydrofuran; among them,

[0060] 1H NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 1 in deuterated tetrahydrofuran;

[0061] 1H NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 2 in deuterated tetrahydrofuran;

[0062] 1H NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 3 in deuterated tetrahydrofuran;

[0063] 1H NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 4 in deuterated tetrahydrofuran;

[0064] 1H NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 5 in deuterated tetrahydrofuran;

[0065] 1H NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 6 in deuterated tetrahydrofuran;

[0066] 13C NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 1 in deuterated tetrahydrofuran;

[0067] 13C NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 2 in deuterated tetrahydrofuran;

[0068] 13C NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 3 in deuterated tetrahydrofuran;

[0069] 13C NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 4 in deuterated tetrahydrofuran;

[0070] 13C NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 5 in deuterated tetrahydrofuran;

[0071] 13C NMR spectrum of the polyacyl dithiocarbamate compound prepared in Example 6 in deuterated tetrahydrofuran.

[0072] Figure 4 Reaction general formula of ammonium thiocyanate, dibilateral acyl chloride and dibilateral mercaptan and structural general formula of polyacyl dithiocarbamate compound.

[0073] Figure 5Infrared absorption spectra of the polyacyl dithiocarbamate compounds prepared in Examples 1 to 6; wherein, A is the infrared absorption spectrum of the polyacyl dithiocarbamate compound prepared in Example 1; B is the infrared absorption spectrum of the polyacyl dithiocarbamate compound prepared in Example 2; C is the infrared absorption spectrum of the polyacyl dithiocarbamate compound prepared in Example 3; D is the infrared absorption spectrum of the polyacyl dithiocarbamate compound prepared in Example 4; E is the infrared absorption spectrum of the polyacyl dithiocarbamate compound prepared in Example 5; F is the infrared absorption spectrum of the polyacyl dithiocarbamate compound prepared in Example 6.

[0074] Figure 6 Refractive index data of the polyacyl dithiocarbamate compounds prepared in Examples 1 to 4 and Example 6.

[0075] Figure 7 The polyacyl dithiocarbamate compound prepared in Example 3 for Cu 2+ , Ni 2+ and Co 2+ Adsorption capacity and adsorption efficiency.

[0076] Figure 8 1H nuclear magnetic resonance spectrum of the polyacyl thiourea compound obtained after the polyacyl dithiocarbamate compound prepared in Example 4 was degraded by 1,4-butanediamine. Detailed implementation manners

[0077] The present invention provides a polyacyl dithiocarbamate compound having a structure shown in Formula I or a structural unit shown in any one of Formula II and Formula III:

[0078]

[0079]

[0080] wherein, n = 2 to 2000 and n is an integer;

[0081] R 1 are each independently one of an aryl group, an alkyl group or an ether group;

[0082] R 2 , R 3 and R 4 are each independently an alkyl group, an ether group or an ester group.

[0083] In the present invention, n is preferably from 8 to 1500, more preferably from 20 to 1000, still more preferably from 22 to 500, further preferably from 30 to 300, still further preferably from 31 to 200, more preferably from 54 to 150, still more preferably from 82 to 130, even more preferably from 84 to 128, and most preferably from 123 to 126.

[0084] In the present invention, R 1 The aryl group preferably has 6 to 80 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms; R 1 The aryl group is preferably meta-phenyl or para-phenyl;

[0085] R 1 The alkyl group is preferably a straight-chain alkyl group, a branched-chain alkyl group or a cycloalkyl group having 1 to 80 carbon atoms, R 1 The alkyl group in R preferably has 4 to 60 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms;

[0086] R 1 The ether group is a straight-chain or branched-chain ether group; R 1 The ether group in R has 1 to 80 carbon atoms, preferably 4 to 60 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms;

[0087] R 2 The alkyl group is a straight-chain alkyl group, a branched-chain alkyl group or a cycloalkyl group having 1 to 80 carbon atoms, R 2 The alkyl group in R preferably has 4 to 60 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms;

[0088] R 2 The ether group is a straight-chain or branched-chain ether group, R 2 The ether group in R has 1 to 80 carbon atoms, preferably 4 to 60 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms; R 2 The ether group is preferably

[0089] R 2 The ester group is a straight-chain ester group or a branched-chain ester group, R 2 The ester group in R has 3 to 80 carbon atoms, preferably 4 to 60 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms; preferably

