CN115466388B - Polythiourea compound and preparation method thereof - Google Patents
Polythiourea compound and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polythiourea compound and a preparation method thereof, belonging to the technical field of organic synthesis. The invention carries out heating stirring reaction on elemental sulfur, malonic acid and polyamine compounds in an organic solvent, and then obtains the polythiourea compounds through separation and sedimentation treatment. The raw materials used in the invention can be purchased commercially, the cost is low, the method is simple, the reaction yield is high, the atom economy is high, and the preparation can be carried out on a large scale.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a polythiourea compound and a preparation method thereof.
Background
In recent years, polythiourea has been widely paid attention to as a novel sulfur-containing functional polymer material, and because the polythiourea has excellent dielectric property and high refractive index property, thiourea groups can also produce coordination with heavy metal ions to enable the polythiourea to adsorb the heavy metal ions, and in addition, recombination of covalent bonds of the polythiourea and hydrogen bonding can realize self-healing. Therefore, the polythiourea has great application potential in the aspects of dielectric materials, high-refraction materials, metal coordination materials, self-healing materials and the like.
Simple substance sulfur is one of the largest byproducts of petrochemical industry, has the characteristics of stability, low toxicity, low cost and the like, and is an ideal raw material for synthesizing the polythiourea. On the other hand, annual yield of elemental sulfur reaches over eight tens of millions of tons, resulting in a large amount of sulfur accumulation. Elemental sulfur also creates serious safety and environmental problems during storage due to its flammability and oxidation reactions in air. Therefore, the direct conversion of economical, nontoxic and odorless elemental sulfur as a sulfur source into polythiourea is also an effective way to solve the problem of sulfur utilization.
The method for synthesizing the polythiourea is mainly prepared by the reaction of diamine monomer with thiourea, thiophosgene, diisothiocyanate and the like. Some of these methods have disadvantages, such as the need for microwave irradiation and expensive catalysts for thiourea, the high toxicity of thiophosgene as a monomer, the expensive thiocarbonyldiimidazole monomer, and the complex synthesis and purification of the diisoisothiocyanate.
Therefore, how to provide an economical and efficient preparation method for directly converting elemental sulfur into polythiourea is a problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a polythiourea compound and a preparation method thereof, which are used for solving the problems of complex preparation of raw materials for preparing the polythiourea compound, high preparation cost and larger toxicity of part of raw materials.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polythiourea compound, which comprises one of the following structural formulas:
wherein n is an integer between 2 and 2000;
R 1 、R 2 、R 3 independently is alkyl, alkoxy or aryl, R 4 、R 5 Independently an aryl group.
Further, R 1 、R 2 、R 3 Wherein the alkyl groups are independently alkyl groups having 1 to 12 carbon atoms.
Further, the polythiourea compound specifically comprises one of the following structural formulas:
wherein n is an integer between 2 and 2000.
The invention provides a preparation method of a polythiourea compound, which comprises the following steps:
mixing elemental sulfur, malonic acid and polyamine compounds in an organic solvent for reaction to obtain the polythiourea compound.
Further, the mole ratio of the elemental sulfur, the malonic acid and the polyamine compound is 1-8: 1 to 4:1 to 2.
Further, the mol volume ratio of the polyamine compound to the organic solvent is 0.05-2 mol:1L;
the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, chloroform, N-hexane, 1, 4-dioxane, methanol, ethanol, toluene, isopropanol and tetrahydrofuran.
Further, the polyamine compound specifically includes one of the following structural formulas: h 2 N-R 6 -NH 2 H 2 N-R 7 -NH 2
；
Wherein R is 6 、R 7 Independently alkyl or alkoxy, and j, k and m independently represent integers of 1-20.
Further, the reaction is carried out under the action of a catalyst, and the catalyst comprises one or more of potassium fluoride, potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, triethylene diamine, N-methylpiperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, bis (triphenylphosphine) ammonium chloride, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene, potassium tert-butoxide, 1, 4-diazabicyclo, 4-dimethylaminopyridine, phosphazene ligand P1-tert-butyl, phosphazene ligand P2-tert-butyl, phosphazene ligand P4-tert-butyl and triethylamine; the mole ratio of the elemental sulfur to the catalyst is 1-8: 0.05 to 14.
Further, the reaction is carried out in air or a protective atmosphere comprising nitrogen and/or argon.
Further, the reaction temperature is 50-130 ℃, and the reaction time is 1-24 h.
