A carbon dioxide-based sulfur-containing terpolymer and its preparation method

Abstract

This invention relates to the field of polymer materials technology, specifically to a carbon dioxide-based sulfur-containing terpolymer and its preparation method. The specific preparation method includes: polymerizing carbon dioxide, a cyclic sulfide, and a third monomer under the action of an organoboron catalyst and a co-catalyst to obtain the carbon dioxide-based sulfur-containing terpolymer. The invention employs a low-cost, simple, and efficient non-metallic Lewis acid catalyst, which, together with the co-catalyst, forms a two-component catalytic system to catalyze the polymerization reaction of carbon dioxide, cyclic sulfide, and the third monomer. The resulting copolymer contains at least one sulfur atom in the repeating unit of its main chain. The incorporation of sulfur atoms into the polymer main chain significantly improves the polymer's mechanical, optical, and thermal properties, as well as its ability to adhere to metal ions.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a carbon dioxide-based sulfur-containing terpolymer and its preparation method. Background Technology

[0002] Polymer materials are widely used in daily life. Among them, polycarbonate is widely used in construction, automotive, and electronics due to its excellent mechanical properties, transparency, and heat resistance. However, the traditional polycarbonate production process consumes a large amount of petroleum resources and generates significant carbon dioxide emissions. Therefore, developing an environmentally friendly polymer material is of great practical significance.

[0003] For example, CN116053575A discloses a process for preparing a carbon dioxide-based terpolymer electrolyte, which involves ring-opening copolymerization of carbon dioxide, propylene oxide, and a third monomer in the presence of a metalloporphyrin catalyst and a co-catalyst to obtain the carbon dioxide-based terpolymer. However, the cost of synthesizing carbon dioxide-based terpolymers using metalloporphyrin catalysts is high, limiting the commercial application of this process. Furthermore, existing catalysts generally suffer from low monomer conversion efficiency. Summary of the Invention

[0004] To address the high cost of synthesizing carbon dioxide-based terpolymers using metalloporphyrin catalysts and the generally low monomer conversion efficiency of existing catalysts, this invention provides a carbon dioxide-based sulfur-containing terpolymer and its preparation method.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows.

[0006] The first aspect of this invention provides a method for preparing a carbon dioxide-based sulfur-containing terpolymer, comprising the following steps: Carbon dioxide, cyclic sulfides, and a third monomer are polymerized under the action of an organoboron catalyst and a co-catalyst to prepare a carbon dioxide-based sulfur-containing terpolymer. The organoboron catalyst is triphenylborane, diphenylchloroborane, tetramethylborane, dichloromethoxyborane, tris(pentafluorophenyl)borane, β-isopinepine-9-boronbicyclo[3.3.1]nonane, or diethyl(3-pyridyl)borane. The co-catalyst is an organic amine, an organic ammonium salt, or an organic phosphorus. The third monomer is at least one of ethylene oxide, propylene oxide, epichlorohydrin, butane oxide, 1,2-epoxy-3,3,3-trifluoropropane, phenyl ethylene oxide, fluoropropane, carbon disulfide, aziridine compounds, cyclic anhydrides, O-carboxylic anhydrides, N-carboxylic anhydrides, thio-N-carboxylic anhydrides, cyclic carbonates, thiolactones, selenolactones, lactones, isocyanates, isothiocyanates, and phthalic anhydrides.

[0007] This invention mainly uses organic amines, organic ammonium salts, or organic phosphorus as co-catalysts, employing low-cost, simple, and efficient organic boron catalysts, and forming a two-component catalytic system with the co-catalysts to catalyze the polymerization reaction of carbon dioxide, cyclic sulfides, and a third monomer to prepare carbon dioxide-based sulfur-containing terpolymers. This reduces process costs while improving monomer conversion efficiency, which reaches over 90%.

