Polytrithiocarbonate compound containing ether oxygen chain and preparation method and application thereof
By introducing ether oxygen chains into polytrithiocarbonate, the problems of high glass transition temperature and poor solubility of the material are solved, resulting in better processing performance and solubility, expanding the application range, and possessing potential value for ion detection.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SOUTH CHINA UNIV OF TECH
- Filing Date
- 2026-05-12
- Publication Date
- 2026-07-31
AI Technical Summary
Polytrithiocarbonate materials suffer from problems such as excessively high glass transition temperature, difficulty in processing, and poor solubility, which limit their application areas.
By introducing an ether oxygen chain structure, polytrithiocarbonate compounds containing ether oxygen chains are synthesized through the reaction of polyethylene glycol dithiol, potassium carbonate, carbon disulfide, and N,N'-dimethylformamide.
It lowers the glass transition temperature of the material, improves its solubility and processing performance, broadens its application range, and exhibits fluorescence response to metal ions such as silver, gold, and iron, making it suitable for ion detection.
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Figure CN122483333A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer materials technology, and in particular to a polytrithiocarbonate compound containing an ether oxygen chain, its preparation method, and its application. Background Technology
[0002] The continuous progress of society has placed higher demands on the functional diversity and performance specificity of polymer materials, greatly promoting the development of novel polymer systems. Against this backdrop, introducing specific heteroatoms (such as sulfur, nitrogen, and oxygen) into the polymer backbone has become a key strategy for regulating the properties of polymer materials. Among them, sulfur atoms, due to their large atomic radius, diverse valence states, and unique electronic structure, have shown extraordinary potential in the design of functionalized polymers. Introducing sulfur into polymers yields structurally rich sulfur-containing polymers, endowing them with a wide range of properties and enabling their extensive applications in optical materials, adhesives, self-healing materials, energy storage materials, metal adsorbents, and biomaterials.
[0003] Among numerous sulfur-containing polymers, polytrithiocarbonates (PTCs) are a class of sulfur-rich polymers with distinctive structural features. The trithiocarbonate groups in the main chain endow them with both the excellent properties of traditional sulfur-containing polymers and the unique dynamic chemical reactivity of trithiocarbonate groups. Through innovative molecular structure design and synthetic methodologies, the chain structure of PTCs can be precisely controlled. PTCs exhibit exceptional mechanical property potential due to their unique trithiocarbonate functional groups (-SC(=S)-S-). Compared to traditional polycarbonate materials, PTCs maintain sufficient strength while exhibiting superior toughness. However, these materials often suffer from problems such as excessively high glass transition temperatures, high toughness, difficulty in processing, and poor solubility.
[0004] Etheroxy chains are a class of flexible segments consisting of alternating repeating ether bonds and methylene groups, with the structure -(CH2-O-CH2)-. They are extremely commonly used structural units in polymer material design. Etheroxy chains possess polarity, amphiphilicity, and ionic coordination ability, and can be introduced into polymers as soft segments to lower the glass transition temperature of polymer materials, thereby improving their flexibility, solubility, and thermodynamic properties. They are indispensable in fields such as polymer design with low glass transition temperatures, solid electrolytes, and biomedicine.
[0005] Therefore, introducing ether oxygen chains into the structure of polytrithiocarbonate is expected to solve the problems of excessively high glass transition temperature, difficulty in processing, and poor solubility of polytrithiocarbonate, and broaden the application fields of polytrithiocarbonate. Summary of the Invention
[0006] The purpose of this invention is to provide a polytrithiocarbonate compound containing an ether oxygen chain, its preparation method, and its application, addressing the shortcomings of existing technologies.
[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a polytrithiocarbonate compound containing an ether oxygen chain, the structural formula of which is: ; Where n is any integer between 2 and 500, p is any integer between 1 and 150, q is any integer between 1 and 150, and when both p and q are less than 10, p ≠ q.
[0008] Preferably, the polytrithiocarbonate compound is any one of the following structural formulas: ; Where n is any integer between 2 and 500.