[0090] R 3 The alkyl group is a branched-chain alkyl group or a cycloalkyl group having 1 to 80 carbon atoms; R 3The carbon atoms of the alkyl group described therein are preferably 4 to 60, more preferably 6 to 50, and may also be preferably 8 to 20;

[0091] R 3 The ether group is a branched ether group or a cycloalkyloxy group having 1 to 80 carbon atoms; R 3 The carbon atoms of the ether group described therein are preferably 4 to 60, more preferably 6 to 50, and may also be preferably 8 to 20;

[0092] R 3 The ester group is a linear ester group or a branched ester group having 3 to 80 carbon atoms; R 3 The carbon atoms of the ester group described therein are preferably 4 to 60, more preferably 6 to 50, and may also be preferably 8 to 20;

[0093] R 4 The alkyl group is a branched alkyl group or a cycloalkyl group having 1 to 80 carbon atoms; R 4 The carbon atoms of the alkyl group described therein are preferably 4 to 60, more preferably 6 to 50, and may also be preferably 8 to 20;

[0094] R 4 The ether group is a branched ether group or a cycloalkyloxy group having 1 to 80 carbon atoms; R 4 The carbon atoms of the ether group described therein are preferably 4 to 60, more preferably 6 to 50, and may also be preferably 8 to 20;

[0095] R 4 The ester group is a linear ester group or a branched ester group having 3 to 80 carbon atoms; R 4 The carbon atoms of the ester group described therein are preferably 4 to 60, more preferably 6 to 50, and may also be preferably 8 to 20;

[0096] In the present invention, the polyacyl dithiocarbamate compounds preferably include any one of the following structural formulas:

[0097]

[0098]

[0099] Among them, n = 2 to 2000, and n is an integer; m = 1 to 20, and m is an integer;

[0100] n is preferably 8 to 1500, preferably 20 to 1000, preferably 22 to 500, preferably 30 to 300, preferably 31 to 200, preferably 54 to 150, preferably 82 to 130, more preferably 84 to 128, and still more preferably 123 to 126;

[0101] m is preferably from 1 to 15, more preferably from 2 to 12, still more preferably from 5 to 10;

[0102] The present invention provides a method for preparing the polyacyl dithiocarbamate compound, comprising the following steps:

[0103] (1) In a protective atmosphere, ammonium thiocyanate, a bilateral acyl chloride compound and a first organic solvent are mixed and then subjected to a substitution reaction to obtain a mixed solution containing an intermediate product;

[0104] (2) The mixed solution containing the intermediate product obtained in step (1), a polysulfhydryl compound and a second organic solvent are mixed and then subjected to an addition reaction to obtain the polyacyl dithiocarbamate compound;

[0105] Wherein, when the bilateral acyl chloride compound is and the polysulfhydryl compound is HS-R 2 -SH, the compound of formula I is prepared, and the R 1 is one of an aryl group, an alkyl group or an ether group, and the R 2 is an alkyl group, an ether group or an ester group;

[0106] When the bilateral acyl chloride compound is and the polysulfhydryl compound is , the compound of formula II is prepared, and the R 3 is an alkyl group, an ether group or an ester group;

[0107] When the bilateral acyl chloride compound is and the polysulfhydryl compound is , the compound of formula III is prepared, and the R 4 is an alkyl group, an ether group or an ester group.

[0108] In the present invention, the bilateral acyl chloride compound is preferably at least one of the following structures:

[0109]

[0110] Wherein, in formula IV, R 5 is an alkyl group or an ether group, and the selected alkyl group is preferably one of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, nonyl, dodecyl, hexadecyl or heptadecyl; the selected ether group is preferably one of ethyl ether group, butanediol ether group, hexanediol ether group, nonanetriol ether group or polyethylene glycol group.

[0111] In the present invention, the molar ratio of ammonium thiocyanate to the bilateral acyl chloride compound is preferably 1 to 12:1 to 4, more preferably 2 to 10:1 to 3, still more preferably 2 to 8:1 to 2, and even more preferably 2 to 6:1.

