An aliphatic polythioamide compound, a preparation method and application thereof
Patent Information
- Application Number
- CN202610661493.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-05-14
- Publication Date
- 2026-08-21
AI Technical Summary
目前，聚硫代酰胺的合成仍然有限，主要集中于半芳香族/芳香族聚硫代酰胺，其方法可分为两种方式：一种是通过含硫代羰基的二元硫酯类化合物与二胺的缩合聚合制备，其缺点在于：二元硫酯的制备成本、聚合反应可能会释放有毒有害副产物；另外一类是通过单质硫、二胺与活性较高的含芳香环的芳香二醛、苄基二羧酸、苄胺、芳香二炔的多组分聚合反应来制备
(1)本发明的制备方法，聚合条件温和，工艺简单，聚合效率高。
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Figure CN122608872A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the fields of polymer chemistry and materials science, and in particular to an aliphatic polythioamide compound, its preparation method, and its application. Background Technology
[0002] Polythioamides, in which the oxygen atom in the amide bond is replaced by a sulfur atom, possess unique properties such as high refractive index with metal ion coordination, non-traditional luminescence, solubility, processability, and crystallinity. Currently, the synthesis of polythioamides remains limited, mainly focusing on semi-aromatic / aromatic polythioamides. The methods can be divided into two categories: one is the condensation polymerization of dithioester compounds containing thiocarbonyl groups with diamines, which has the disadvantages of high preparation costs and the potential release of toxic and harmful byproducts during polymerization; the other is the multi-component polymerization reaction of elemental sulfur, diamines, and highly reactive aromatic dialdehydes, benzyl dicarboxylic acids, benzylamines, and aromatic diynes containing aromatic rings. Furthermore, based on the hexavalent sulfur-fluorine exchange reaction (SuFEx), thiocarbonyl fluorides have also been developed as substitutes for thioester compounds, undergoing condensation reactions with diboronic acid monomers to construct aromatic polythioamides. This method mainly solves the problem of constructing polythioamides containing secondary amines, especially low-activity, highly sterically hindered aromatic secondary amine units. However, due to the requirement for monomer activity in polymerization reactions, the synthesis of aliphatic polythioamides is limited to the preparation of semi-aromatic / aromatic polythioamides. There is still no efficient polymerization method for the synthesis of aliphatic polythioamides.
[0003] The Willgerodt–Kindler reaction is a major method for constructing thioamides. It typically involves reacting elemental sulfur, an amine, and a third electrophilic substrate, such as an aromatic ketone or aldehyde, at high temperatures. The types of the third substrate have gradually expanded to include alkyl aldehydes, acetals, alkenes, alkynes, benzylamines, benzyl alcohols, benzyl thiols, imines, benzyl halides, and cinnamic acids, exhibiting different functional group tolerances and enabling the preparation of more diverse thioamide derivatives. The Willgerodt–Kindler reaction involves the oxidation or rearrangement of electron-deficient substrates. The aromatic group attached to these substrates can enhance the reactivity of the substrate through an inductive effect; therefore, aromatic substrates often exhibit higher reactivity than aliphatic substrates, and C=S formation is easier. Based on the idea of enhancing the reactivity of C=O in electrophiles through the inductive effect of aromatic rings, we propose to design a reaction using a diacid instead of an aldehyde to achieve efficient conversion from imines to C=S-NH- through decarboxylation and polysulfide-induced oxidation. Summary of the Invention
[0004] The purpose of this invention is to provide an aliphatic polythioamide compound, its preparation method, and its application, in order to solve the above-mentioned technical problems.
[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides an aliphatic polythioamide compound having the following general structural formula: ; Where n is an integer between 2 and 400, R 1 and R 2 It can be either alkyl or alkoxy.
[0006] Furthermore, the aliphatic polythioamide compound is selected from one of the following structural formulas: , , , , , , , , , , , , .
[0007] This invention also provides a method for preparing aliphatic polythioamide compounds, comprising the following steps: Elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds are polymerized in the presence of an organic solvent. After the reaction is completed, the aliphatic polythioamide compounds are obtained through post-treatment.
[0008] Furthermore, the aliphatic diamine is selected from any of the following structural formulas: .
[0009] Furthermore, the tetraacid compound is selected from any one of the following structural formulas: .
[0010] Furthermore, the molar ratio of the elemental sulfur, aliphatic diamine compound, and tetracarboxylic acid compound is 4~6:1:1~2.
[0011] Furthermore, the concentration of the aliphatic diamine compound in the organic solvent is 0.25~0.5 mol / L, and the organic solvent is dimethyl sulfoxide.
[0012] Furthermore, the polymerization reaction is carried out under stirring conditions, with a stirring speed of 250~800 rpm, a polymerization temperature of 100~130℃, and a polymerization time of 4~12 h.
