A method for preparing and applying a polythioamide compound.
By using the polymerization reaction of elemental sulfur, multi-halogenated compounds, and multi-amine compounds, the problem of high raw material cost in the synthesis of polythioamides has been solved, enabling low-cost and high-efficiency preparation and application of polythioamides.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SOUTH CHINA UNIV OF TECH
- Filing Date
- 2023-12-05
- Publication Date
- 2026-07-31
AI Technical Summary
Existing methods for synthesizing polythioamides suffer from high raw material costs and complex processes, which limit their development and application.
Polythioamide compounds were prepared by polymerizing elemental sulfur, polyhalogenated compounds, polyamine compounds, and base compounds in an organic solvent under reaction conditions of 80–100 °C and 6–15 hours.
This method enables the synthesis of polythioamides with readily available raw materials, simple process, and high efficiency. The product yield is high, the price is low, and it has good thermal stability and processability. Furthermore, it has good coordination ability with noble metal ions.
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Figure CN117866192B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the fields of polymer chemistry and materials science, and in particular to a method for preparing and applying polythioamide compounds. Background Technology
[0002] Polythioamides have attracted attention due to their excellent properties, such as luminescence. However, while there are many reported methods for synthesizing polythioamides, their development is limited by the complexity and high cost of raw materials. The reported synthesis methods also have certain drawbacks, severely hindering the development and application of polythioamides. The synthesis methods for polythioamides are shown in formula (I). Method A: In 1999, Japanese scientists developed a multi-component polymerization method for preparing polythioamides using elemental sulfur, aromatic aldehydes, and aliphatic amines. Method B: In 2015, our research group reported a multi-component polymerization method for preparing polythioamides using elemental sulfur, aromatic alkynes, and aliphatic amines. Method C: In 2017, Professor Chen Youming's research group synthesized polythioamides using a three-component polymerization of elemental sulfur, benzylamine, and aliphatic amines; however, the substrate applicability of this method is relatively limited. Method D: Tang Benzhong's research group efficiently prepared polythioamides using multi-component polymerization of phenylacetic acid monomers with elemental sulfur and diamine monomers. Method E: Tang Benzhong's research group prepared polythioamides using pyridine-activated diyne as a monomer at room temperature or 40°C. However, these methods for preparing polythioamides have a problem: the monomers are expensive.
[0003] Therefore, it is essential to explore new methods for preparing polythioamides, develop more efficient and convenient polymerization systems, and explore new applications for polythioamides. Literature review reveals that elemental sulfur is a simple, inexpensive, and readily available raw material. Using elemental sulfur as a raw material not only reduces costs but also allows for wider applications in industrial production, particularly in polymer synthesis, where it imparts excellent mechanical and processability properties. Literature research indicates that the reactivity of halogenated hydrocarbons is as follows: 1,4-di(iodomethyl)benzene > 1,4-di(bromomethyl)benzene > 1,4-di(chloromethyl)benzene. Among halogenated hydrocarbons, 1,4-di(bromomethyl)benzene is a relatively inexpensive commercial monomer. Therefore, utilizing elemental sulfur and some commercial monomers to achieve low-cost and large-scale preparation of polythioamides holds promise for its further development. (Synthesis, 1986, 1986 (11): 894-899.; J Polym Sci Pol Chem. 2001, 39, 3739.; Macromolecules 2015, 48, 7747.; Macromolecules 2017,50,8505.; J.Am.Chem.Soc.2019,142,978.; Chem.Commun.,2022,58,1994.)
[0004] Summary of the Invention
[0005] The purpose of this invention is to provide a method for preparing polythioamide compounds that uses readily available raw materials, has a simple process, and is highly efficient, as well as its applications.
[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:
[0007] A method for preparing a polythioamide compound includes the following steps:
[0008] Elemental sulfur, polyhalogenated compounds, polyamine compounds, and base compounds are mixed in an organic solvent and polymerized to obtain polythioamide compounds.