[0008] This invention prepares a polymer whose main chain repeating unit contains at least one sulfur atom by using carbon dioxide, cyclic sulfides and a third monomer as raw materials. By incorporating sulfur atoms into the polymer main chain, the prepared polymer exhibits significant improvements in mechanical properties, optical properties, thermal properties and adhesion to metal ions, and also possesses excellent biodegradability.

[0009] Preferably, the molar ratio of cyclic sulfide to third monomer is 1:3 to 20; the molar ratio of cyclic sulfide to cocatalyst is 1:0.002 to 0.1; and the molar ratio of organoboron catalyst to cocatalyst is 2 to 0.5:1.

[0010] Preferably, the organic amine is triethylamine, tributylamine, tetrabutylamine succinate, or 1,8-diazabicyclo[5.4.0]undec-7-ene; the organic ammonium salt is bis(triphenylphosphine)ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, or tetrabutylamine terephthalate; and the organic phosphorus is triethylphosphorus, triphenylphosphorus, or tetrabutylphosphorus chloride.

[0011] Preferably, the cyclic sulfide is cyclothioethane, 2-(chloromethyl)cyclothioethane, or 2-methylcyclothioethane.

[0012] Preferably, the polymerization temperature is 40℃~180℃, the polymerization pressure is 0.5MPa~20MPa, and the polymerization time is 2 hours~48 hours.

[0013] Preferably, the polymerization reaction is carried out in an anhydrous and oxygen-free environment.

[0014] The second aspect of the present invention provides a carbon dioxide-based sulfur-containing terpolymer, which is prepared by the method for preparing the carbon dioxide-based sulfur-containing terpolymer described in the first aspect.

[0015] The beneficial effects of this invention are: 1. This invention employs a low-cost, simple, and efficient organoboron catalyst and co-catalyst to form a two-component catalytic system, which is used to catalyze the polymerization reaction of carbon dioxide, cyclic sulfides, and a third monomer to prepare a carbon dioxide-based sulfur-containing terpolymer polymer. This reduces process costs while improving monomer conversion efficiency, which reaches over 90%.

[0016] 2. This invention prepares a polymer whose main chain repeating units contain at least one sulfur atom by using carbon dioxide, cyclic sulfides, and a third monomer as raw materials. The incorporation of sulfur atoms into the polymer main chain endows the prepared terpolymer with excellent mechanical properties, thermal stability, and chemical stability. By adjusting the content of cyclic sulfides and carbon dioxide, the performance of the terpolymer can be optimized, making it suitable for various applications such as packaging materials, building materials, biomedical materials, and new energy materials.

[0017] 3. The preparation method of the present invention is simple and easy to implement, and is easy to scale up for production; moreover, it uses carbon dioxide as one of the raw materials, which reduces the dependence on petroleum resources and is green and environmentally friendly. Attached Figure Description

[0018] Figure 1 The image shows the hydrogen NMR spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 1 of this invention.

[0019] Figure 2 The image shows the hydrogen NMR spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 of this invention.

[0020] Figure 3 The image shows the hydrogen NMR spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 3 of this invention.

[0021] Figure 4 The image shows the DSC spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 1 of this invention.

[0022] Figure 5 The image shows the DSC spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 of this invention.

[0023] Figure 6 The DSC spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 3 of this invention. Figure 7 The TG curve is shown for the carbon dioxide-based sulfur-containing terpolymer prepared in Example 1 of this invention.

[0024] Figure 8 The TG curve is shown for the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 of this invention.

[0025] Figure 9 The TG curve is shown for the carbon dioxide-based sulfur-containing terpolymer prepared in Example 3 of this invention.

[0026] Figure 10 The tensile curve is shown for the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 of this invention. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0028] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] The technical solution of the present invention will be further described below through specific embodiments.

[0030] In the following embodiments, unless otherwise specified, the methods described are conventional methods; and unless otherwise specified, the reagents and materials described are commercially available.

[0031] In the following examples, the concentration of the triethylboron solution is 1 mol / L.