[0112] In the present invention, the protective atmosphere in step (1) preferably contains nitrogen and argon;

[0113] The temperature of the substitution reaction in step (1) is preferably 0 to 100 °C, more preferably 10 to 70 °C, further preferably 15 to 60 °C, and even more preferably 20 to 50 °C;

[0114] The time of the substitution reaction in step (1) is preferably 10 to 120 min, more preferably 12 to 100 min, and further preferably 15 to 60 min;

[0115] The dosage ratio of the first organic solvent to ammonium thiocyanate is preferably 1 mL: 1 to 10 mmol, more preferably 1 mL: 1.1 to 9 mmol, further preferably 1 mL: 1.2 to 7 mmol, and even more preferably 1 mL: 1.25 to 5 mmol;

[0116] The first organic solvent preferably contains one or more of chloroform, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, toluene, acetonitrile, dichloromethane, 1,2-dichloroethane, acetone, and tetrahydrofuran; when there are two or more of the above organic solvents, the present invention has no special limitation on the ratio of different types of organic solvents, and any ratio is acceptable.

[0117] In the present invention, the substitution reaction in step (1) is preferably carried out under stirring, and the stirring speed is 100 to 1000 r / min, preferably 200 to 900 r / min, further preferably 400 to 800 r / min, and even more preferably 500 to 600 r / min.

[0118] In the present invention, the polyhydric thiol compound is preferably at least one of the following structural formulas:

[0119]

[0120] Among them, R in formula V 6 is an alkyl group or an ether group; the polyhydric thiol compound is preferably 1,2-propanedithiol, ethanedithiol, 1,3-propanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 3,6-dioxa-1,8-octanedithiol, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate);

[0121] In the present invention, the molar ratio of the polyhydric thiol compound to ammonium thiocyanate is preferably 1 to 2: 1 to 16, preferably 1 to 1.5: 2 to 14, further preferably 1 to 1.2: 2 to 10, and even more preferably 1: 2.5 to 8.

[0122] In the present invention, the temperature of the addition reaction in step (2) is preferably 0 to 130 °C, more preferably 10 to 125 °C, further preferably 20 to 120 °C, and even more preferably 30 to 120 °C;

[0123] The time of the addition reaction in step (2) is preferably 1 to 72 h, more preferably 2 to 60 h, further preferably 3 to 50 h, and even more preferably 4 to 40 h;

[0124] The addition reaction in step (2) is carried out in an air atmosphere or a protective atmosphere; the protective atmosphere preferably contains nitrogen and argon;

[0125] The dosage ratio of ammonium thiocyanate to the second organic solvent is preferably 0.5 to 10 mmol: 1.5 mL, more preferably 0.75 to 8 mmol: 1.5 mL, further preferably 1 to 7 mmol: 1.5 mL, and even more preferably 1.2 to 6 mmol: 1.5 mL;

[0126] The second organic solvent is preferably one or more of chloroform, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, toluene, acetonitrile, dichloromethane, 1,2-dichloroethane, acetone and tetrahydrofuran; when there are two or more of the above organic solvents, the present invention has no special limitation on the ratio of different kinds of organic solvents, and any ratio can be used.

[0127] In the present invention, the addition reaction in step (2) is preferably carried out under stirring, and the stirring speed is 100 to 1000 r / min, preferably 200 to 900 r / min, further preferably 400 to 800 r / min, and even more preferably 500 to 600 r / min;

[0128] After the addition reaction of the mixed solution containing the intermediate product, the polyhydric thiol compound and the second organic solvent in step (2) is completed, it is preferably further included to sequentially filter, wash, stand, filter and dry the obtained product;

[0129] The reagent used for washing is preferably water, and the amount of deionized water used in the washing process is adjusted according to actual needs;

[0130] The drying temperature is preferably 30 to 55 °C, further preferably 35 to 50 °C, and even more preferably 40 to 45 °C;

[0131] The drying time is preferably 3 to 8 h, further preferably 4 to 7 h, and even more preferably 5 to 6 h.

[0132] The present invention also provides the application of polyacyl dithiocarbamate compounds in refractive materials.

[0133] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0134] Example 1

[0135] Prepare the polyacyl dithiocarbamate compound shown as P1, and the reaction equation is as shown in Equation (1):

[0136]

[0137] Among them, M1 is ammonium thiocyanate, which can be purchased from the market. In this example, it is purchased from Energy Chemical; M2 is isophthaloyl chloride, which can be purchased from the market. In this example, it is purchased from Aladdin; M3 is 1,6-hexanedithiol, which can be purchased from the market. In this example, it is purchased from Energy Chemical.