[0009] Furthermore, the polyamine compound is selected from at least one of diamine compounds, triamine compounds, and tetraamine compounds;
[0010] Preferably, the polyamine compound is selected from at least one of the following structural formulas:
[0011] H2N-C k H 2k -NH2
[0012] Where k is an integer from 1 to 20;
[0013] More preferably, the polyamine compound is selected from at least one of the following structural formulas:
[0014]
[0015]
[0016] Furthermore, the multi-halogenated compound is selected from at least one of dihalogenated compounds, ternary halogenated compounds, and quaternary halogenated compounds.
[0017] Preferably, the dihalogenated compound is selected from at least one of the following structural formulas:
[0018] XC k H 2k -X
[0019] Where Ar is an aryl group, k is an integer from 1 to 20, and X is one of the elements Cl, Br, or I.
[0020] More preferably, the dihalogenated compound is selected from at least one of the following structural formulas:
[0021]
[0022] Furthermore, the alkali compound is selected from one or more of N-methylpiperidine, DBU (1,8-diazabicycloundec-7-ene), and sodium hydroxide;
[0023] Preferably, the base compound is N-methylpiperidine and / or DBU.
[0024] Furthermore, the organic solvent is N,N-dimethylformamide;
[0025] Further, the concentration of the polyhalogenated compound in the organic solvent is 0.1–1 mol / L. Preferably, the concentration of the polyhalogenated compound in the organic solvent is 0.5–1 mol / L; more preferably, the concentration of the polyhalogenated compound in the organic solvent is 0.5 mol / L.
[0026] Furthermore, the molar ratio of elemental sulfur, the amino group in the polyamine compound, the halogenated carbon atom in the polyhalogenated compound, and the base compound is 1–6:1:1–6:2–6.
[0027] Furthermore, the polymerization reaction temperature is 80–100°C, and the polymerization reaction time is 6–15 h; preferably, the polymerization reaction temperature is 90–100°C, and the polymerization reaction time is 14 h.
[0028] Furthermore, after the polymerization reaction, the mother liquor after the polymerization reaction is dissolved in organic solvent 1, then added to a precipitant, and the precipitate is collected and dried to obtain a polythioamide compound.
[0029] Preferably, the drying temperature is 20-30°C; more preferably, the drying temperature is 22-28°C; and even more preferably, the drying temperature is 25°C.
[0030] Preferably, the organic solvent 1 is one or more of N,N-dimethylformamide and dimethyl sulfoxide;
[0031] Preferably, the precipitant is selected from one or more of methanol, n-hexane, and ethanol. More preferably, the precipitant is n-hexane and / or ethanol.
[0032] Furthermore, the polythioamide compound comprises the following general structural formula:
[0033]
[0034] Where n is an integer between 2 and 400; R 1 It is an alkyl group, R 2 For aryl, R 3 It is aryl or alkyl, R 4 It is aryl or alkyl, R 5 It is aryl or alkyl.
[0035] Preferably, the polythioamide compound specifically comprises the following structural formula:
[0036]
[0037]
[0038] In this context, i, m, and n are each independent integers between 2 and 400.
[0039] More preferably, the polythioamide compound specifically comprises the following structural formula:
[0040]
[0041] Where i, m, and n are all integers between 2 and 400.
[0042] Application of polythioamide compounds prepared by the above method in the adsorption of noble metal ions and / or heavy metal ions.
[0043] Furthermore, the noble metal ion is a gold ion.
[0044] Furthermore, the application includes the following steps:
[0045] First, polythioamide is added to a solution containing noble metal ions and / or heavy metal ions, and the mixture is stirred and then centrifuged.
[0046] Preferably, the solution containing noble metal ions and / or heavy metal ions is further mixed with 5 wt% hydrochloric acid aqueous solution to obtain a mixed solution, and then polythioamide is added.
[0047] Preferably, the concentration of noble metal ions and / or heavy metal ions in the solution containing noble metal ions and / or heavy metal ions is 10ug / L to 1000mg / L; 1mg to 10mg of polythioamide is added to every 1mL to 10mL of the mixed solution.
