Polythioether as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of polymer preparation, and particularly relates to polythioether as well as a preparation method and application thereof. The preparation method of the polythioether, provided by the invention, comprises the following step: carrying out polymerization reaction on multi-element chalcone derived olefin and a sulfhydryl compound in an organic solvent to obtain the polythioether. In the preparation method, multi-chalcone derived olefin is selected to provide alkenyl, the alkenyl can directly react with a sulfhydryl compound without the action of a catalyst and an initiator, and the preparation method is mild in polymerization condition and simple in process. The polythioether provided by the invention has a specific structure and can be used for cation detection.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer preparation, and specifically relates to a polysulfide and a preparation method and application thereof. Background Art

[0002] Sulfur-containing polymers are widely used in optoelectronics, energy storage, and environmental fields because of their rich monomer sources and various functional groups. Abundant sulfur-containing monomers, such as sulfur (S8), carbon disulfide (CS2), thiols, and carbonyl sulfide (COS), can generate functional groups such as thioethers, thioketones, and thiocarbonates through polymerization pathways, thereby giving polymers different application properties. Among them, thiols are widely used because of their economic availability and strong nucleophilicity. The methods for preparing sulfur-containing polymers using thiols as monomers are mainly divided into four categories: thiol-olefins, thiol-epoxides, thiol-isocyanates, and thiol-dihalides. Thiol-ene / hydrocarbon click polymerization is widely used because of its simple operation, mild reaction conditions, and high monomer universality.

[0003] Traditional thiol-ene click reactions usually have two reaction pathways: free radical and nucleophilic attack, but usually require initiators or catalysts to promote the smooth progress of the polymerization reaction. In the prior art, there is a lack of a method for preparing polysulfide by thiol-ene reaction without the action of initiators or catalysts. Summary of the invention

[0004] The purpose of the present invention is to overcome the problem in the prior art that there is a lack of a method for preparing polysulfide by mercapto-ene reaction without an initiator or catalyst, and further to provide a polysulfide and a preparation method and application thereof.

[0005] In the present invention, -* represents a connecting bond.

[0006] The scheme adopted by the present invention is as follows:

[0007] The present invention provides a method for preparing polysulfide, comprising the following steps:

[0008] Polymerization reaction of polychalcone-derived olefin and mercapto compound is carried out in an organic solvent to obtain polysulfide.

[0009] Preferably, the polychalcone-derived olefin contains at least two vinyl groups; and the thiol compound contains at least two thiol groups.

[0010] Preferably, the polychalcone-derived olefin has a structure as shown in the following formula (V) or (VI):

[0011]

[0012]

[0013] The thiol compound has a structure as shown in the following formula (VII) or (VIII) or (IX):

[0014]

[0015] Preferably, R 1 , R 1’ , R 2 , R 2’ , R 3 , R 4 Each is independently selected from a substituted or unsubstituted C1-C60 aliphatic group or a substituted or unsubstituted C3-C60 aromatic group;

[0016] Preferably, R 3’ , R 3” Each is independently selected from a substituted or unsubstituted C1-C60 aliphatic group;

[0017] Among them, the substituents in the substituted C1-C60 aliphatic group and the substituted C3-C60 aromatic group are selected from any one or a combination of at least two of halogen, cyano, nitro, hydroxyl, amino, aldehyde, ester, C1-C30 straight or branched alkyl, C2-C10 alkenyl, C1-C30 alkoxy, C6-C60 aromatic, and C3-C60 heteroaromatic groups.

[0018] Preferably, R 1 , R 1’ , R 2 , R 2’ , R 3 , R 4 Each is independently selected from a substituted or unsubstituted C1-C30 aliphatic group or a substituted or unsubstituted C3-C30 aromatic group;

[0019] Preferably, R 3’ , R 3” Each is independently selected from a substituted or unsubstituted C1-C30 aliphatic group;

[0020] Among them, the substituents in the substituted C1-C30 aliphatic group and the substituted C3-C30 aromatic group are selected from any one or a combination of at least two of halogen, cyano, nitro, hydroxyl, amino, aldehyde, ester, C1-C30 straight or branched alkyl, C2-C10 alkenyl, C1-C30 alkoxy, C6-C60 aromatic, and C3-C60 heteroaromatic groups.

[0021] Preferably, the polysulfide has the following structure:

[0022]

[0023]

[0024] Among them, R 1 , R 1’ , R 2 , R 2’ , R 3 , R 3’ , R 3” , R 4 The definition is the same as above, and n is an integer from 2 to 200.