[0138] The preparation steps of the polyacyl dithiocarbamate compound P1 are as follows:

[0139] Add ammonium thiocyanate (190 mg, 2.5 mmol) and isophthaloyl chloride (203 mg, 1 mmol) successively into a 5 mL polymerization tube, evacuate and replace with nitrogen three times, add 1 mL of tetrahydrofuran with a syringe, and stir and react at 25 °C at a rotation speed of 250 r / min for 30 min to obtain isophthaloyl diisothiocyanate;

[0140] After the reaction is completed, in an air atmosphere, add 1,6-hexanedithiol (153 μL, 1 mmol) and N,N-dimethylacetamide (1.5 mL) to the obtained reaction solution, and stir and react at 25 °C at a rotation speed of 500 r / min for 12 h; after the reaction is completed, separate the precipitate by filtration, wash it with stirring with deionized water, finally let it stand, filter, and dry at 40 °C for 6 h to obtain the light yellow solid P1 of the polyacyl dithiocarbamate compound.

[0141] After determination and analysis, the yield of the final product polyacyl dithiocarbamate compound P1 is 85%, the number average molecular weight is 12100 g / mol, and the molecular weight distribution is 1.32.

[0142] Example 2

[0143] Prepare the polyacyl dithiocarbamate compound shown as P2, and the reaction equation is as shown in Equation (2):

[0144]

[0145] Among them, M1 is ammonium thiocyanate, which can be purchased from the market and is purchased from Aladdin Industrial Corporation in this example; M2 is isophthaloyl chloride, which can be purchased from the market and is purchased from Adamas-beta in this example; M4 is 1,8-octanediol, which can be purchased from the market and is purchased from Aladdin Industrial Corporation in this example.

[0146] The preparation steps of the polyacyl dithiocarbamate compound P2 are as follows:

[0147] Add ammonium thiocyanate (190 mg, 2.5 mmol) and isophthaloyl chloride (203 mg, 1 mmol) into a 5 mL polymerization tube in sequence, evacuate and replace with nitrogen three times, add 1 mL of tetrahydrofuran with a syringe, and stir and react at 25 °C at a rotation speed of 250 r / min for 30 min to obtain isophthaloyl diisothiocyanate;

[0148] After the reaction is completed, under an air atmosphere, add 1,8-octanedithiol (184 μL, 1 mmol) and N,N-dimethylacetamide (1.5 mL) to the obtained reaction solution, and stir and react at 25 °C at a rotation speed of 500 r / min for 12 h; after the reaction is completed, separate the precipitate by filtration, wash it with stirring with deionized water, finally let it stand, filter, and dry at 40 °C for 6 h to obtain the light yellow solid P2 of the polyacyl dithiocarbamate compound.

[0149] After determination and analysis, the yield of the final product polyacyl dithiocarbamate compound P2 is 85%, the number average molecular weight is 12700 g / mol, and the molecular weight distribution is 1.36.

[0150] Example 3

[0151] Prepare the polyacyl dithiocarbamate compound as shown in P3, and the reaction equation is as shown in formula (III):

[0152]

[0153] Among them, M1 is ammonium thiocyanate, which can be purchased from the market and is purchased from Aladdin Industrial Corporation in this example; M2 is isophthaloyl chloride, which can be purchased from the market and is purchased from Adamas-beta in this example; M5 is 2,2'-(1,2-ethylenedioxy)bis(ethanethiol), which can be purchased from the market and is purchased from Aladdin Industrial Corporation in this example.

[0154] The preparation steps of the polyacyl dithiocarbamate compound P3 are as follows:

[0155] In a 5 mL polymerization tube, ammonium thiocyanate (190 mg, 2.5 mmol) and isophthaloyl chloride (203 mg, 1 mmol) were added successively. The tube was evacuated and filled with nitrogen three times. 1 mL of tetrahydrofuran was added using a syringe, and the mixture was stirred at 25 °C at a speed of 250 r / min for 30 min to obtain isophthaloyl diisothiocyanate;

[0156] After the reaction was completed, under an air atmosphere, 2,2'-(1,2-ethylenedioxy)bis(ethanethiol) (163 μL, 1 mmol) and N,N-dimethylacetamide (1.5 mL) were added to the obtained reaction solution, and the mixture was stirred at 25 °C at a speed of 500 r / min for 12 h for the reaction; after the reaction ended, the precipitate was separated by filtration, washed by stirring with deionized water, finally allowed to stand, filtered, and dried at 40 °C for 6 h to obtain the pale yellow solid P3 of the polyacyl dithiocarbamate compound.