[0048] More preferably, the concentration of noble metal ions and / or heavy metal ions in the solution containing noble metal ions and / or heavy metal ions is 5 mg / L to 1000 mg / L; 10 mg of polythioamide is added to every 1 mL of solution containing noble metal ions and / or heavy metal ions.
[0049] Preferably, the stirring rate of the stirring reaction is 800 rpm, and the stirring reaction time is 1 min to 60 min.
[0050] Preferably, the centrifugation rate of the centrifugation process is 8000 rpm.
[0051] Preferably, the centrifugation time is 10 minutes.
[0052] Furthermore, the structure of the polythioamide is as follows:
[0053]
[0054] Where n is 2 to 300.
[0055] The beneficial effects of this invention are:
[0056] (1) The preparation method of the present invention has readily available reaction raw materials that can be directly purchased commercially and are inexpensive; the reaction process is simple and the product yield is high.
[0057] (2) Elemental sulfur and dihalogenated hydrocarbons are inexpensive. This method can not only introduce sulfur into polymers in a simple way, but also provides a way to develop and utilize abundant elemental sulfur resources.
[0058] (3) The polythioamide of the present invention is inexpensive and has a simple and efficient synthesis process;
[0059] (4) The preparation method of the present invention has strong group tolerance and can introduce a variety of functional groups into the monomer;
[0060] (5) The polythioamide compounds prepared by this invention have good coordination ability with gold ions and have potential application value in ion adsorption; in particular, they have high efficiency and high sensitivity in enriching gold. Attached Figure Description
[0061] Figure 1 Comparison of the proton NMR spectra of the polythioamide compound, its corresponding monomer, and the model compound prepared in Example 1 of this invention in deuterated DMSO;
[0062] Figure 2 Comparison of carbon NMR spectra of the polythioamide compound, its corresponding monomer, and the model compound prepared in Example 1 of this invention in deuterated DMSO;
[0063] Figure 3 The infrared absorption spectra of the polythioamide compound, its corresponding monomer, and the model compound prepared in Example 1 of this invention are shown below; Figure 1 , Figure 2 and Figure 3In this context, A is 1,4-di(bromomethyl)benzene, B is 1,6-hexanediamine, C is a monomer of polythioamide compound P1, and D is polythioamide compound P1.
[0064] Figure 4 The thermogravimetric curve of the polythioamide compound prepared in Example 1 of this invention is shown.
[0065] Figure 5 The image shows the DSC curve of the polythioamide compound prepared in Example 1 of this invention. Detailed Implementation
[0066] 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.
[0067] Example 1
[0068] A polythioamide compound, the structural formula of which is shown in P1:
[0069]
[0070] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (II):
[0071]
[0072] In this example, monomer M1 is elemental sulfur, which is commercially available; in this instance, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this instance, it was purchased from Anengji Company. M3 is 1,6-hexanediamine, which is commercially available; in this instance, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0073] The preparation steps of the polythioamide compound are as follows:
[0074] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 116.2 mg) of M3 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. Allow the mixture to stand, filter, and dry at 20 °C to obtain the polythioamide compound P1.
[0075] Analysis showed that the yield of polythioamide compound P1 was 91%, with a weight-average molecular weight of 11300 and a molecular weight distribution of 1.55. A comparison of the proton NMR spectra of this polythioamide compound and its corresponding monomer (* represents solvent peaks) is shown below. Figure 1 The comparison of their carbon NMR spectra is as follows: Figure 2 , Figure 1 The chemical shift at 10.34 ppm corresponds to the characteristic peak of the hydrogen atom on the -NH atom in the polythioamide compound. Figure 2 The chemical shift of 196.53 ppm corresponds to the characteristic peak of the carbon atom at C=S in polythioamide compounds, therefore, the polymer can be identified as a polythioamide compound. Furthermore, Figure 3 The images show the infrared absorption spectra of the polythioamide compound, its corresponding monomer, and the model compound prepared in Example 1 of this invention. Figure 3 The formation of the C=S peak can also be observed in the middle. Figure 4 The thermogravimetric curve of P1 is shown below. Figure 4 As can be seen, the temperature corresponding to a 5% weight loss is 268℃, indicating good thermal stability. Figure 5 For the DSC curve of P1, from Figure 5 It can be seen that the glass transition temperature of P1 is 126℃, which is much lower than its thermal decomposition temperature, thus ensuring the thermal processing performance of this type of compound.