[0025] It can be understood that n is a polymer, and for formula (III) and formula (IV), the degree of polymerization is 2-200.

[0026] Preferably, R 1 , R 1’ , R 3 Each independently selected from the following groups:

[0027]

[0028] Wherein, h, i, j, k, l, and m are integers from 1 to 20, and X is selected from O or S elements;

[0029] Preferably, R 3’ Independently selected from groups having the following structures;

[0030]

[0031] Preferably, R 3” A group independently selected from the following structures:

[0032]

[0033] Preferably, R 2 , R 2’ , R 4 Each independently selected from the following groups:

[0034]

[0035] Wherein, o, p, q are integers of 1 to 20, X is selected from O or S elements, and Y is selected from methoxy.

[0036] Preferably, the polysulfide has the following structure:

[0037]

[0038] The definition of n is the same as above.

[0039] Preferably, the organic solvent is selected from at least one of tetrahydrofuran, dichloromethane, chloroform, toluene, benzene, chlorobenzene, m-xylene, mesitylene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylacetamide and N,N-dimethylformamide;

[0040] Preferably, the molar ratio of the vinyl group in the polychalcone-derived olefin to the thiol group in the thiol compound is (0.25-4):1

[0041] Preferably, the concentration of the polychalcone-derived olefin in the organic solvent is 0.05 to 5 mol / L.

[0042] Preferably, the polymerization reaction temperature is 10 to 100° C.; the polymerization reaction time is 5 min to 36 h;

[0043] Preferably, the polymerization reaction is carried out under air, oxygen, carbon dioxide, nitrogen or an inert atmosphere.

[0044] Preferably, the polymerization reaction further includes precipitation and drying processes.

[0045] Preferably, the precipitation process is to mix the system after the polymerization reaction with a precipitant and let it stand;

[0046] Preferably, the standing time is 5-15h;

[0047] Preferably, the precipitation process further includes a process of adding a diluent to dissolve before mixing with the precipitant and after the polymerization reaction is completed;

[0048] Preferably, the diluent is selected from at least one of dichloromethane, chloroform and tetrahydrofuran;

[0049] Preferably, the precipitant is selected from at least one of water, methanol, ethanol, n-hexane, petroleum ether, ether and acetone;

[0050] Preferably, the addition ratio of the diluent to the polychalcone-derived olefin is (5-1000):(0.1-5), and the ratio unit is mL:mmol;

[0051] Preferably, the drying is vacuum drying at a drying temperature of 25-80°C.

[0052] Preferably, after standing, the process further includes pouring out the clear liquid and washing the product; wherein the washing agent used for washing the product is selected from at least one of water, methanol, ethanol, n-hexane, petroleum ether, ether, and acetone;

[0053] Preferably, the volume ratio of the cleaning agent to the precipitating agent is (5-20):100.

[0054] The present invention also provides a polysulfide, which is prepared by the above-mentioned preparation method.

[0055] The polysulfide prepared by the preparation method described above or the use of the polysulfide described above in a fluorescent probe is characterized in that the fluorescent probe is used to detect cations;

[0056] Preferably, the cation includes Fe 3+ or Ag + .

[0057] Beneficial effects of the present invention:

[0058] The present invention provides a method for preparing a polysulfide, comprising the following steps: polymerizing a polychalcone-derived olefin and a thiol compound in an organic solvent to obtain a polysulfide. In the preparation method, a polychalcone-derived olefin is selected to provide an olefin group, which can directly react with the thiol compound without a catalyst and an initiator. The preparation method has mild polymerization conditions and a simple process.

[0059] The preparation method provided by the present invention has easy-to-obtain reaction raw materials, which can be directly purchased or prepared through simple reactions, has high atom economy, and the reaction yield is as high as 99%;

[0060] The polymerization process of the preparation method provided by the present invention generates no by-products, and is green polymerization that complies with atom economy;

[0061] The preparation method provided by the present invention can prepare polysulfide with good structure and adjustable performance;

[0062] The polysulfide provided by the present invention has good thermodynamic properties and excellent processability, and has good application prospects;