The invention has the beneficial effects that:
(1) The method has the advantages that the adopted reaction raw materials are easy to obtain, can be directly purchased commercially, is low in price, consumes elemental sulfur, and relieves the problem of massive accumulation of the elemental sulfur; the invention has mild reaction condition, simple process and high reaction efficiency.
(2) According to the preparation method disclosed by the invention, malonic acid is used as a monomer, and the polythiourea compound is efficiently prepared.
(3) The preparation method of the invention can be carried out under the air condition, and can be used for large-scale gram-scale preparation.
(4) The preparation method of the invention has good universality and can be suitable for various monomers with different types.
Drawings
FIG. 1 is a chart showing the comparison of nuclear magnetic resonance hydrogen spectra of the polythiourea compound prepared in example 1 of the present invention and its corresponding monomers and model compounds in deuterated dimethyl sulfoxide;
FIG. 2 is a chart showing the nuclear magnetic resonance carbon spectrum of the polythiourea compound prepared in example 1 of the present invention and the corresponding monomer and model compound in deuterated dimethyl sulfoxide;
FIG. 3 is a chart showing nuclear magnetic resonance hydrogen spectra of the polythiourea compounds prepared in examples 2 to 9 of the present invention in deuterated dimethyl sulfoxide;
FIG. 4 is a chart showing nuclear magnetic resonance carbon spectra of the polythiourea compounds prepared in examples 2 to 9 of the present invention in deuterated dimethyl sulfoxide;
FIG. 5 is an infrared absorption spectrum of the polythiourea compound prepared in example 1 of the present invention and its corresponding monomer and model compound.
Detailed Description
The invention provides a polythiourea compound, which comprises one of the following structural formulas:
wherein n is an integer between 2 and 2000, preferably an integer between 10 and 1500, more preferably an integer between 50 and 1200;
R 1 、R 2 、R 3 independently is alkyl, alkoxy or aryl, R 4 、R 5 Independently an aryl group.
In the present invention, R 1 、R 2 、R 3 The alkyl group is independently an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 3 to 10 carbon atoms, and more preferably an alkyl group having 5 to 8 carbon atoms.
In the present invention, the polythiourea compound is preferably one of the following structural formulas:
wherein n is an integer of 2 to 2000, preferably 10 to 1500, and more preferably 50 to 1200.
The invention provides a preparation method of a polythiourea compound, which comprises the following steps:
mixing elemental sulfur, malonic acid and polyamine compounds in an organic solvent for reaction to obtain the polythiourea compound.
In the invention, the mole ratio of the elemental sulfur, the malonic acid and the polyamine compound is 1-8: 1 to 4:1 to 2, preferably 2 to 6: 2-3: 1 to 1.5, more preferably 3 to 5:2.5:1.2.
in the invention, the mol volume ratio of the polyamine compound to the organic solvent is 0.05-2 mol:1L, preferably 0.1 to 1.5mol:1L, more preferably 0.5 to 1.0mol:1L.
In the present invention, the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, chloroform, N-hexane, 1, 4-dioxane, methanol, ethanol, toluene, isopropanol and tetrahydrofuran, preferably one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, chloroform, N-hexane and 1, 4-dioxane.
In the present invention, the polyamine compound is preferably one of the following structural formulas: h 2 N-R 6 -NH 2 H 2 N-R 7 -NH 2
The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 6 、R 7 Independently alkyl or alkoxy, and j, k and m independently represent integers of 1-20.
In the present invention, j, k, and m are independently an integer of preferably 5 to 15, more preferably 8 to 12.
In the present invention, the reaction is carried out under the action of a catalyst comprising one or more of potassium fluoride, potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, triethylenediamine, N-methylpiperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, bis (triphenylphosphine) ammonium chloride, 1,5, 7-triazobicyclo (4.4.0) dec-5-ene, potassium t-butoxide, 1, 4-diazabicyclo, 4-dimethylaminopyridine, phosphazene ligand P1-t-butyl, phosphazene ligand P2-t-butyl, phosphazene ligand P4-t-butyl and triethylamine, preferably potassium fluoride, potassium carbonate, sodium carbonate, 4-dimethylaminopyridine, N-methylpiperidine, bis (triphenylphosphine) ammonium chloride and one or more preferably one or more of potassium fluoride, phosphazene ligand P4-t-butyl and phosphazene ligand P4-t-butyl phosphate, and further preferably one or more of 4-methyl-4-aminopyridine.