[0013] Furthermore, the post-processing steps are as follows: after the reaction is completed, the reaction solution is cooled, diluted with 1 to 4 times the volume of the reaction solution with dimethyl sulfoxide, and then the diluted solution is dropped into a settling agent for sedimentation. The precipitate is collected and dried at 40 to 60°C to constant weight; the settling agent is diethyl ether.
[0014] This invention also provides the application of the above-mentioned aliphatic polythioamide compounds in high-temperature heat-resistant materials.
[0015] The beneficial effects of this invention are: (1) The preparation method of the present invention has mild polymerization conditions, simple process and high polymerization efficiency.
[0016] (2) The preparation method of the present invention has a wide range of substrate applications.
[0017] (3) The polyacylthiourea compounds of the present invention have high molecular weight and good thermal stability. Attached Figure Description
[0018] Figure 1 The images show the 1H NMR spectra of the aliphatic polythioamide compounds, thioamide compounds, and their corresponding monomers prepared in Example 1 of this invention in deuterated dimethyl sulfoxide, where A is the 1H NMR spectrum of 1,6-hexanediamine in deuterated dimethyl sulfoxide; B is the 1H NMR spectrum of decane-1,1,10,10-tetracarboxylic acid in deuterated dimethyl sulfoxide; C is the 1H NMR spectrum of the thioamide compounds in deuterated dimethyl sulfoxide; and D is... The NMR spectra of aliphatic polythioamide compounds in deuterated dimethyl sulfoxide are shown in the following figures: 1H NMR spectrum (E), 1,6-hexanediamine in deuterated dimethyl sulfoxide; 1C NMR spectrum (F), decane-1,1,10,10-tetracarboxylic acid in deuterated dimethyl sulfoxide; 1C NMR spectrum (G), thioamide compounds in deuterated dimethyl sulfoxide; and 1C NMR spectrum (H), aliphatic polythioamide compounds in deuterated dimethyl sulfoxide. Figure 2 Thermogravimetric curves of the aliphatic polythioamide compounds prepared in Examples 1-7 of this invention; Figure 3 The thermogravimetric curves of the aliphatic polythioamide compounds prepared in Examples 8-13 of this invention are shown. Detailed Implementation
[0019] This invention provides an aliphatic polythioamide compound having the following general structural formula: ; Where n is an integer between 2 and 400, R 1 and R 2It can be either alkyl or alkoxy.
[0020] In this invention, n is preferably an integer between 10 and 300, and R 1 and R 2 The independent component is preferably one of C2 to C40 alkyl or alkoxy groups, and more preferably C4 to C20 alkyl groups.
[0021] In this invention, the aliphatic polythioamide compound is preferably selected from one of the following structural formulas: , , , , , , , , , , , , .
[0022] This invention also provides a method for preparing aliphatic polythioamide compounds, comprising the following steps: Elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds are polymerized in the presence of an organic solvent. After the reaction is completed, the aliphatic polythioamide compounds are obtained through post-treatment.
[0023] In this invention, the preparation equation for the aliphatic polythioamide compound is as follows: .
[0024] In this invention, the aliphatic diamine is preferably selected from any of the following structural formulas: .
[0025] In this invention, the tetraacid compound is preferably selected from any one of the following structural formulas: .
[0026] In this invention, the molar ratio of elemental sulfur, aliphatic diamine compound and tetracarboxylic acid compound is 4~6:1:1~2, preferably 4.5~5.4:1:1.2.
[0027] In this invention, the concentration of the aliphatic diamine compound in the organic solvent is 0.25~0.5 mol / L, preferably 0.3~0.4 mol / L, and more preferably 0.32~0.35 mol / L; the organic solvent is preferably dimethyl sulfoxide.
[0028] In this invention, the polymerization reaction is carried out under stirring conditions, with a stirring speed of 250~800 rpm, preferably 300~700 rpm, and more preferably 400~600 rpm; the polymerization reaction temperature is 100~130℃, preferably 105~125℃, and more preferably 110~120℃; and the polymerization reaction time is 4~12h, preferably 5~10h, and more preferably 6~8h.
[0029] In this invention, the post-processing steps are as follows: after the reaction is completed, the reaction solution is cooled and diluted with 1 to 4 times the volume of the reaction solution, preferably 2 to 3 times the volume of dimethyl sulfoxide; then the diluted solution is dropped into a settling agent for sedimentation, the precipitate is collected and dried at 40 to 60°C to constant weight, preferably at 45 to 55°C to constant weight; the settling agent is preferably diethyl ether.
[0030] The polyacylthiourea compounds of the present invention have high molecular weight and good thermal stability.
[0031] This invention also provides the application of the above-mentioned aliphatic polythioamide compounds in high-temperature heat-resistant materials.