[0063] The polysulfide provided by the present invention has good cluster luminescence characteristics, shows obvious fluorescence, and Fe 3+ After the reaction, the fluorescence is quenched, and Fe can be detected 3+ , and can be regulated by solvent + After the action, the fluorescence was enhanced. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0065] Figure 1The hydrogen nuclear magnetic resonance spectra of the polysulfide P1, the model small molecule compound and its corresponding monomers prepared in Example 1 in CDCl3; wherein (a) is the spectrum of monomer 1a, (b) is the spectrum of monomer 2a, (c) is the spectrum of the model compound, and (d) is the spectrum of the polysulfide P1 prepared in Example 1;

[0066] Figure 2 This is a thermogravimetric curve of the polysulfide P1 prepared in Example 1;

[0067] Figure 3 is the fluorescence intensity ratio of the polysulfide P14 prepared in Example 14 in a DMF / H2O mixed solvent when reacting with different cations;

[0068] Figure 4 The polysulfide P14 prepared in Example 14 was reacted with different concentrations of Fe in a DMF / H2O mixed solvent. 3+ Linear relationship diagram of

[0069] Figure 5 is the fluorescence intensity ratio of the polysulfide P14 prepared in Example 14 in a THF / H2O mixed solvent when reacting with different cations;

[0070] Figure 6 The polysulfide P14 prepared in Example 14 was reacted with different concentrations of Ag in a THF / H2O mixed solvent. + Linear relationship diagram. DETAILED DESCRIPTION

[0071] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall be within the protection scope of the present invention.

[0072] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0073] The room temperature in the embodiment is 10-35°C.

[0074] Example 1

[0075] The present embodiment provides a method for synthesizing monomer 1a: add a magnet, isophthalaldehyde (1.34 g, 10 mmol) (commercially available, purchased from Anaiji Chemical in this example), NaOH (1.00 g, 25 mmol) (commercially available, purchased from McLean Reagent in this example) and 40 mL of methanol into a 250 mL two-necked bottle, add acetophenone (2.40 g, 20 mmol) (commercially available, purchased from Anaiji Chemical in this example) drop by drop, react at room temperature for 12 hours (speed of 500 rpm) after the addition is complete, filter after the reaction is completed, and dry the solid substance in a vacuum oven to constant weight to obtain a white solid with structure 1a with a yield of 65%. The structure of 1a is

[0076] The structure of monomer 1a in this embodiment is 2a is 1,8-octanedithiol, which is commercially available and was purchased from Anaiji Chemical in this example.

[0077] The present invention provides a method for preparing a polysulfide (P1), comprising the following steps:

[0078] (1) A magnet and monomer 1a (338.40 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2a (183.90 μL, 1 mmol) and 1 mL of chloroform were injected into the tube using a syringe under air atmosphere. The mixture was stirred and reacted at 60° C. under air atmosphere for 24 hours (rotation speed was 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0079] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) is added dropwise to 100 mL of methanol, and then allowed to stand (standing time is 12 h), the supernatant is poured out, the product is rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature is 50° C.) to obtain polysulfide P1.

[0080] The results of analysis showed that the yield of polysulfide P1 was 90%, the weight average molecular weight was 14,000, and the molecular weight distribution was 2.08.

[0081] The present invention also provides a model compound The preparation method comprises the following steps: adding a magnetic particle and a substrate chalcone (1.20 g, 6 mmol) (commercially available, purchased from Anaiji Chemical in this example) into a 25 mL polymerization tube, injecting a substrate 1-octanethiol (1.00 mL, 6 mmol) (commercially available, purchased from Anaiji Chemical in this example) and 2 mL of chloroform with a syringe under an air atmosphere; placing the polymerization tube at 60° C. and stirring for reaction for 24 hours (the speed is 400 rpm), cooling to room temperature after the reaction is completed, vacuum drying to remove the solvent, and vacuum drying to constant weight (drying temperature is 50° C.), to obtain a light yellow solid with a yield of 95%.

[0082] The H NMR spectra of the polysulfide P1, its corresponding monomer and the model compound (* represents the solvent peak) are as follows: Figure 1 (where (a) is the spectrum of monomer 1a, (b) is the spectrum of monomer 2a, (c) is the spectrum of the model compound, and (d) is the spectrum of polysulfide P1). The peak near δ7.83 ppm is attributed to the proton H of the olefin in monomer 1a. 1 ( Figure 1 a), which is in the model compound MC1 ( Figure 1 c) and P1( Figure 1 d) 1 H NMR spectrum disappeared. Correspondingly, it appeared at δ3.52 (H 9 ,H 11 ), 4.55ppm(H 10 ,H 12 ), corresponding to the proton at the original olefin addition site, indicating that the thiol has been successfully added to the olefin.