[0157] After determination and analysis, the yield of the final product polyacyl dithiocarbamate compound P3 was 72%, the number average molecular weight was 10400 g / mol, and the molecular weight distribution was 1.28.

[0158] Example 4

[0159] Prepare the polyacyl dithiocarbamate compound such as P4, and the reaction equation is as shown in Equation (IV):

[0160]

[0161] Among them, M1 is ammonium thiocyanate, which can be purchased from the market. In this example, it was purchased from Energy Chemical; M2 is isophthaloyl chloride, which can be purchased from the market. In this example, it was purchased from Aladdin; M6 is 1,10-decanedithiol, which can be purchased from the market. In this example, it was purchased from Energy Chemical.

[0162] The preparation steps of the polyacyl dithiocarbamate compound P4 are as follows:

[0163] In a 5 mL polymerization tube, ammonium thiocyanate (190 mg, 2.5 mmol) and isophthaloyl chloride (203 mg, 1 mmol) were added successively. The tube was evacuated and filled with nitrogen three times. 1 mL of tetrahydrofuran was added using a syringe, and the mixture was stirred at 25 °C at a speed of 250 r / min for 30 min to obtain isophthaloyl diisothiocyanate;

[0164] After the reaction was completed, under an air atmosphere, 1,10-decanedithiol (217 μL, 1 mmol) and N,N-dimethylacetamide (1.5 mL) were added to the obtained reaction solution, and the reaction was carried out with stirring at 500 r / min at 25 °C for 12 h; after the reaction was completed, the precipitate was separated by filtration, washed with stirring with deionized water, and finally allowed to stand, filtered, and dried at 40 °C for 6 h to obtain the pale yellow solid P4 of the polyacyl dithiocarbamate compound.

[0165] After determination and analysis, the yield of the final product polyacyl dithiocarbamate compound P4 was 93%, the number-average molecular weight was 12,800 g / mol, and the molecular weight distribution was 1.41.

[0166] According to the above steps, an acyl dithiocarbamate model small molecule was prepared, in which benzoyl chloride (132 μL, 1 mmol) was used to replace isophthaloyl chloride (203 mg, 1 mmol) to obtain an acyl dithiocarbamate model small molecule, and its structure is

[0167] 1,10-Decanedithiol, the acyl dithiocarbamate model small molecule and the polyacyl dithiocarbamate compound P4 prepared from 1,10-decanedithiol used in Example 4 were subjected to NMR characterization, and the obtained nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum are as Figure 1 shown;

[0168] Through Figure 1 (* represents the solvent peak), it can be found that for 1,10-decanedithiol ( Figure 1 A), there is a mercapto hydrogen at 1.52 ppm. In the NMR hydrogen spectrum of the polyacyl dithiocarbamate compound P1 ( Figure 1 C), the chemical shift value of the hydrogen in the acyl dithiocarbamate group -NH- is at a low field of 11.66 ppm, which is consistent with the chemical shift value of 11.51 ppm of the hydrogen in the acyl thiocarbamate group -NH- in the acyl thiocarbamate model small molecule ( Figure 1 B). The chemical shift value of the hydrogen of -CH- on the benzene ring of the product polyacyl dithiocarbamate compound P4 is 8.54 ppm, and the hydrogens on the alkyl chain are located at 3.27 ppm and 1.80 ppm respectively.

[0169] Through Figure 1 (* represents the solvent peak), it can be found that in the carbon spectrum of the polyacyl dithiocarbamate compound P1 ( Figure 1 F), the chemical shifts of C=S and C=O are at 206.00 ppm and 164.62 ppm, which are the same as those of the model molecule ( Figure 1The chemical shift values of C=S and C=O in E) are consistent at 205.09 and 164.42 ppm.

[0170] The polyacyl dithiocarbamate compound P1 prepared according to formula (I) and the acyl dithiocarbamate model small molecule were subjected to infrared absorption spectroscopy detection, and the obtained infrared absorption spectra are as Figure 2 shown;

[0171] Among them, A is the infrared absorption spectrum of the acyl thiocarbamate model small molecule, and B is the infrared absorption spectrum of the polyacyl dithiocarbamate compound prepared in Example 1;

[0172] From Figure 2 it can be seen that the stretching vibration absorption peak of the C=S bond in the polyacyl dithiocarbamate compound P1 is located at 1603 cm -1 , and the stretching vibration peak of N-H is located at 3266 cm -1 .