In the invention, the mole ratio of the elemental sulfur to the catalyst is 1-8: 0.05 to 14, preferably 2 to 6:0.1 to 12, more preferably 3 to 5:2 to 10, more preferably 4:4 to 6.
In the present invention, the reaction is carried out in air or a protective atmosphere comprising nitrogen and/or argon, preferably nitrogen.
In the invention, the reaction temperature is 50-130 ℃, and the reaction time is 1-24 hours; preferably, the reaction temperature is 80-120 ℃, and the reaction time is 5-20 hours; more preferably, the reaction temperature is 100℃and the reaction time is 10 to 15 hours.
In the present invention, the reaction is carried out under stirring at a rotation speed of 100 to 1000r/min, preferably 400 to 600r/min, and more preferably 500r/min.
In the invention, after the reaction is finished, a reaction product system is separated to obtain a pure polythiourea compound;
the separation operation is to add the reaction liquid after removing the solids into a precipitator for sedimentation, collect the precipitate and dry the precipitate to constant weight, thus obtaining the pure polythiourea compound.
In the present invention, the precipitant is preferably an aqueous methanol solution, wherein the volume ratio of methanol to water is 3 to 5:1, preferably 4:1.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A polythiourea compound has a structural formula shown as P1:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 1, 6-hexamethylenediamine monomers in an organic solvent, and the reaction equation is shown as the formula (I):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m3 is 1, 6-hexamethylenediamine, commercially available, in this example from Boschniakia corporation.
The preparation method of the thiourea compound P1 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (256 mg,8.0 mmol), malonic acid M2 (270 mg,2.6 mmol) and 1, 6-hexamethylenediamine M3 (232 mg,2.0 mmol) were successively added, and the mixture was evacuated and replaced with nitrogen three times, 1mL of dimethyl sulfoxide was added by syringe, and reacted at 100℃under 500r/min with stirring for 8 hours. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the red-brown solid P1 of the polythiourea compound; the yield of the final product, polythiourea compound P1, was 85%, the weight average molecular weight was 65100g/mol, the molecular weight distribution was 1.93, and the degree of polymerization n was 213, as determined and analyzed.
The comparative chart of nuclear magnetic resonance hydrogen spectrum of the polythiourea compound and the corresponding monomer thereof in deuterated dimethyl sulfoxide is shown in figure 1 (representing solvent peak), and compared with carboxyl hydrogen of monomer M2 (figure 1A) at 12.58ppm, and carboxyl hydrogen of monomer M3 (figure 1B) at 1.33ppm 2 In the nuclear magnetic hydrogen spectrum of the polythiourea compound P1 (FIG. 1D), the chemical shift value of hydrogen in the thiourea group-NH-was located at a low field of 7.30ppm, which is consistent with the chemical shift value of hydrogen of the thiourea group-NH-in the model molecule (FIG. 1C) of 7.28 ppm. Methylene hydrogen-CH on alkyl chain 2 Chemical shift values were located at 3.33ppm, 1.46ppm and 1.26ppm, respectively.
The nmr carbon spectrum contrast in deuterated dimethyl sulfoxide is shown in fig. 2 (representing the solvent peak), and the chemical shift of c=s in the carbon spectrum of polythiourea compound P1 (fig. 2D) is at 181.97ppm, which coincides with the chemical shift value 181.94ppm of c=s in the model molecule (fig. 2C), compared to the carboxyl carbon at 168.87ppm of monomer M2 (fig. 2A) and monomer M3 (fig. 2B).
The infrared absorption spectrum is shown in FIG. 3, and the telescopic vibration absorption peak of C=S bond in the polythiourea compound P1 is located at 1553cm -1 The N-H stretching vibration peak is 3240cm -1 。
Example 2
A polythiourea compound has a structural formula shown as P2:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and octanediamine monomers in an organic solvent, and the reaction equation is shown as a formula (II):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m4 is octanediamine, commercially available from Ann Ji corporation in this example.
The preparation method of the thiourea compound P2 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (256 mg,8.0 mmol), malonic acid M2 (270 mg,2.6 mmol) and subemine M4 (288 mg,2.0 mmol) were successively added, and the mixture was evacuated and replaced with nitrogen three times, 1mL of dimethyl sulfoxide was added by syringe, and reacted at 100℃and 500r/min with stirring for 8 hours. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the red-brown solid P2 of the polythiourea compound; the yield of the final product, polythiourea compound P2, was 83%, the weight average molecular weight was 32300g/mol, the molecular weight distribution was 1.43, and the degree of polymerization n was 120, as determined and analyzed.