[0083] Figure 2 The thermogravimetric diagram of polysulfide P1 shows that the thermal decomposition temperature (corresponding to the temperature when the weight loss is 5%) is 235°C;

[0084] The structural formula of the polysulfide P1 is:

[0085]

[0086] Example 2

[0087] In this embodiment, monomer 1a is the same as in Example 1; 2b is 3,6-dioxa-1,8-octanedithiol, which can be purchased from the market, and in this embodiment, it is purchased from Anage Chemical.

[0088] The present invention provides a method for preparing a polysulfide (P2), comprising the following steps:

[0089] (1) A magnet and monomer 1a (338.40 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2b (162.80 μL, 1 mmol) and 1 mL of chloroform were injected into the tube using a syringe under air atmosphere. The mixture was stirred at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0090] (2) Under stirring conditions (speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was washed with 5-10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.), to obtain polysulfide P2. After determination and analysis, the yield of polysulfide P2 was 66%, the weight average molecular weight was 4000, and the molecular weight distribution was 1.17.

[0091] The polysulfide P2 has the structural formula:

[0092]

[0093] Example 3

[0094] In this embodiment, monomer 1a is the same as in embodiment 1; 2c is 1,6-hexanedithiol, which can be purchased from the market, and in this embodiment, purchased from Anaiji Chemical. The present invention provides a method for preparing a polysulfide (P3), and the steps are as follows:

[0095] (1) A magnet and monomer 1a (338.40 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2c (152.90 μL, 1 mmol) and 1 mL of chloroform were injected using a syringe under air atmosphere; the polymerization tube was placed at 60° C. and stirred for reaction for 24 hours (at a speed of 400 rpm). After the reaction was completed, the reaction solution was cooled to room temperature and diluted to 5 mL with dichloromethane to obtain a diluted polymer solution;

[0096] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) is added dropwise to 100 mL of methanol, and then allowed to stand (standing time is 12 h), the supernatant is poured out, the product is rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature is 50° C.) to obtain polysulfide P3.

[0097] The results of analysis showed that the yield of polysulfide P3 was 82%, the weight average molecular weight was 12 800, and the molecular weight distribution was 1.60.

[0098] The polysulfide P3 has the structural formula:

[0099]

[0100] Example 4

[0101] The synthesis method of monomer 1b in this embodiment is as follows: a magnetic particle, terephthalaldehyde (1.34 g, 10 mmol) (available on the market, purchased from Anaiji Chemical in this embodiment), NaOH (1.00 g, 25 mmol) (available on the market, purchased from Macklin Reagent in this embodiment) and 40 mL of methanol are added to a 250 mL two-necked bottle, and acetophenone (2.40 g, 20 mmol) (available on the market, purchased from Anaiji Chemical in this embodiment) is added dropwise. After the addition is completed, the reaction is carried out at room temperature for 12 hours (the speed is 500 rpm). After the reaction is completed, the solid material is filtered and dried in a vacuum oven to constant weight. The light yellow solid with structure 1b is obtained by passing it through a silica gel column with a developing agent of dichloromethane: petroleum ether = 1:1, and the yield is 87%. The structure of 1b is

[0102] The structure of monomer 1b in this embodiment is 2a is 1,8-octanedithiol, which can be purchased commercially, and in this example, it is purchased from Anaiji Chemical. The present invention provides a method for preparing a polysulfide (P4), and the steps are as follows:

[0103] (1) A magnet and monomer 1b (338.40 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2a (183.90 μL, 1 mmol) was injected into the tube using a syringe under air atmosphere. The mixture was stirred and reacted with 1 mL of chloroform at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution;

[0104] (2) Under stirring conditions (speed of 450 rpm), the diluted polymer solution obtained in step (1) is added to 100 mL of methanol, and then allowed to stand (standing time is 12 h), the supernatant is poured out, the product is rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature is 50° C.) to obtain polysulfide P4.

[0105] The results of analysis showed that the yield of polysulfide P4 was 72%, the weight average molecular weight was 400, and the molecular weight distribution was 1.17.

[0106] The polysulfide P4 has the structural formula:

[0107]

[0108] Example 5

[0109] In this embodiment, monomer 1b is the same as in embodiment 4; 2b is 3,6-dioxa-1,8-octanedithiol, which can be purchased from the market, and in this embodiment, it was purchased from Anergy Chemical.