[0076] Example 2
[0077] A polythioamide compound, the structural formula of which is shown in P2:
[0078]
[0079] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (III):
[0080]
[0081] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M4 is 1,8-octanediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0082] The preparation steps of the polythioamide compound are as follows:
[0083] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 144.3 mg) of M4 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P2.
[0084] Analysis showed that the yield of polythioamide compound P2 was 89%, the weight-average molecular weight was 12,500, and the molecular weight distribution was 1.45.
[0085] Example 3
[0086] A polythioamide compound, the structural formula of which is shown on page 3:
[0087]
[0088] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (iv):
[0089]
[0090] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M5 is 1,4-phenylenediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0091] The preparation steps of the polythioamide compound are as follows:
[0092] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 136.2 mg) of M5 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P3.
[0093] Analysis showed that the yield of polythioamide compound P3 was 96%, the weight-average molecular weight was 14,500, and the molecular weight distribution was 1.91.
[0094] Example 4
[0095] A polythioamide compound, the structural formula of which is shown on P4:
[0096]
[0097] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (V):
[0098]
[0099] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M6 is trans-1,4-cyclohexanediamine, which is commercially available; in this example, it was purchased from TCI Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0100] The preparation steps of the polythioamide compound are as follows:
[0101] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 114.2 mg) of M6 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P4.
[0102] Analysis showed that the yield of polythioamide compound P4 was 67%, the weight-average molecular weight was 11,200, and the molecular weight distribution was 1.64.
[0103] Example 5
[0104] A polythioamide compound, the structural formula of which is shown on page 5:
[0105]
[0106] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (VI):
[0107]
[0108] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M7 is 1,8-diamino-3,6-dioxaoctane, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0109] The preparation steps of the polythioamide compound are as follows:
[0110] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 148.2 mg) of M7 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P5.
[0111] Analysis showed that the yield of polythioamide compound P5 was 97%, the weight-average molecular weight was 11,400, and the molecular weight distribution was 1.74.
[0112] Example 6
[0113] A polythioamide compound, the structural formula of which is shown on page 6:
[0114]
[0115] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (VII):
[0116]
[0117] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M8 is 4,4'-diaminodicyclohexylmethane, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0118] The preparation steps of the polythioamide compound are as follows:
[0119] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 210.4 mg) of M8 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P6.
[0120] Analysis showed that the yield of polythioamide compound P6 was 63%, the weight-average molecular weight was 11,100, and the molecular weight distribution was 1.70.
[0121] Example 7
[0122] A polythioamide compound, the structural formula of which is shown on page 7:
[0123]
[0124] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (viii):
[0125]
[0126] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M6 is 4,4'-diaminodiphenylmethane, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0127] The preparation steps of the polythioamide compound are as follows:
[0128] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 198.3 mg) of M6 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P7.
[0129] Analysis revealed that the yield of polythioamide compound P7 was 85%, the weight-average molecular weight was 6600, and the molecular weight distribution was 1.26.
[0130] Example 8
[0131] A polythioamide compound, the structural formula of which is shown on page 8:
[0132]
[0133] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (IX):
[0134]
[0135] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M10 is p-phenylenediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0136] The preparation steps of the polythioamide compound are as follows:
[0137] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 108.1 mg) of M10 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P8.
[0138] Analysis revealed that the yield of polythioamide compound P8 was 81%, the weight-average molecular weight was 6100, and the molecular weight distribution was 1.27.
[0139] Example 9
[0140] A polythioamide compound, the structural formula of which is shown on page 9:
[0141]
[0142] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (x):
[0143]
[0144] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anaiji Company. M11 is 4,4'-diaminodiphenyl ether, which is commercially available; in this example, it was purchased from TCI Company. N-methylpiperidine in this example was purchased from Anaiji Company.