[0009] The present invention also provides a method for preparing the aforementioned polytrithiocarbonate compound containing an ether oxygen chain, comprising the following steps: 1) Mix polyethylene glycol dithiol, potassium carbonate, carbon disulfide and N,N'-dimethylformamide to carry out the first reaction to obtain a reaction solution; 2) Add dibromopolyethylene glycol to the reaction solution to carry out the second reaction, thereby obtaining polytrithiocarbonate compounds containing ether oxygen chains.
[0010] Preferably, the structural formula of the polyethylene glycol dithiol in step 1) is: , where p is any integer between 1 and 150.
[0011] Preferably, the structural formula of the dibromopolyethylene glycol in step 2) is as follows: , where q is any integer between 1 and 150, and p ≠ q when both p and q are less than 10.
[0012] Preferably, the molar ratio of polyethylene glycol dithiol, potassium carbonate, carbon disulfide and dibromopolyethylene glycol is 1:2~4:2~4:1, and the molar ratio of polyethylene glycol dithiol and N,N'-dimethylformamide in step 1) is 0.1~2.0 mol:1 L.
[0013] Preferably, the temperature of the first reaction is 20~30℃, and the reaction time is 1~2h; The temperature of the second reaction is 20~30℃, and the reaction time is 1~8h.
[0014] Preferably, stirring is performed during both the first and second reactions. The stirring speed is 200~600 rpm.
[0015] The present invention also provides the application of the aforementioned polytrithiocarbonate compounds containing ether oxygen chains in ion detection.
[0016] The beneficial effects of this invention are: Polymerizing dithiol monomers and dibromo monomers with ether-oxygen chains of different structures yields a variety of polytrithiocarbonate compounds with ether-oxygen chains. These compounds exhibit novel structures, high molecular weight, good thermal stability and solubility, and low glass transition temperatures. The polytrithiocarbonate compounds with ether-oxygen chains of this invention show significant fluorescence responses to metal ions such as silver, gold, and iron, demonstrating potential application value in the field of ion detection and improving the accuracy of ion detection. Attached Figure Description
[0017] Figure 1 The NMR spectra of polymers P2, P4, P11, and P15 in deuterated chloroform are shown below. In the NMR spectrum, A is the proton NMR spectrum of P2, B is the proton NMR spectrum of P4, C is the proton NMR spectrum of P11, D is the proton NMR spectrum of P15, E is the carbon NMR spectrum of P2, F is the carbon NMR spectrum of P4, G is the carbon NMR spectrum of P11, and H is the carbon NMR spectrum of P15. Figure 2 The ultraviolet absorption and fluorescence emission spectra of polymers P2, P4, P11, and P15 are shown, where A is the ultraviolet absorption spectrum and B is the fluorescence emission spectrum. Figure 3 The fluorescence emission spectra of polymers P2, P4, P11, and P15 before and after interaction with silver ions are shown. Figure 4 The graph shows the ratio of the maximum fluorescence emission intensity of polymers P2, P4, P11, and P15 before and after interaction with silver ions. In this graph, I represents the maximum fluorescence emission intensity after interaction with silver ions, and I0 represents the maximum fluorescence emission intensity before interaction with silver ions. Detailed Implementation
[0018] This invention provides a polytrithiocarbonate compound containing an ether oxygen chain, the structural formula of which is: ; Where n is any integer between 2 and 500, p is any integer between 1 and 150, q is any integer between 1 and 150, and when both p and q are less than 10, p ≠ q.
[0019] In this invention, in the structural formula of the polytrithiocarbonate compound, n is preferably any integer between 5 and 450, more preferably any integer between 10 and 400, and even more preferably any integer between 30 and 350; p is preferably any integer between 2 and 100, more preferably any integer between 3 and 80, and even more preferably any integer between 4 and 60; q is preferably any integer between 2 and 100, more preferably any integer between 3 and 80, and even more preferably any integer between 4 and 60, and when both p and q are <10, p ≠ q.
[0020] In this invention, the polytrithiocarbonate compound is any one of the following structural formulas: ; Wherein, n is any integer between 2 and 500, preferably any integer between 5 and 450, more preferably any integer between 10 and 400, and even more preferably any integer between 30 and 350.