[0110] The present invention provides a method for preparing polysulfide (P5), comprising the following steps:

[0111] (1) A magnetic particle and monomer 1b (338.40 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2b (162.80 μL, 1 mmol) and 1 mL of chloroform were injected into the tube using a syringe under air atmosphere. The mixture was stirred at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0112] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) is added dropwise to 100 mL of methanol, and then allowed to stand (standing time is 12 h), the supernatant is poured out, the product is rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature is 50° C.) to obtain polysulfide P5.

[0113] The results of analysis showed that the yield of polysulfide P5 was 80%, the weight average molecular weight was 6300, and the molecular weight distribution was 1.36.

[0114] The polysulfide P5 has the structural formula:

[0115]

[0116] Example 6

[0117] In this embodiment, monomer 1b is the same as in embodiment 4; 2c is 1,6-hexanedithiol, which can be purchased from the market, and in this embodiment, purchased from Anaiji Chemical. The present invention provides a method for preparing polysulfide (P6), and the steps are as follows:

[0118] (1) A magnet and monomer 1b (338.40 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2c (152.90 μL, 1 mmol) and 1 mL of chloroform were injected into the tube using a syringe under air atmosphere. The mixture was stirred at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0119] (2) Under stirring conditions (speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, and then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was rinsed with 5-10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.) to obtain polysulfide P6.

[0120] The results of analysis showed that the yield of polysulfide P6 was 90%, the weight average molecular weight was 10,000, and the molecular weight distribution was 1.81.

[0121] The polysulfide P6 has the structural formula:

[0122]

[0123] Example 7

[0124] In this embodiment, monomer 1b is the same as in embodiment 4; 2d is 4,4'-thiobisthiophenol, which can be purchased from the market, and in this embodiment, purchased from Anaiji Chemical. The present invention provides a method for preparing a polysulfide (P7), and the steps are as follows:

[0125] (1) A magnet and monomer 1b (338.40 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2d (250.40 mg, 1 mmol) and 1 mL of chloroform were injected into the tube using a syringe under air atmosphere. The mixture was stirred at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0126] (2) Under stirring conditions (speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, and then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was rinsed with 5-10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.) to obtain polysulfide P7.

[0127] The results of analysis showed that the yield of polysulfide P7 was 97%, the weight average molecular weight was 11,500, and the molecular weight distribution was 1.62.

[0128] The polysulfide P7 has the structural formula:

[0129]

[0130] Example 8

[0131] The synthesis method of monomer 1c in this embodiment is as follows: a magnetic particle, isophthalaldehyde (1.34 g, 10 mmol) (available on the market, purchased from Anaiji Chemical in this embodiment), NaOH (1.00 g, 25 mmol) (available on the market, purchased from Macklin Reagent in this embodiment) and 40 mL of methanol are added to a 250 mL two-necked bottle, and p-methoxyacetophenone (3.00 g, 20 mmol) (available on the market, purchased from Anaiji Chemical in this embodiment) dissolved in 20 mL of methanol is added dropwise. After the addition is completed, the reaction is carried out at room temperature for 12 hours (the speed is 500 rpm). After the reaction is completed, the solid material is filtered and dried in a vacuum oven to constant weight. The solid material is passed through a silica gel column with a developing agent of dichloromethane: petroleum ether = 1:1 to obtain a white solid with a structure of 1c with a yield of 55%. The structure of 1c is

[0132] The structure of monomer 1c in this embodiment is 2a is 1,8-octanedithiol, which can be purchased from the market, and in this example is purchased from Anaiji Chemical. The present invention provides a method for preparing a polysulfide (P8), and the steps are as follows:

[0133] (1) A magnet and monomer 1c (398.46 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2a (183.90 μL, 1 mmol) and 1 mL of chloroform were injected into the tube using a syringe under air atmosphere. The mixture was stirred at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0134] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, and then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.) to obtain polysulfide P8.

[0135] The results of analysis showed that the yield of polysulfide P8 was 96%, the weight average molecular weight was 12,000, and the molecular weight distribution was 1.96.

[0136] The polysulfide P8 has the structural formula:

[0137]

[0138] Example 9

[0139] In this embodiment, monomer 1c is the same as in Example 8; 2c is 1,6-hexanedithiol, which can be purchased from the market, and in this embodiment, it was purchased from Anaiji Chemical.

[0140] The present invention provides a method for preparing polysulfide (P9), comprising the following steps:

[0141] (1) A magnet and monomer 1c (398.46 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2c (152.90 μL, 1 mmol) and 1 mL of chloroform were injected into the tube using a syringe under air atmosphere. The mixture was stirred at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0142] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, and then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.) to obtain polysulfide P9.