[0145] The preparation steps of the polythioamide compound are as follows:
[0146] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 200.2 mg) of M11 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P9.
[0147] Analysis showed that the yield of polythioamide compound P9 was 91%, the weight-average molecular weight was 5900, and the molecular weight distribution was 1.26.
[0148] Example 10
[0149] A polythioamide compound, the structural formula of which is shown on P10:
[0150]
[0151] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (XI):
[0152]
[0153] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M2 is 1,4-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anaiji Company. M12 is 4,4-diaminodiphenyl sulfide, which is commercially available; in this example, it was purchased from TCI Company. N-methylpiperidine in this example was purchased from Anaiji Company.
[0154] The preparation steps of the polythioamide compound are as follows:
[0155] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M2, and (1 mmol, 216.3 mg) of M12 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P10.
[0156] Analysis showed that the yield of polythioamide compound P10 was 66%, the weight-average molecular weight was 8100, and the molecular weight distribution was 1.55.
[0157] Example 11
[0158] A polythioamide compound, the structural formula of which is shown on page 11:
[0159]
[0160] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (xii):
[0161]
[0162] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M13 is 1,3-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M3 is 1,6-hexanediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0163] The preparation steps of the polythioamide compound are as follows:
[0164] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M13, and (1 mmol, 116.2 mg) of M3 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P11.
[0165] Analysis showed that the yield of polythioamide compound P11 was 89%, the weight-average molecular weight was 11,100, and the molecular weight distribution was 1.68.
[0166] Example 12
[0167] A polythioamide compound, the structural formula of which is shown on page 12:
[0168]
[0169] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (xiii):
[0170]
[0171] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M13 is 1,3-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M5 is 1,4-phenylenediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0172] The preparation steps of the polythioamide compound are as follows:
[0173] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M13, and (1 mmol, 136.2 mg) of M5 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P12.
[0174] Analysis showed that the yield of polythioamide compound P12 was 84%, the weight-average molecular weight was 12,100, and the molecular weight distribution was 1.38.
[0175] Example 13
[0176] A polythioamide compound, the structural formula of which is shown on page 13:
[0177]
[0178] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (XIV):
[0179]
[0180] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M13 is 1,3-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M4 is 1,8-octanediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0181] The preparation steps of the polythioamide compound are as follows:
[0182] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M13, and (1 mmol, 144.3 mg) of M4 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P13.
[0183] Analysis showed that the yield of polythioamide compound P13 was 78%, the weight-average molecular weight was 16,900, and the molecular weight distribution was 2.01.
[0184] Example 14
[0185] A polythioamide compound, the structural formula of which is shown on page 14:
[0186]
[0187] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine under the action of N-methylpiperidine, as shown in equation (XV):
[0188]
[0189] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M13 is 1,3-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M10 is 1,4-phenylenediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0190] The preparation steps of the polythioamide compound are as follows:
[0191] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M13, and (1 mmol, 108.1 mg) of M10 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P14.
[0192] Analysis revealed that the yield of polythioamide compound P14 was 58%, the weight-average molecular weight was 6900, and the molecular weight distribution was 2.01.
[0193] Example 15
[0194] A polythioamide compound, the structural formula of which is shown on page 15:
[0195]
[0196] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (xvii):
[0197]
[0198] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M13 is 1,3-di(bromomethyl)benzene, which is commercially available; in this example, it was purchased from Anengji Company. M9 is 4,4'-diaminodiphenylmethane, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0199] The preparation steps of the polythioamide compound are as follows:
[0200] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 264 mg) of M13, and (1 mmol, 198.3 mg) of M9 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P15.
[0201] Analysis revealed that the yield of polythioamide compound P15 was 58%, the weight-average molecular weight was 7000, and the molecular weight distribution was 1.33.