[0021] The present invention also provides a method for preparing the aforementioned polytrithiocarbonate compound containing an ether oxygen chain, comprising the following steps: 1) Mix polyethylene glycol dithiol, potassium carbonate, carbon disulfide and N,N'-dimethylformamide to carry out the first reaction to obtain a reaction solution; 2) Add dibromopolyethylene glycol to the reaction solution to carry out the second reaction, thereby obtaining polytrithiocarbonate compounds containing ether oxygen chains.
[0022] In this invention, the structural formula of polyethylene glycol dithiol in step 1) is as follows: Where p is any integer between 1 and 150, preferably any integer between 2 and 100, more preferably any integer between 3 and 80, and more preferably any integer between 4 and 60.
[0023] In this invention, the structural formula of the dibromopolyethylene glycol in step 2) is as follows: Where q is any integer between 1 and 150, preferably any integer between 2 and 100, more preferably any integer between 3 and 80, and more preferably any integer between 4 and 60, and when both p and q are < 10, p ≠ q.
[0024] In this invention, the molar ratio of polyethylene glycol dithiol, potassium carbonate, carbon disulfide, and dibromopolyethylene glycol is preferably 1:2~4:2~4:1, more preferably 1:2.5~3.5:2.5~3.5:1, and even more preferably 1:3:3:1; the ratio of polyethylene glycol dithiol to N,N'-dimethylformamide in step 1) is preferably 0.1~2.0 mol:1 L, more preferably 0.4~1.5 mol:1 L, and even more preferably 1.0 mol:1 L.
[0025] In this invention, step 2) preferably further includes the addition of N,N'-dimethylformamide.
[0026] In this invention, the temperature of the first reaction is preferably 20~30℃, more preferably 22~28℃, and even more preferably 25℃; the time of the first reaction is preferably 1~2h, more preferably 1.2~1.8h, and even more preferably 1.5h. The temperature of the second reaction is preferably 20~30℃, more preferably 22~28℃, and even more preferably 25℃; the time of the second reaction is preferably 1~8h, more preferably 2~7h, and even more preferably 3~6h.
[0027] In this invention, stirring is preferably performed during the first reaction and during the second reaction. The stirring speed is preferably 200~600 rpm, more preferably 300~500 rpm, and even more preferably 400 rpm.
[0028] In this invention, after the second reaction in step 2) is completed, the reaction solution is preferably dropped into a settling agent for sedimentation, the precipitate is collected and washed, and then dried to constant weight to obtain a polytrithiocarbonate compound containing an ether oxygen chain. The settling agent is preferably a mixed solution of methanol and water, or a mixed solution of methanol, water and saturated salt water; In the methanol and water mixture, the volume ratio of methanol to water is preferably 0.2 to 2:1, more preferably 0.5 to 1.5:1, and even more preferably 1:1.
[0029] In this invention, the drying temperature is preferably 40~70℃, more preferably 50~60℃, and even more preferably 55℃.
[0030] The present invention also provides the application of the aforementioned polytrithiocarbonate compounds containing ether oxygen chains in ion detection.
[0031] 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.
[0032] Example 1
[0033] The structural formula of polytrithiocarbonate compounds containing ether oxygen chains is as follows: .
[0034] The synthetic route is as follows: .
[0035] The preparation method is as follows: At 25℃, 1 mmol of monomer M1 (bis(2-mercaptoethyl) ether), 3 mmol of potassium carbonate (purchased from Anaiji), and 2 mL of N,N'-dimethylformamide were mixed in a Schlenk tube and stirred at 500 rpm. Then, 3 mmol of carbon disulfide was added dropwise to the Schlenk tube. After the addition was complete, the first reaction was continued at 500 rpm for 1 h to obtain the reaction solution. 1 mmol of monomer M4 (1,2-bis(2-bromoethoxy)ethane, purchased from Leyan) was added to the reaction solution, and 1 mL of N,N'-dimethylformamide was added. The second reaction was continued at 500 rpm for 1 h. After the reaction was completed, a solid residue remained at the bottom of the Schlenk tube, and the upper layer was a yellow transparent liquid. The upper yellow transparent liquid was added dropwise to 100 mL of a methanol-water mixture (methanol and water volume ratio of 1:1) for precipitation. After the addition was complete, a yellow, viscous solid precipitated, which adhered to the container wall. The liquid was poured off, and the precipitate was washed three times with a 1:1 (v / v) methanol-water mixture. The washed precipitate was dissolved in 2 mL of tetrahydrofuran and dried in a vacuum oven at 65°C for 4 hours to remove the solvent. It was then ultrasonically washed with deionized water for 2 hours, followed by ultrasonic washing with methanol for 2 hours, and finally dried again in a vacuum oven at 65°C for 8 hours to obtain a yellow, oily polymer, which is a polytrithiocarbonate compound containing an ether oxygen chain, labeled P2.