Example 3
A polythiourea compound has a structural formula shown as P3:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 1, 2-bis (2-aminoethoxy) ethane monomer in an organic solvent, and the reaction equation is shown as the formula (III):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m5 is 1, 2-bis (2-aminoethoxy) ethane, commercially available from Annaiji corporation in this example.
The preparation method of the thiourea compound P3 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (256 mg,8.0 mmol), malonic acid M2 (270 mg,2.6 mmol), 1, 2-bis (2-aminoethoxy) ethane M5 (298 mg,2.0 mmol) were successively added, the nitrogen was replaced three times by vacuum, 1mL of dimethyl sulfoxide was added by syringe, and the reaction was stirred at 100℃for 8 hours at 500r/min. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the red-brown solid P3 of the polythiourea compound; the yield of the final product, polythiourea compound P3, was 90%, the weight average molecular weight was 28300g/mol, the molecular weight distribution was 1.36, and the degree of polymerization n was 109, as determined and analyzed.
Example 4
A polythiourea compound has a structural formula shown as P4:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 4,4' -diamino dicyclohexyl methane monomer in an organic solvent, and the reaction equation is shown as a formula (IV):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m6 is 4,4' -diaminodicyclohexylmethane, commercially available, in this example from Aba Ding Gongsi.
The preparation method of the thiourea compound P4 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (256 mg,8.0 mmol), malonic acid M2 (270 mg,2.6 mmol), 4' -diaminodicyclohexylmethane M6 (420 mg,2.0 mmol) were successively added, and the mixture was evacuated and replaced with nitrogen three times, 1mL of dimethyl sulfoxide was added by syringe, and reacted at 100℃under 500r/min with stirring for 8 hours. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the solution is stood, filtered and dried to obtain the white solid P4 of the polythiourea compound; the yield of the final product, polythiourea compound P4, was 99%, the weight average molecular weight was 32600g/mol, the molecular weight distribution was 1.66, and the degree of polymerization n was 78, as determined and analyzed.
Example 5
A polythiourea compound has a structural formula shown as P5:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 1, 4-xylylenediamine monomers in an organic solvent, and the reaction equation is shown as a formula (five):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m7 is 1, 4-xylylenediamine, commercially available from Annaiji corporation in this example.
The preparation method of the thiourea compound P5 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (256 mg,8.0 mmol), malonic acid M2 (270 mg,2.6 mmol), 1, 4-xylylenediamine M7 (272 mg,2.0 mmol) were successively added, the nitrogen was replaced three times by vacuum, 1mL of dimethyl sulfoxide was added by syringe, and the reaction was stirred at 500r/min at 100℃for 8 hours. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, standing, filtering and drying are carried out, so that the pink solid P5 of the polythiourea compound is obtained; the yield of the final product, polythiourea compound P5, was 97%, the weight average molecular weight was 31200g/mol, the molecular weight distribution was 1.47, and the degree of polymerization n was 119, as determined and analyzed.
Example 6
A polythiourea compound has a structural formula shown as P6:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 4,4' -diaminodiphenyl ether monomer in an organic solvent, and the reaction equation is shown as a formula (six):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m8 is 4,4' -diaminodiphenyl ether, commercially available from Boschniakia corporation in this example.
The preparation method of the thiourea compound P6 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (192 mg,6.0 mmol), malonic acid M2 (312 mg,3.0 mmol), 4' -diaminodiphenyl ether M8 (400 mg,2.0 mmol) were successively added, the nitrogen was replaced three times by vacuum, 2mL of dimethyl sulfoxide was added by syringe, and the reaction was stirred at 100℃for 12 hours at 500r/min. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the yellow solid P6 of the polythiourea compound; the yield of the final product, polythiourea compound P6, was 86%, the weight average molecular weight was 20200g/mol, the molecular weight distribution was 2.06, and the degree of polymerization n was 40, as determined and analyzed.
Example 7
A polythiourea compound has a structural formula shown as P7:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and p-phenylenediamine monomers in an organic solvent, and the reaction equation is shown as a formula (seventh):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m9 is p-phenylenediamine, commercially available from Ann Ji, inc. in this example.