[0202] Example 16
[0203] A polythioamide compound, the structural formula of which is shown on page 16:
[0204]
[0205] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine in the presence of N-methylpiperidine, as shown in equation (XVII):
[0206]
[0207] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M14 is 2,6-di(bromomethyl)pyridine, which is commercially available; in this example, it was purchased from Anengji Company. M3 is 1,6-hexanediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0208] The preparation steps of the polythioamide compound are as follows:
[0209] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 265 mg) of M14, and (1 mmol, 116.2 mg) of M3 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P16.
[0210] Analysis showed that the yield of polythioamide compound P16 was 78%, the weight-average molecular weight was 15,100, and the molecular weight distribution was 1.94.
[0211] Example 17
[0212] A polythioamide compound, the structural formula of which is shown on page 17:
[0213]
[0214] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine under the action of N-methylpiperidine, as shown in equation (XVIII):
[0215]
[0216] Monomer M1 is elemental sulfur, which is commercially available; in this example, it was purchased from Guangzhou Reagent Factory. M14 is 2,6-di(bromomethyl)pyridine, which is commercially available; in this example, it was purchased from Anengji Company. M4 is 1,8-octanediamine, which is commercially available; in this example, it was purchased from Anengji Company. N-methylpiperidine in this example was purchased from Anengji Company.
[0217] The preparation steps of the polythioamide compound are as follows:
[0218] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 265 mg) of M14, and (1 mmol, 144.3 mg) of M4 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P17.
[0219] Analysis revealed that the yield of polythioamide compound P17 was 78%, with a weight-average molecular weight of 9100 and a molecular weight distribution of 1.34.
[0220] Example 18
[0221] A hyperbranched polythioamide compound, the structural formula of which is shown on page 18.
[0222]
[0223] The polythioamide compound is prepared by direct reaction of elemental sulfur, a brominated compound, and an amine under the action of N-methylpiperidine, as shown in equation (19):
[0224]
[0225] In this example, monomer M1 is elemental sulfur, which is commercially available; in this instance, it was purchased from Guangzhou Reagent Factory. Monomer M15 is 1,3,5-tris(bromomethyl)benzene, which is commercially available; in this instance, it was purchased from Merrill Chemicals. M3 is 1,6-hexanediamine, which is commercially available; in this instance, it was purchased from Amex. In this example, N-methylpiperidine was purchased from Amex.
[0226] The preparation steps of the polythioamide compound are as follows:
[0227] Add 96 mg (3 mmol) of monomer M1, (1 mmol, 356.9 mg) of M15, and (1.5 mmol, 174.3 mg) of M3 to a 10 mL polymerization tube. Then, add 2 mL of N,N-dimethylformamide and 1 mL of N-methylpiperidine sequentially using a syringe. Raise the temperature to 90 °C and maintain the temperature while stirring at 360 rpm for 8 hours. After the reaction is complete, dissolve the mother liquor in 2 mL of DMSO and then add it dropwise to methanol. After standing, filter and dry at 20 °C to obtain the polythioamide compound P18.
[0228] Analysis revealed that the yield of polythioamide compound P18 was 60%, with a weight-average molecular weight of 14,200 and a molecular weight distribution of 1.64.
[0229] As can be seen from the above embodiments, the present invention provides a method for preparing polythioamide compounds. The raw materials for the preparation method of the present invention are readily available, can be directly purchased commercially and are inexpensive, the reaction conditions are mild, the process is simple, and the yield is high.
[0230] The gold standard solution (1000 mg / L) was diluted to 100 mg / L with 5 wt% HCl. This solution was divided into several 10 mL portions, and 0, 0.5, 1, 3, 5, and 10 mg of polythioamide compounds P1, P11, P3, or P12 were added to each portion, respectively. The reaction system was stirred at room temperature for 1 h. The solution was then centrifuged at 8000 rpm for 10 min, and the supernatant was filtered through a filter membrane to obtain the final test solution. The atomic absorption spectra of the supernatant were measured, and the gold extraction rate in the gold-containing solution was calculated (see Table 1).