[0036] In this embodiment, the yield of P2 was 85%, and the number-average molecular weight of P2 was 6300 g / mol and the molecular weight distribution was 1.44, as determined by an ultra-high performance polymer chromatography (APC) system.
[0037] Examples 2-4 describe the preparation of polytrithiocarbonate compounds containing ether oxygen chains using monomers M1 and M4 with different structures. The preparation methods are the same as in Example 1. Table 1 shows the structural formulas of the monomers and products of Examples 1-4, and Table 2 shows the yield and molecular weight distribution of the polytrithiocarbonate compounds prepared in Examples 1-4.
[0038] Table 1. Structural formulas of monomers and products from Examples 1-4
[0039] Table 2. Yields and molecular weight distribution of polytrithiocarbonate compounds prepared in Examples 1-4
[0040] Figure 1 The NMR spectra of polymers P2, P4, P11, and P15 in deuterated chloroform are shown below. In the NMR spectrum, A is the proton NMR spectrum of P2, B is the proton NMR spectrum of P4, C is the proton NMR spectrum of P11, D is the proton NMR spectrum of P15, E is the carbon NMR spectrum of P2, F is the carbon NMR spectrum of P4, G is the carbon NMR spectrum of P11, and H is the carbon NMR spectrum of P15.
[0041] Depend on Figure 1 It can be seen from the proton NMR spectrum that ( Figure 1 (A), chemical shifts of 3.75~3.70ppm and 3.63~3.58ppm correspond to the characteristic peaks of the hydrogen atom on the methylene group of the ether oxygen chain; in the carbon NMR spectrum ( Figure 1 The E), chemical shift of 223.84 ppm corresponds to the characteristic peak of the carbon atom on the C=S of the trithiocarbonate group, indicating that a polytrithiocarbonate compound containing an ether oxygen chain was successfully synthesized.
[0042] The ultraviolet absorption and fluorescence emission intensity of the polytrithiocarbonate compounds containing ether oxygen chains prepared in Examples 1-4 were tested. The test method was as follows: 20.2 mg of the polytrithiocarbonate compound containing ether oxygen chains was placed in a 20 mL glass bottle, and 10 mL of tetrahydrofuran (THF) (analytical grade) was added. The mixture was shaken and mixed until the compound was completely dissolved, obtaining a THF solution of the polytrithiocarbonate compound. 2700 μL of tetrahydrofuran (THF) (analytical grade) was added to a 4 mL glass bottle, followed by 300 μL of the THF solution of the polytrithiocarbonate compound. The mixture was shaken and mixed, and then placed in a quartz cuvette for testing.
[0043] Figure 2 The UV absorption and fluorescence emission spectra of polymers P2, P4, P11, and P15 are shown, where A is the UV absorption spectrum and B is the fluorescence emission spectrum.
[0044] The fluorescence emission spectra of polytrithiocarbonate compounds containing ether oxygen chains before and after interaction with silver ions were tested. The method was as follows: 20.2 mg of the polytrithiocarbonate compound containing ether oxygen chains was placed in a 20 mL glass bottle, and 10 mL of tetrahydrofuran (THF) (analytical grade) was added. The mixture was shaken and stirred until the compound was completely dissolved, obtaining a THF solution of the polytrithiocarbonate compound. 17 mg of silver nitrate was placed in a 20 mL glass bottle, and 10 mL of ultrapure water was added. The mixture was shaken and stirred until the silver nitrate was completely dissolved, obtaining a silver ion solution. 2400 μL of tetrahydrofuran (THF) (analytical grade) was added to a 4 mL glass bottle, followed by 300 μL of the polytrithiocarbonate compound THF solution and 300 μL of ultrapure water. The mixture was shaken and stirred, and then placed in a quartz cuvette for testing. This is the fluorescence emission spectrum before interaction with silver ions. In a separate 4 mL glass bottle, add 2400 μL of tetrahydrofuran (THF) (analytical grade), then add 300 μL of a polytrithiocarbonate compound THF solution and 300 μL of a silver ion solution. Start timing, shake to mix, and then transfer to a quartz cuvette. Begin testing after 1 minute of timing. This is the fluorescence emission spectrum after interaction with silver ions.