[0032] Example 1 A method for preparing a carbon dioxide-based sulfur-containing terpolymer includes the following steps: Weigh out cyclothioethane, propylene oxide, triethylamine, and a triphenylborane solution according to the following molar ratios: cyclothioethane and propylene oxide 1:16, cyclothioethane and triethylamine 1:0.04, and triphenylborane and triethylamine 0.5:1.

[0033] In an anhydrous and oxygen-free environment, cyclothioethane, propylene oxide, triethylamine, and triphenylborane solutions were sequentially added to a 50 mL high-pressure reactor, which was then charged with 0.5 MPa of carbon dioxide. The reactor was reacted at 180 °C for 2 h. After the reaction was completed, the carbon dioxide pressure was released, the product was dissolved in dichloromethane, and precipitated in ethanol to obtain a carbon dioxide-based sulfur-containing terpolymer.

[0034] The carbon dioxide-based sulfur-containing terpolymer prepared in Example 1 was subjected to molecular weight testing, NMR, thermal properties analysis, and mechanical property analysis after vacuum drying.

[0035] The 1H NMR spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 1 is shown below. Figure 1 As shown. The DSC spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 1 is shown below. Figure 4 As shown. The TG curve of the obtained carbon dioxide-based sulfur-containing terpolymer is shown in the figure. Figure 7 As shown. The DSC spectrum represents the differential scanning calorimetry (DSC) spectrum. The TG curve represents the thermogravimetric curve.

[0036] Depend on Figure 1 , Figure 4 and Figure 7The results verified that the structural formula of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 1 is as follows: .

[0037] Based on the results of molecular weight testing, NMR, thermal properties, and mechanical property analysis, Mn = 4.5 kg / mol, PDI = 1.7, and T... g = -20℃; Mn represents number-average molecular weight; PDI represents polydispersity index; T g It indicates the glass transition temperature.

[0038] Example 2 A method for preparing a carbon dioxide-based sulfur-containing terpolymer includes the following steps: Weigh out cyclothionane, propylene oxide, tetrabutylammonium chloride, and a diphenyl chloroborane solution according to the following molar ratios: cyclothionane and propylene oxide are 1:19, cyclothionane and tetrabutylammonium chloride are 1:0.01, and diphenyl chloroborane and tetrabutylammonium chloride are 1:1.

[0039] In an anhydrous and oxygen-free environment, cyclothioethane, propylene oxide, tetrabutylammonium chloride, and diphenyl chloroborane solution were sequentially added to a 50 mL high-pressure reactor, which was then charged with 0.5 MPa carbon dioxide and reacted at 180 °C for 2 h. After the reaction was completed, the carbon dioxide pressure was released, the product was dissolved in dichloromethane, and precipitated in ethanol to obtain a carbon dioxide-based sulfur-containing terpolymer.

[0040] The carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 was subjected to molecular weight testing, NMR, thermal properties analysis, and mechanical property analysis after vacuum drying.

[0041] The 1H NMR spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 is shown below. Figure 2 As shown; the DSC spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 is as follows. Figure 5 As shown; the TG curve of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 is shown. Figure 8 As shown.

[0042] Depend on Figure 2 , Figure 5 and Figure 8 The results verified that the structural formula of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 is as follows: .

[0043] The tensile curve of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 is shown below. Figure 10 As shown. Figure 10The results showed that the carbon dioxide-based sulfur-containing terpolymer prepared in Example 2 possessed certain mechanical strength. Based on molecular weight testing, NMR, thermal properties, and mechanical property analysis, the values ​​were: Mn = 6.5 kg / mol, PDI = 1.4, and Tg = 25 °C.

[0044] Example 3 A method for preparing a carbon dioxide-based sulfur-containing terpolymer includes the following steps: The following solutions of cyclothioethane, propylene oxide, triethylamine, and tetramethylborane were weighed according to the following molar ratios: cyclothioethane and propylene oxide 1:9, cyclothioethane and triethylamine 1:0.02, and tetramethylborane and triethylamine 0.5:1.