[0032] 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.
[0033] Example 1
[0034] An aliphatic polythioamide compound, the structural formula of which is shown in P1: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula:
[0035] Among them, monomer M1 is decane-1,1,10,10-tetracarboxylic acid. M2 is 1,6-diaminohexane, purchased from Energie.
[0036] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S 864.1 mg, 2 mmol), M1 (164.3 mg, 0.5 mmol), and M2 (58.1 mg, 0.5 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 2 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 500 rpm for 4 h. After the reaction was completed, 2 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 50 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 50 mL of methanol was added to obtain a black solid. The solid was filtered, washed with 20 mL of methanol, and finally dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P1. Analysis showed that the yield of polyacrylthiourea P1 was 86%, the number average molecular weight was 13400, and the molecular weight distribution was 2.35.
[0037] Example 2
[0038] An aliphatic polythioamide compound, the structural formula of which is shown in P2: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0039] Among them, monomer M1 is decane-1,1,10,10-tetracarboxylic acid. M3 is 1,8-diaminooctane, purchased from Leyan Company.
[0040] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S 81.92 g, 60 mmol), M1 (3.88 g, 12 mmol), and M3 (1.44 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 400 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P2.
[0041] Example 3
[0042] An aliphatic polythioamide compound, the structural formula of which is shown on page 3: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0043] Among them, monomer M1 is decane-1,1,10,10-tetracarboxylic acid. M4 is 1,10-diaminodecane, purchased from Leyan Company.
[0044] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S 81.92 g, 60 mmol), M1 (3.88 g, 12 mmol), and M4 (1.72 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 600 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P3.
[0045] Example 4
[0046] An aliphatic polythioamide compound, the structural formula of which is shown on page 4:
[0047] The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0048] Of these, monomer M5 is dodecane-1,1,12,12-tetracarboxylic acid. M2 is 1,6-diaminohexane, purchased from Energie.
[0049] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S 81.92 g, 60 mmol), M5 (4.22 g, 12 mmol), and M2 (1.16 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 500 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P4.
[0050] Example 5
[0051] An aliphatic polythioamide compound, the structural formula of which is shown on page 5: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0052] Among them, monomer M5 is dodecane-1,1,12,12-tetracarboxylic acid. M6 is 1,7-diaminoheptane, purchased from Leyan Company.
[0053] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S8 1.92 g, 60 mmol), M5 (4.22 g, 12 mmol), and M6 (1.30 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 500 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P5.
[0054] Example 6
[0055] An aliphatic polythioamide compound, the structural formula of which is shown on page 6: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0056] Among them, monomer M5 is decane-1,1,12,12-tetracarboxylic acid. M7 is 1,8-diaminooctane, purchased from Leyan Company.
[0057] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S8 1.92 g, 60 mmol), M5 (4.22 g, 12 mmol), and M7 (1.44 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 600 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P6.
[0058] Example 7
[0059] An aliphatic polythioamide compound, the structural formula of which is shown on page 7: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0060] Among them, monomer M5 is dodecane-1,1,12,12-tetracarboxylic acid. M8 is 1,9-diaminononane, purchased from Leyan Company.
[0061] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S8 1.92 g, 60 mmol), M5 (4.22 g, 12 mmol), and M8 (1.58 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 600 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P7.
[0062] Example 8
[0063] An aliphatic polythioamide compound, the structural formula of which is shown on page 8: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0064] Among them, monomer M5 is dodecane-1,1,12,12-tetracarboxylic acid. M9 is 1,10-diaminodecane, purchased from Leyan Company.
[0065] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S8 1.92 g, 60 mmol), M5 (4.22 g, 12 mmol), and M9 (1.72 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 500 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P8.
[0066] Example 9
[0067] An aliphatic polythioamide compound, the structural formula of which is shown on page 9: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0068] Among them, monomer M5 is dodecane-1,1,12,12-tetracarboxylic acid. M10 is 1,12-diaminododecane, purchased from Leyan Company.
[0069] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S 81.92 g, 60 mmol), M5 (4.22 g, 12 mmol), and M10 (2.00 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 500 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P9.
[0070] Example 10
[0071] An aliphatic polythioamide compound, the structural formula of which is shown on page 10: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0072] Among them, monomer M11 is octane-1,1,8,8-tetracarboxylic acid. M10 is 1,12-diaminododecane, purchased from Leyan Company.
[0073] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S 81.92 g, 60 mmol), M11 (3.51 g, 12 mmol), and M10 (2.00 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 500 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P10.
[0074] Example 11
[0075] An aliphatic polythioamide compound, the structural formula of which is shown on page 11: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0076] Among them, monomer M12 is nonane-1,1,9,9-tetracarboxylic acid. M10 is 1,12-diaminododecane, purchased from Leyan Company.