[0173] Example 5

[0174] Prepare the polyacyl dithiocarbamate compound shown as P5, and the reaction equation is as formula (V):

[0175]

[0176] Among them, M1 is ammonium thiocyanate, which can be purchased from the market. In this example, it is purchased from Energy Chemical; M7 is terephthaloyl chloride, which can be purchased from the market. In this example, it is purchased from Aladdin; M6 is 1,10-decanedithiol, which can be purchased from the market. In this example, it is purchased from Energy Chemical.

[0177] The preparation steps of the polyacyl dithiocarbamate compound P5 are as follows:

[0178] In a 5 mL polymerization tube, add ammonium thiocyanate (190 mg, 2.5 mmol) and terephthaloyl chloride (203 mg, 1 mmol) in sequence, evacuate and replace with nitrogen three times, add 1 mL of tetrahydrofuran with a syringe, and stir and react at 25 °C at a rotation speed of 250 r / min for 30 min to prepare m-phthaloyl diisothiocyanate;

[0179] After the reaction is completed, in an air atmosphere, add 1,10-decanedithiol (217 μL, 1 mmol) and N,N-dimethylacetamide (1.5 mL) to the obtained reaction solution, and stir at 25 °C at a rotation speed of 500 r / min for 12 h for reaction; after the reaction is completed, separate the precipitate by filtration, wash it with stirring with deionized water, finally let it stand, filter, and dry at 40 °C for 6 h to obtain the pale yellow solid P5 of the polyacyl dithiocarbamate compound.

[0180] After determination and analysis, the yield of the final product polyacyl dithiocarbamate compound P5 was 87%, the number-average molecular weight was 6900 g / mol, and the molecular weight distribution was 1.09.

[0181] Example 6

[0182] Prepare the polyacyl dithiocarbamate compound shown as P6, and the reaction equation is as shown in Equation (VI):

[0183]

[0184] Among them, M1 is ammonium thiocyanate, which can be purchased from the market. In this example, it is purchased from Anyij Co., Ltd.; M8 is 4,4'-chlorocarbonyl phenyl ether, which can be purchased from the market. In this example, it is purchased from Aladdin Co., Ltd.; M6 is 1,10-decanedithiol, which can be purchased from the market. In this example, it is purchased from Anyij Co., Ltd.

[0185] The preparation steps of the polyacyl dithiocarbamate compound P6 are as follows:

[0186] Sequentially add ammonium thiocyanate (190 mg, 2.5 mmol) and 4,4'-chlorocarbonyl phenyl ether (295 mg, 1 mmol) into a 5 mL polymerization tube, evacuate and replace with nitrogen three times, add 1 mL of tetrahydrofuran with a syringe, and stir and react at 25 °C at a rotation speed of 250 r / min for 30 min to prepare 4,4'-chlorocarbonyl phenyl ether-based diisothiocyanate;

[0187] After the reaction is completed, under an air atmosphere, add 1,10-decanedithiol (217 μL, 1 mmol) and N,N-dimethylacetamide (1.5 mL) to the obtained reaction solution, and stir and react at 25 °C at a rotation speed of 500 r / min for 12 h; after the reaction is completed, separate the precipitate by filtration, wash it with stirring with deionized water, finally let it stand, filter, and dry at 40 °C for 6 h to obtain the light yellow solid P6 of the polyacyl dithiocarbamate compound.

[0188] After determination and analysis, the yield of the final product polyacyl dithiocarbamate compound P6 was 85%, the number-average molecular weight was 15,100 g / mol, and the molecular weight distribution was 1.45.

[0189] Perform nuclear magnetic characterization on the polyacyl dithiocarbamate compounds prepared in Examples 1 to 6, and the obtained nuclear magnetic resonance hydrogen spectrum and synthetic resonance carbon spectrum are as Figure 3 shown.

[0190] Perform Fourier transform infrared spectroscopy characterization on the polyacyl dithiocarbamate compounds prepared in Examples 1 to 6, as Figure 5as shown

[0191] From Figure 3 and 5 it can be seen that the polyacyl dithiocarbamate compound of the present invention has been successfully synthesized.