[0045] In an anhydrous and oxygen-free environment, cyclothioethane, propylene oxide, triethylamine, and tetramethylboron solution were sequentially added to a 50 mL high-pressure reactor, which was then charged with 10 MPa of carbon dioxide and reacted at 80 °C for 15 h. After the reaction was completed, the carbon dioxide pressure was released, the product was dissolved in dichloromethane, and precipitated in ethanol to obtain a carbon dioxide-based sulfur-containing terpolymer.

[0046] The carbon dioxide-based sulfur-containing terpolymer prepared in Example 3 was subjected to molecular weight testing, NMR, thermal properties analysis, and mechanical property analysis after vacuum drying. The 1H NMR spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 3 is shown below. Figure 3 As shown; the DSC spectrum of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 3 is as follows. Figure 6 As shown; the TG curve of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 3 is shown. Figure 9 As shown.

[0047] Depend on Figure 3 , Figure 6 and Figure 9 The results verified that the structural formula of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 3 is as follows: .

[0048] Based on the results of molecular weight testing, NMR, thermal properties and mechanical properties analysis, Mn = 2.5 kg / mol, PDI = 1.9, Tg = -0.5℃.

[0049] Example 4 A method for preparing a carbon dioxide-based sulfur-containing terpolymer includes the following steps: Weigh out cyclothioethane, epichlorohydrin, tetrabutylammonium chloride, and dichloromethoxyboron solution according to the following molar ratios: cyclothioethane and epichlorohydrin are 1:10, cyclothioethane and triethylamine are 1:0.005, and dichloromethoxyboron and tetrabutylammonium chloride are 2:1.

[0050] In an anhydrous and oxygen-free environment, cyclothioethane, epichlorohydrin, tetrabutylammonium chloride, and dichloromethoxyboron solution were sequentially added to a 50 mL high-pressure reactor, which was then charged with 10 MPa of carbon dioxide and reacted at 80 °C for 15 h. After the reaction was completed, the carbon dioxide pressure was released, the product was dissolved in dichloromethane, and precipitated in ethanol to obtain a carbon dioxide-based sulfur-containing terpolymer.

[0051] The carbon dioxide-based sulfur-containing terpolymer prepared in Example 4 was subjected to molecular weight testing, NMR, thermal properties analysis, and mechanical property analysis after vacuum drying.

[0052] Based on the 1H NMR spectrum, DSC spectrum, and TG curve of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 4, it can be concluded that the carbon dioxide-based sulfur-containing terpolymer was successfully prepared in Example 4. The molecular weight test, NMR, thermal properties, and mechanical properties analysis results show that Mn = 5.0 kg / mol, PDI = 1.4, and Tg = 17 °C.

[0053] Example 5 A method for preparing a carbon dioxide-based sulfur-containing terpolymer includes the following steps: Weigh out 2-(chloromethyl)cyclothioethane, phthalic anhydride, triethylamine, and tri(pentafluorophenyl)boron solution according to the following molar ratios: 1:19 for cyclothioethane and 1:0.1 for cyclothioethane and triethylamine, and 1:1 for tri(pentafluorophenyl)boron.

[0054] In an anhydrous and oxygen-free environment, 2-(chloromethyl)cyclothioethane, phthalic anhydride, triethylamine, and tris(pentafluorophenyl)boron solution were sequentially added to a 50 mL high-pressure reactor, which was then charged with 15 MPa of carbon dioxide and reacted at 90 °C for 10 h. After the reaction was completed, the carbon dioxide pressure was released, the product was dissolved in dichloromethane, and precipitated in ethanol to obtain a carbon dioxide-based sulfur-containing terpolymer.

[0055] The carbon dioxide-based sulfur-containing terpolymer prepared in Example 5 was subjected to molecular weight testing, NMR, thermal properties analysis, and mechanical property analysis after vacuum drying. The results from these analyses yielded the following parameters: Mn = 2.5 kg / mol, PDI = 1.9, and Tg = 20 °C.