[0231] Table 1. Effect of polymer dosage on gold extraction efficiency (initial gold concentration of 1 mg / 10 ml)
[0232]
[0233] The gold standard solution (1000 mg / L) was diluted to 100 mg / L with 5 wt% HCl, and divided into several 10 mL portions. 10 mg of polythioamide compound P1, P11, P3, or P12 was added to each portion, and the solutions were stirred at room temperature for 1, 2, 5, 10, 20, 30, 40, and 60 min, respectively. The solutions were centrifuged at 8000 rpm for 10 min, and the supernatant was filtered through a filter membrane to obtain the final test solution. The atomic absorption spectra of the supernatant were then measured using AAS, and the gold extraction rate in the gold-containing solution was calculated (see Table 2).
[0234] Table 2. Effect of reaction time on gold extraction efficiency (initial gold concentration of 1 mg / 10 ml)
[0235]
[0236] The gold standard solution (1000 mg / L) was diluted with 5 wt% HCl to concentrations of 100 mg / L, 50 mg / L, 10 mg / L, 1 mg / L, 0.1 mg / L, and 0.01 mg / L, respectively. 10 mL of each gold-containing solution was then added to 300, 150, 30, 3, 0.3, and 0.03 μL of DMF solution of polythioamide compound P3 or P12, respectively, to a concentration of 33.3 mg / mL. The reaction system was stirred at room temperature for 1 h. The solution was then centrifuged at 8000 rpm for 10 min. The atomic absorption spectra of the supernatant were measured, and the gold extraction rate from the gold-containing solution was calculated (see Table 3).
[0237] Table 3 Effect of initial ion concentration on gold extraction efficiency
[0238]
[0239] Vp(uL): Volume of polymer DMF solution added
[0240] As can be seen from Tables 1-3, the polythioamide compounds prepared in this application have excellent adsorption effects on precious metal ions (gold ions) and can be used for the extraction / removal of precious metal ions / heavy metal ions.
[0241] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for producing a polythioamide compound, characterized by, Includes the following steps: Elemental sulfur, polyhalogenated compounds, polyamine compounds, and a base compound are mixed in an organic solvent and subjected to a polymerization reaction. The mother liquor after the polymerization reaction is dissolved in organic solvent 1, then added to a precipitating agent. The precipitate is collected and dried to obtain a polythioamide compound. The base compound is N-methylpiperidine. The organic solvent is... N,N -Dimethylformamide; the molar ratio of elemental sulfur, amino group in polyamine compounds, halogenated carbon atom in polyhalogenated compounds, and base compounds is 1~6:1:1~6:2~6; The polymerization reaction is carried out at a temperature of 80-100°C for 6-15 hours; the organic solvent 1 is dimethyl sulfoxide.
2. The production method according to claim 1, characterized by, The polyamine compound is selected from at least one of diamine compounds, triamine compounds, and tetraamine compounds; The multi-halogenated compound is selected from at least one of dihalogenated compounds, ternary halogenated compounds, and quaternary halogenated compounds.
3. The preparation method according to claim 2, characterized in that, The polyamine compound is selected from at least one of the following structural formulas: Where k is an integer from 1 to 20; The binary halogenated compound is selected from at least one of the following structural formulas: ； Where Ar is an aryl group, k is an integer from 1 to 20, and X is one of the elements Cl, Br, or I.
4. The preparation method according to claim 1, characterized in that, The concentration of the polyhalogenated compound in the organic solvent is 0.1~1 mol / L.
5. The preparation method according to claim 1, characterized in that, The drying temperature is 20~30℃; the precipitant is selected from one or more of methanol, n-hexane and ethanol.
6. The method of claim 1, wherein, The polythioamide compounds comprise the following general structural formula: , , and ; Where n is an integer between 2 and 400; R 1 It is an alkyl group, R 2 For aryl, R 3 It is aryl or alkyl, R 4 It is aryl or alkyl, R 5 It is aryl or alkyl.
7. The production method according to claim 6, wherein The polythioamide compounds specifically include the following structural formulas: In this context, i, m, and n are each independent integers between 2 and 400.