The preparation method of the thiourea compound P7 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (192 mg,6.0 mmol), malonic acid M2 (312 mg,3.0 mmol), p-phenylenediamine M9 (216 mg,2.0 mmol) were successively added, the vacuum was pulled and nitrogen was changed three times, 2mL of dimethyl sulfoxide was added by syringe, and the reaction was stirred at 500r/min at 100℃for 1 hour. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the dark brown solid P7 of the polythiourea compound; the yield of the final product, polythiourea compound P7, was 45%, the weight average molecular weight was 13600g/mol, the molecular weight distribution was 1.86, and the degree of polymerization n was 49, as determined and analyzed.
Example 8
A polythiourea compound has a structural formula shown as P8:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 1, 2-bis (4-aminophenoxy) ethane monomer in an organic solvent, and the reaction equation is shown as the formula (eight):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m10 is 1, 2-bis (4-aminophenoxy) ethane, commercially available, in this example from Pichia pharmaceutical company.
The preparation method of the thiourea compound P8 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (256 mg,8.0 mmol), malonic acid M2 (270 mg,2.6 mmol), 1, 2-bis (4-aminophenoxy) ethane M10 (488 mg,2.0 mmol) were successively added, the nitrogen was changed three times by vacuum, 1mL of dimethyl sulfoxide was added by syringe, and the reaction was stirred at 100℃for 8 hours at 500r/min. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the light brown solid P8 of the polythiourea compound; the yield of the final polythiourea compound P8 was 90%, the weight average molecular weight was 19800g/mol, the molecular weight distribution was 2.16, and the polymerization degree n was 32, as determined and analyzed.
Example 9
A polythiourea compound has a structural formula shown as P9:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 4,4' -diaminodiphenylmethane monomer in an organic solvent, and the reaction equation is shown as a formula (nine):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m11 is 4,4' -diaminodiphenylmethane, commercially available from Annaiji corporation in this example.
The preparation method of the thiourea compound P9 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (192 mg,6.0 mmol), malonic acid M2 (312 mg,3.0 mmol), 4' -diaminodiphenylmethane M11 (390 mg,2.0 mmol) were successively added, the nitrogen was replaced three times by vacuum, 2mL of dimethyl sulfoxide was added by syringe, and the reaction was stirred at 500r/min at 100℃for 12 hours. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the yellow solid P9 of the polythiourea compound; the yield of the final product, polythiourea compound P9, was 92%, the weight average molecular weight was 27200g/mol, the molecular weight distribution was 1.40, and the degree of polymerization n was 80, as determined and analyzed.
Example 10
A polythiourea compound has a structural formula shown as P9:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 4,4' -diaminodiphenylmethane monomer in an organic solvent, and the reaction equation is shown as the formula (ten):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m11 is 4,4' -diaminodiphenylmethane, commercially available from Annaiji corporation in this example; KF is potassium fluoride, commercially available from Annaiji, inc. in this example; DMAP is 4-dimethylaminopyridine, commercially available from merrill in this example.
The preparation method of the thiourea compound P9 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (192 mg,6.0 mmol), malonic acid M2 (312 mg,3.0 mmol), 4' -diaminodiphenylmethane M11 (390 mg,2.0 mmol), potassium fluoride KF (116 mg,2.0 mmol), 4-dimethylaminopyridine DMAP (244 mg,2.0 mmol) were successively added, the nitrogen was purged three times, 2mL of dimethyl sulfoxide was added by syringe, and the reaction was stirred at 500r/min at 100℃for 12 hours. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the yellow solid P9 of the polythiourea compound; the yield of the final product, polythiourea compound P9, was 99%, the weight average molecular weight was 75500g/mol, the molecular weight distribution was 3.52, and the degree of polymerization n was 90, as determined and analyzed.
Example 11
A polythiourea compound has a structural formula shown as P1:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 1, 6-hexamethylenediamine monomers in an organic solvent, and the reaction equation is shown as formula (eleven):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m3 is 1, 6-hexamethylenediamine, commercially available, in this example from Boschniakia corporation.
The preparation method of the thiourea compound P1 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (256 mg,8.0 mmol), malonic acid M2 (270 mg,2.6 mmol) and 1, 6-hexamethylenediamine M3 (232 mg,2.0 mmol) were successively added, and the mixture was evacuated and replaced with nitrogen three times, 1mL of dimethyl sulfoxide was added by syringe, and reacted at a rotation speed of 500r/min at 50℃for 24 hours under stirring. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the red-brown solid P1 of the polythiourea compound; the yield of the final polythiourea compound P1 was 51%, the weight average molecular weight was 8400g/mol, the molecular weight distribution was 1.29, and the polymerization degree n was 41, as determined and analyzed.