[0045] Figure 3 The fluorescence emission spectra of polymers P2, P4, P11, and P15 before and after interaction with silver ions are shown. Figure 4 The graph shows the ratio of the maximum fluorescence emission intensity of polymers P2, P4, P11, and P15 before and after interaction with silver ions. In this graph, I represents the maximum fluorescence emission intensity after interaction with silver ions, and I0 represents the maximum fluorescence emission intensity before interaction with silver ions.
[0046] Depend on Figures 2-4 It can be seen that polymers P2, P4, P11, and P15 exhibit similar maximum UV absorption values, all around 326 nm, and all possess a certain fluorescence emission intensity. Compared to pure tetrahydrofuran, the fluorescence emission intensity of the polymers is enhanced in the tetrahydrofuran / water mixed solution, which is due to the cluster luminescence properties of the polymers. After the polymers react with silver ions, the fluorescence emission intensity of the solution is significantly enhanced, and the shorter the ether oxygen chain segment in the polymer, the stronger the enhancement effect on fluorescence emission intensity.
[0047] As can be seen from the above embodiments, the present invention provides polytrithiocarbonate compounds containing ether oxygen chains, which have novel structures, high molecular weight, good thermal stability and solubility, low glass transition temperature, and significant fluorescence response to metal ions such as silver, gold, and iron, and have potential application value in the field of ion detection.
[0048] 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 polytrithiocarbonate compound containing an ether oxygen chain, characterized by, The structural formula of the polytrithiocarbonate compound is: ； Where n is any integer between 2 and 500, p is any integer between 1 and 150, q is any integer between 1 and 150, and when both p and q are less than 10, p ≠ q.
2. The ether-oxygen chain-containing polytrithiocarbonate compound according to claim 1, wherein The polytrithiocarbonate compound is any one of the following structural formulas: ； Where n is any integer between 2 and 500.
3. The method for preparing the polytrithiocarbonate compound containing an ether oxygen chain as described in claim 1 or 2, characterized in that, It includes the following steps: 1) Mix polyethylene glycol dithiol, potassium carbonate, carbon disulfide and N,N'-dimethylformamide to carry out the first reaction to obtain a reaction solution; 2) Add dibromopolyethylene glycol to the reaction solution to carry out the second reaction, thereby obtaining polytrithiocarbonate compounds containing ether oxygen chains.
4. The preparation method according to claim 3, characterized in that, Step 1) The structural formula of the polyethylene glycol dithiol is: , where p is any integer between 1 and 150.
5. The preparation method according to claim 3 or 4, characterized in that, Step 2) The structural formula of the dibromopolyethylene glycol is: , where q is any integer between 1 and 150, and p ≠ q when both p and q are less than 10.
6. The preparation method according to claim 5, characterized in that, The molar ratio of polyethylene glycol dithiol, potassium carbonate, carbon disulfide and dibromopolyethylene glycol is 1:2~4:2~4:1, and the ratio of polyethylene glycol dithiol and N,N'-dimethylformamide in step 1) is 0.1~2.0 mol:1 L.
7. The preparation method according to claim 6, characterized in that, The temperature of the first reaction is 20~30℃, and the reaction time is 1~2h; The temperature of the second reaction is 20~30℃, and the reaction time is 1~8h.
8. The preparation method according to claim 7, characterized in that, Stirring is performed during the first reaction and during the second reaction. The stirring speed is 200~600 rpm.
9. The application of the polytrithiocarbonate compound containing an ether oxygen chain as described in claim 1 or 2 in ion detection.