[0077] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S 81.92 g, 60 mmol), M12 (3.71 g, 12 mmol), and M10 (2.00 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 450 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P11.
[0078] Example 12
[0079] An aliphatic polythioamide compound, the structural formula of which is shown on page 12: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0080] Among them, monomer M13 is undecane-1,1,11,11-tetracarboxylic acid. M10 is 1,12-diaminododecane, purchased from Leyan Company.
[0081] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S 81.92 g, 60 mmol), M13 (4.05 g, 12 mmol), and M10 (2.00 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 500 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P12.
[0082] Example 13
[0083] An aliphatic polythioamide compound, the structural formula of which is shown on page 13: ; The aliphatic polythioamide compounds are prepared by direct reaction of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds, as shown in the following reaction formula: .
[0084] Of these, monomer M5 is dodecane-1,1,12,12-tetracarboxylic acid. M14 is 1,2-bis(2-aminoethoxy)ethane, purchased from Energie.
[0085] The preparation steps of the aliphatic polythioamide are as follows: Elemental sulfur (1 / 8S8 1.92 g, 60 mmol), M5 (4.22 g, 12 mmol), and M14 (1.48 g, 10 mmol) were added to a 250 mL reaction flask equipped with a magnetic stirrer. The reaction flask was evacuated three times with nitrogen gas through a double-row tube. Then, 40 mL of dimethyl sulfoxide was added, and the reaction was carried out at 110 °C and 500 rpm for 4 h. After the reaction was completed, 20 mL of dimethyl sulfoxide was added to quench the reaction. After cooling, the reaction solution was added dropwise to 500 mL of diethyl ether and stirred until sedimentation, resulting in a viscous black liquid. After standing, the supernatant was aspirated, and 500 mL of methanol was added to obtain a black solid. The solid was filtered and washed with 200 mL of methanol. Finally, it was dried in a vacuum oven at 40 °C for 12 h to obtain the black solid product P13.
[0086] The yields, number-average molecular weights, and molecular weight distributions of the polymers prepared in Examples 1 to 13 are shown in Table 1 below.
[0087] Table 1
[0088] As can be seen from the above embodiments, the present invention provides an aliphatic polythioamide compound, its preparation method, and its application. The preparation method of the present invention achieves the direct synthesis of aliphatic polythioamides, with high reaction efficiency, yielding high-yield aliphatic polythioamide compounds. The thermal decomposition temperature of the prepared polymer is as follows: Figure 2 and Figure 3 This aliphatic polythioamide compound has high molecular weight and good thermal stability, making it suitable for structural components used at high temperatures; it also has broad application prospects in the field of mechanical materials.
[0089] 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. An aliphatic polythioamide compound, characterized in that, The aliphatic polythioamide compounds have the following general structural formula: ； Where n is an integer between 2 and 400, R 1 and R 2 It can be either alkyl or alkoxy.
2. The aliphatic polythioamide compound according to claim 1, characterized in that, The aliphatic polythioamide compound is selected from one of the following structural formulas: 、 、 、 、 、 、 、 、 、 、 、 、 。 3. The method for preparing the aliphatic polythioamide compound according to any one of claims 1 or 2, characterized in that, Includes the following steps: Elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds are polymerized in the presence of an organic solvent. After the reaction is completed, the aliphatic polythioamide compounds are obtained through post-treatment.
4. The preparation method according to claim 3, characterized in that, The aliphatic diamine is selected from any of the following structural formulas: 。 5. The preparation method according to claim 3 or 4, characterized in that, The tetracarboxylic acid compound is selected from any one of the following structural formulas: 。 6. The preparation method according to claim 5, characterized in that, The molar ratio of elemental sulfur, aliphatic diamine compounds, and tetracarboxylic acid compounds is 4~6:1:1~2.
7. The preparation method according to claim 3 or 6, characterized in that, The concentration of the aliphatic diamine compound in the organic solvent is 0.25~0.5 mol / L, and the organic solvent is dimethyl sulfoxide.
8. The preparation method according to claim 7, characterized in that, The polymerization reaction is carried out under stirring conditions, with a stirring speed of 250~800 rpm, a polymerization temperature of 100~130℃, and a polymerization time of 4~12 h.
9. The preparation method according to claim 3, characterized in that, The post-processing steps are as follows: after the reaction is completed, the reaction solution is cooled, diluted with 1 to 4 times the volume of the reaction solution with dimethyl sulfoxide, and then the diluted solution is added dropwise to a settling agent for sedimentation. The precipitate is collected and dried at 40 to 60°C to constant weight; the settling agent is diethyl ether.
10. The application of the aliphatic polythioamide compound according to claim 1 or 2 in high-temperature heat-resistant materials.