Example 12
A polythiourea compound has a structural formula shown as P1:
the polythiourea compound is prepared by directly reacting elemental sulfur, malonic acid and 1, 6-hexamethylenediamine monomers in an organic solvent, and the reaction equation is shown as formula (twelve):
wherein M1 is sublimed sulfur, commercially available from Aba Ding Gongsi in this example; m2 is malonic acid, commercially available, in this example from Boschniakia corporation; m3 is 1, 6-hexamethylenediamine, commercially available, in this example from Boschniakia corporation.
The preparation method of the thiourea compound P1 comprises the following steps:
to a 10mL polymerization tube, sublimed sulfur M1 (256 mg,8.0 mmol), malonic acid M2 (270 mg,2.6 mmol) and 1, 6-hexamethylenediamine M3 (232 mg,2.0 mmol) were successively added, the nitrogen was replaced three times by vacuum, 1mL of dimethyl sulfoxide was added by syringe, and the reaction was stirred at 130℃for 8 hours at 500r/min. After the reaction is finished, 2mL of dimethyl sulfoxide is used for diluting the reaction solution, then the obtained solution is filtered by suction to remove solid in the solution, then the reaction solution is dripped into a mixed solution with the volume ratio of methanol to water being 4:1 for sedimentation, and finally, the mixture is stood, filtered and dried to obtain the red-brown solid P1 of the polythiourea compound; the yield of the final product, polythiourea compound P1, was 70%, the weight average molecular weight was 22700g/mol, the molecular weight distribution was 1.49, and the degree of polymerization n was 96, as determined and analyzed.
From the above examples, the present invention provides a polythiourea compound and a preparation method thereof. The invention carries out heating stirring reaction on elemental sulfur, malonic acid and polyamine compounds in an organic solvent, and then obtains the polythiourea compounds through separation and sedimentation treatment. The raw materials used in the invention can be purchased commercially, no catalyst is needed, the cost is low, the method is simple, the reaction yield is high, the atom economy is high, and the preparation can be carried out on a large scale.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The polythiourea compound is characterized by comprising one of the following structural formulas:
wherein n is an integer between 2 and 2000;
R 1 、R 2 、R 3 independently is an alkyl group, an alkoxy group or an aryl group,R 4 、R 5 independently an aryl group.
2. The polythiourea of claim 1 wherein R 1 、R 2 、R 3 Wherein the alkyl groups are independently alkyl groups having 1 to 12 carbon atoms.
3. The polythiourea compound of claim 1 or 2, wherein the polythiourea compound specifically comprises one of the following structural formulas:
wherein n is an integer between 2 and 2000.
4. A method for producing a polythiourea compound as defined in any one of claims 1 to 3, comprising the steps of:
mixing elemental sulfur, malonic acid and polyamine compounds in an organic solvent for reaction to obtain the polythiourea compound.
5. The method according to claim 4, wherein the mole ratio of elemental sulfur, malonic acid and polyamine is 1 to 8:1 to 4:1 to 2.
6. The method according to claim 4 or 5, wherein the molar volume ratio of the polyamine compound to the organic solvent is 0.05 to 2mol:1L;
the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, chloroform, N-hexane, 1, 4-dioxane, methanol, ethanol, toluene, isopropanol and tetrahydrofuran.
7. The method of claim 6, wherein the polyamine compound specifically comprises one of the following structural formulas:
；
wherein R is 6 、R 7 Independently alkyl or alkoxy, and j, k and m independently represent integers of 1-20.
8. The preparation method according to claim 4, 5 or 7, wherein the reaction is carried out under the action of a catalyst comprising one or more of potassium fluoride, potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, triethylenediamine, N-methylpiperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, bis (triphenylphosphine) ammonium chloride, 1,5, 7-triazidovicyclo (4.4.0) dec-5-ene, potassium t-butoxide, 1, 4-diazabicyclo, 4-dimethylaminopyridine, phosphazene ligand P1-t-butyl, phosphazene ligand P2-t-butyl, phosphazene ligand P4-t-butyl and triethylamine; the mole ratio of the elemental sulfur to the catalyst is 1-8: 0.05 to 14.
9. The method of claim 8, wherein the reaction is carried out in air or a protective atmosphere comprising nitrogen and/or argon.
10. The method according to claim 9, wherein the reaction temperature is 50 to 130 ℃ and the reaction time is 1 to 24 hours.
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