[0192] Example 7

[0193] Preparation for testing the refractive index of the polyacyl dithiocarbamate compounds shown in P1 - P4 and P6:

[0194] Take 20 mg of the samples of P1 - P4 and P6 in a glass bottle, add 0.5 mL each of 1,2 - dichlorobenzene and N,N - dimethylacetamide. After complete dissolution, use a pipette to take 60 μL of the above solution onto a silicon wafer, and prepare a uniform and smooth film by spin - coating. Then use an ellipsometer to test and fit to obtain the refractive index and Abbe number. The obtained refractive index and Abbe number are shown in Figure 6 and Table 1.

[0195] Table 1 Refractive index (n) and Abbe number (v D ) a

[0196]

[0197] a Calculation of Abbe number: v D =(n D - 1) / (n F - n C ), (n D = n 589.2 , n F = n 486.1 , n C = n 656.3 ).

[0198] Example 8

[0199] Experimental steps for the metal ion adsorption of the polyacyl dithiocarbamate compounds shown in P1 - P6: Dissolve 20 mg of P3 completely in 1 mL of THF, then use a pipette to take 250 μL of the solution and add it to a glass bottle containing 10 mL of a prepared specific metal ion solution (50 mg / L). After stirring for 1 h, filter through an aqueous phase filter head, and test the residual metal ion concentration by ICP - OES. Finally, calculate the adsorption capacity and efficiency of different metal ions. The obtained adsorption capacity and efficiency of metal ions are shown in Figure 7 as shown.

[0200] Example 9

[0201] Degradation behavior of P4 polyacyl dithiocarbamate compound, and the reaction equation is as shown in Equation (VII):

[0202]

[0203] Wherein, M9 is 1,4-butanediamine, which can be commercially purchased. In this example, it is purchased from Energy Chemical Co., Ltd.;

[0204] The experimental steps for the degradation behavior of the polyacyl dithiocarbamate compound P1 are as follows:

[0205] Add P4 (221 mg, 0.5 mmol), 2 mL of tetrahydrofuran and 1,4-butanediamine (50 μL, 0.5 mmol) into a 5 mL polymerization tube, and stir and react at 25 °C at a rotation speed of 300 r / min for 4 h to synthesize polyacyl thiourea P7;

[0206] After determination and analysis, the yield of the final product polyacyl thiourea P7 is 37%, the number average molecular weight is 5000 g / mol, and the molecular weight distribution is 1.20.

[0207] Perform NMR characterization on the polyacyl thiourea compound prepared in Example 9, and the obtained nuclear magnetic resonance hydrogen spectrum Figure 8 is shown as follows.

[0208] As can be seen from the above examples, the present invention provides a polyacyl dithiocarbamate compound and a preparation method thereof. In the present invention, ammonium thiocyanate, bilateral acyl chloride compound and polyhydric thiol compound are subjected to stepwise room temperature stirring reaction in an organic solvent to obtain a polyacyl dithiocarbamate compound. The raw materials used in the present invention can all be commercially purchased, with low cost, simple method, high atom economy, and can be prepared on a large scale. The synthesized polyacyl dithiocarbamate compound has excellent refractive properties, metal ion adsorption properties and degradability.

[0209] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A polyacyl dithiocarbamate compound, characterized in that, Having the structure shown in Formula I or the structural unit shown in any one of Formula II and Formula III: wherein n is an integer from 2 to 2000; R 1 each independently being one of an aryl group, an alkyl group or an ether group; R 2 、R 3 and R 4 are each independently an alkyl group, an ether group or an ester group.