[0056] Example 6 A method for preparing a carbon dioxide-based sulfur-containing terpolymer includes the following steps: According to the molar ratio of cyclothioethane to propylene oxide being 1:3, the molar ratio of cyclothioethane to triethylamine being 1:0.002, and the molar ratio of β-isopinepine-9-boron-bicyclo[3.3.1]nonane to tetrabutylammonium chloride being 0.5:1, cyclothioethane, isothiocyanate, tetrabutylammonium chloride, and β-isopinepine-9-boron-bicyclo[3.3.1]nonane solution were weighed.

[0057] In an anhydrous and oxygen-free environment, cyclothioethane, isothiocyanate, tetrabutylammonium chloride, and β-isopinepine-9-boron-bicyclo[3.3.1]nonane solution were sequentially added to a 50 mL high-pressure reactor, which was then charged with 20 MPa of carbon dioxide and reacted at 40 °C for 48 h. After the reaction was completed, the carbon dioxide pressure was released, the product was dissolved in dichloromethane, and precipitated in ethanol to obtain a carbon dioxide-based sulfur-containing terpolymer.

[0058] The carbon dioxide-based sulfur-containing terpolymer prepared in Example 6 was subjected to molecular weight testing, NMR, thermal properties analysis, and mechanical property analysis after vacuum drying. The results from these analyses yielded the following parameters: Mn = 8.0 kg / mol, PDI = 1.5, and Tg = -25 °C.

[0059] Example 7 A method for preparing a carbon dioxide-based sulfur-containing terpolymer includes the following steps: A solution of cyclothioethane, epichlorohydrin, tetrabutylammonium chloride, and diethyl(3-pyridyl)borane was weighed according to the following conditions: the molar ratio of cyclothioethane to epichlorohydrin was 1:10, the molar ratio of cyclothioethane to triethylamine was 1:0.005, and the molar ratio of diethyl(3-pyridyl)borane to tetrabutylammonium chloride was 2:1.

[0060] In an anhydrous and oxygen-free environment, cyclothioethane, epichlorohydrin, tetrabutylammonium chloride, and diethyl(3-pyridyl)borane solution were sequentially added to a 50 mL high-pressure reactor, which was then charged with 10 MPa of carbon dioxide and reacted at 80 °C for 15 h. After the reaction was completed, the carbon dioxide pressure was released, the product was dissolved in dichloromethane, and precipitated in ethanol to obtain a carbon dioxide-based sulfur-containing terpolymer.

[0061] The carbon dioxide-based sulfur-containing terpolymer prepared in Example 7 was subjected to molecular weight testing, NMR, thermal properties analysis, and mechanical property analysis after vacuum drying. Based on the 1H NMR spectrum, DSC spectrum, and TG curve of the carbon dioxide-based sulfur-containing terpolymer prepared in Example 7, it can be concluded that the carbon dioxide-based sulfur-containing terpolymer was successfully prepared in Example 7.

[0062] The difference from Example 1 lies in the use of a different organoboron catalyst. See Table 1 for details.

[0063] Table 1. Feeding conditions for different catalysts Table 1 shows a comparison of the number-average molecular weight, polydispersity index, and glass transition temperature of the carbon dioxide-based sulfur-containing terpolymers prepared in Examples 1 to 7.

[0064] Table 2 Number-average molecular weight, polydispersity index, and glass transition temperature Note: Mn represents number-average molecular weight; PDI represents polydispersity index; T g It indicates the glass transition temperature.

[0065] Analysis of the results in Table 2 shows that the number-average molecular weights of the carbon dioxide-based sulfur-containing terpolymers prepared in Examples 1 to 6 range from 2.5 kg / mol to 8.0 kg / mol; the polydispersity index ranges from 1.4 to 1.9; and the glass transition temperature is adjustable within a wide range of -25°C to 25°C. In particular, the lower glass transition temperature means that the material can maintain its elasticity at lower temperatures, avoiding embrittlement failure.