2. The polyacyl dithiocarbamate compound according to claim 1, characterized in that R 1 The aryl group is a diphenyl ether group, a substituted or unsubstituted benzophenone group, a m-phenylene group, a p-phenylene group or a biphenyl group; the substituent in the substituted benzophenone group is a halogen, a straight-chain alkyl group having 1 to 80 carbon atoms, a branched-chain alkyl group having 3 to 80 carbon atoms, a cycloalkyl group having 3 to 80 carbon atoms or an aryl group having 6 to 80 carbon atoms; R 1 The alkyl group is a straight-chain alkyl group, branched-chain alkyl group or cycloalkyl group having 1 to 80 carbon atoms; R 1 The ether group is a straight-chain or branched-chain ether group having 1 to 80 carbon atoms; R 2 The alkyl group is a straight-chain alkyl group, branched-chain alkyl group or cycloalkyl group having 1 to 80 carbon atoms; R 2 The ether group is a straight-chain or branched-chain ether group having 1 to 80 carbon atoms; R 2 The ester group is a straight-chain ester group or a branched-chain ester group having 3 to 80 carbon atoms; R 3 The alkyl group is a branched alkyl group or a cycloalkyl group having 1 to 80 carbon atoms; R 3 The ether group is a branched-chain ether group or a cycloalkyloxy group having 1 to 80 carbon atoms; R 3 The ester group is a straight-chain or branched-chain ester group having 3 to 80 carbon atoms; R 4 The alkyl group is a branched alkyl group or cycloalkyl group having 1 to 80 carbon atoms; R 4 The ether group is a branched-chain ether group or a cycloalkyloxy group having 1 to 80 carbon atoms; R 4 The ester group is a linear or branched ester group having 3 to 80 carbon atoms.

3. The polyacyl dithiocarbamate compound according to claim 1 or 2, characterized in that the polyacyl dithiocarbamate compound comprises any one of the following structural formulas: wherein n is an integer from 2 to 2000; m is an integer from 1 to 20.

4. The preparation method of the polyacyl dithiocarbamate compound according to any one of claims 1 to 3, characterized in that, Comprising the following steps: (1) In a protective atmosphere, ammonium thiocyanate, a bilateral acyl chloride compound and a first organic solvent are mixed and then subjected to a substitution reaction to obtain a mixed solution containing an intermediate product; (2) The mixed solution containing the intermediate product obtained in step (1), a polyhydric thiol compound and a second organic solvent are mixed and then subjected to an addition reaction to obtain the polyacyl dithiocarbamate compound; Among them, when the bis-acyl chloride compound is and the polyhydric thiol compound is HS-R 2 -SH, the compound of formula I is obtained, wherein R 1 is one of aryl, alkyl or ether group, and R 2 is alkyl, ether group or ester group; When the bis-acyl chloride compound is and the poly-thiol compound is a compound of Formula II is obtained, where R 3 is an alkyl group, an ether group or an ester group; When the bis-acyl chloride compound is and the polyhydric thiol compound is a compound of Formula III is prepared, wherein R 4 is an alkyl group, an ether group or an ester group.

5. The preparation method according to claim 4, characterized in that, The bilateral acyl chloride compound is at least one of the following structures: Among them, R in formula IV 5 is alkyl or ether group; The molar ratio of ammonium thiocyanate to the bilateral acyl chloride compound is 1-12:1-4.

6. The preparation method according to claim 4 or 5, characterized in that, The polyhydric thiol compound is at least one of the following structural formulas: HS-R 6 -SH Formula V; Among them, R in formula V 6 is alkyl or ether group; The molar ratio of the polyhydric thiol compound to ammonium thiocyanate is 1-2:1-16.

7. The preparation method according to claim 4 or 5, characterized in that the temperature of the substitution reaction in step (1) is 0-100 °C, and the time of the substitution reaction is 10-120 min; the temperature of the addition reaction in step (2) is 0-130 °C, and the time of the addition reaction is 1-72 h; the protective atmosphere in step (1) comprises one of nitrogen and argon; the addition reaction in step (2) is carried out in an air atmosphere or a protective atmosphere; The dosage ratio of the first organic solvent to ammonium thiocyanate is 1.0 mL:1-10 mmol; The dosage ratio of ammonium thiocyanate to the second organic solvent is 0.5-10 mmol:1.5 mL; The first organic solvent and the second organic solvent each independently comprise one or more of chloroform, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, toluene, acetonitrile, dichloromethane, 1,2-dichloroethane, acetone and tetrahydrofuran.

8. The preparation method according to claim 7, characterized in that The addition reaction in step (2) is carried out in an air atmosphere or a protective atmosphere comprising one of nitrogen and argon.

9. Application of the polyacyl dithiocarbamate compound according to any one of claims 1-3 or the polyacyl dithiocarbamate compound prepared by the preparation method according to any one of claims 4-8 as a refractive material or as a metal ion adsorption material.

10. Application of the polyacyl dithiocarbamate compound according to any one of claims 1-3 or the polyacyl dithiocarbamate compound prepared by the preparation method according to any one of claims 4-8 for degradation and recycling.

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