[0066] In summary, the embodiments of the present invention prepare a polymer whose repeating unit in the main chain contains at least one sulfur atom by using carbon dioxide, cyclic sulfides, and a third monomer as raw materials. The incorporation of sulfur atoms into the polymer main chain endows the prepared terpolymer with excellent mechanical properties, thermal stability, and chemical stability. By adjusting the content of cyclic sulfides and carbon dioxide, the performance of the terpolymer can be optimized, making it suitable for various applications such as packaging materials, building materials, biomedical materials, and new energy materials.

[0067] Table 3 Monomer Conversion Efficiency Note: The monomer conversion efficiency is calculated from NMR data based on cyclothioethane.

[0068] As can be seen from the data in Table 3, the embodiments of the present invention utilize an organoboron catalyst and a co-catalyst to form a two-component catalytic system, which reduces process costs while improving monomer conversion efficiency. Specifically, the monomer conversion rates of Examples 2 to 7 can reach over 90%, with Example 4 achieving a monomer conversion efficiency of 98%.

[0069] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a carbon dioxide-based sulfur-containing terpolymer, characterized in that, Includes the following steps: Carbon dioxide, cyclic sulfides, and a third monomer are polymerized under the action of an organoboron catalyst and a co-catalyst to prepare a carbon dioxide-based sulfur-containing terpolymer; the organoboron catalyst is triphenylborane, diphenylchloroborane, tetramethylborane, dichloromethoxyborane, tris(pentafluorophenyl)borane, β-isopinepine-9-boronbicyclo[3.3.1]nonane, or diethyl(3-pyridyl)borane; the co-catalyst is an organic amine, an organic ammonium salt, or an organic phosphorus. The third monomer is at least one of ethylene oxide, propylene oxide, epichlorohydrin, butane oxide, 1,2-epoxy-3,3,3-trifluoropropane, phenylene oxide, fluoropropylene oxide, carbon disulfide, aziridine compounds, cyclic anhydrides, O-carboxylic anhydrides, N-carboxylic anhydrides, thio-N-carboxylic anhydrides, cyclic carbonates, thiolactones, selenolactones, lactones, isocyanates, isothiocyanates, and phthalic anhydrides.

2. The method for preparing the carbon dioxide-based sulfur-containing terpolymer according to claim 1, characterized in that, The molar ratio of cyclic sulfide to the third monomer is 1:3 to 20; The molar ratio of cyclic sulfide to co-catalyst is 1:0.002–0.1; The molar ratio of organoboron catalyst to co-catalyst is 2 to 0.5:

1.

3. The method for preparing the carbon dioxide-based sulfur-containing terpolymer according to claim 1, characterized in that, The organic amine is triethylamine, tributylamine, tetrabutylamine succinate, or 1,8-diazabicyclo[5.4.0]undec-7-ene; The organic ammonium salt is bis(triphenylphosphine)ammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, or tetrabutylamine terephthalate; The organophosphorus compound is triethylphosphorus, triphenylphosphorus, or tetrabutylphosphorus chloride.

4. The method for preparing the carbon dioxide-based sulfur-containing terpolymer according to claim 1, characterized in that, The cyclic sulfide is cyclothioethane, 2-(chloromethyl)cyclothioethane, or 2-methylcyclothioethane.

5. The method for preparing the carbon dioxide-based sulfur-containing terpolymer according to claim 1, characterized in that, The polymerization temperature is 40℃~180℃, the polymerization pressure is 0.5MPa~20MPa, and the polymerization time is 2 hours~48 hours.

6. The method for preparing the carbon dioxide-based sulfur-containing terpolymer according to claim 1, characterized in that, The polymerization reaction is carried out in an anhydrous and oxygen-free environment.

7. A carbon dioxide-based sulfur-containing terpolymer, characterized in that, It is prepared by the method for preparing carbon dioxide-based sulfur-containing terpolymers according to any one of claims 1 to 6.

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