[0143] The results of analysis showed that the yield of polysulfide P9 was 75%, the weight average molecular weight was 17,000, and the molecular weight distribution was 2.39.

[0144] The polysulfide P9 has the structural formula:

[0145]

[0146] Example 10

[0147] The structure of monomer 1d in this embodiment is 2a is 1,8-octanedithiol, which can be purchased from the market, and in this example is purchased from Anaiji Chemical. The present invention provides a method for preparing a polysulfide (P10), and the steps are as follows:

[0148] (1) A magnet and monomer 1d (414.50 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2a (183.90 μL, 1 mmol) was injected into the tube using a syringe under air atmosphere. The mixture was stirred and reacted with 1 mL of chloroform at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution;

[0149] (2) Under stirring conditions (speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, and then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.) to obtain polysulfide P10.

[0150] The results of analysis showed that the yield of polysulfide P10 was 85%, the weight average molecular weight was 2300, and the molecular weight distribution was 1.22.

[0151] The polysulfide P10 has the structural formula:

[0152]

[0153] Embodiment 11

[0154] In this embodiment, monomer 1d is the same as in embodiment 10; 2b is 3,6-dioxa-1,8-octanedithiol, which can be purchased from the market, and in this embodiment, purchased from Anaiji Chemical. The present invention provides a method for preparing a polysulfide (P11), and the steps are as follows:

[0155] (1) A magnet and monomer 1d (414.50 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2b (162.80 μL, 1 mmol) was injected into the tube using a syringe under air atmosphere. The mixture was stirred and reacted with 1 mL of chloroform at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0156] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, and then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.) to obtain polysulfide P11.

[0157] The results of analysis showed that the yield of polysulfide P11 was 57%, the weight average molecular weight was 2600, and the molecular weight distribution was 1.15.

[0158] The polysulfide P11 has the structural formula:

[0159]

[0160] Example 12

[0161] In this embodiment, monomer 1d is the same as in Example 10; 2c is 1,6-hexanedithiol, which can be purchased from the market, and in this embodiment, it is purchased from Anaiji Chemical.

[0162] The present invention provides a method for preparing polysulfide (P12), comprising the following steps:

[0163] (1) A magnet and monomer 1d (414.50 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2c (152.90 μL, 1 mmol) was injected into the tube using a syringe under air atmosphere. The mixture was stirred and reacted with 1 mL of chloroform at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution;

[0164] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) is added dropwise to 100 mL of methanol, and then allowed to stand (standing time is 12 h), the supernatant is poured out, the product is rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature is 50° C.) to obtain polysulfide P12.

[0165] The results of analysis showed that the yield of polysulfide P12 was 86%, the weight average molecular weight was 2300, and the molecular weight distribution was 1.12.

[0166] The polysulfide P12 has the structural formula:

[0167]

[0168] Embodiment 13

[0169] In this embodiment, monomer 1d is the same as in embodiment 10; 2d is 4,4'-thiobisthiophenol, which can be purchased from the market, and in this embodiment, purchased from Anaiji Chemical. The present invention provides a method for preparing a polysulfide (P13), and the steps are as follows:

[0170] (1) A magnet and monomer 1d (414.50 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2d (250.40 mg, 1 mmol) and 1 mL of chloroform were injected into the tube using a syringe under air atmosphere. The mixture was stirred at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution.

[0171] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, and then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.) to obtain polysulfide P13.

[0172] The results of analysis showed that the yield of polysulfide P13 was 96%, the weight average molecular weight was 14 300, and the molecular weight distribution was 1.42.

[0173] The polysulfide P13 has the structural formula:

[0174]

[0175] Embodiment 14

[0176] The structure of monomer 1e in this embodiment is 2a is 1,8-octanedithiol, which is commercially available and was purchased from Anaiji Chemical in this example.

[0177] The present invention provides a method for preparing polysulfide (P14), comprising the following steps:

[0178] (1) A magnetron and monomer 1e (562.40 mg, 1 mmol) were added to a 25 mL polymerization tube, and monomer 2a octanedithiol (183.90 μL, 1 mmol) was injected into the tube using a syringe under air atmosphere. The mixture was stirred and reacted with 1 mL of chloroform at 60° C. for 24 hours (at a speed of 400 rpm). After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was diluted to 5 mL with dichloromethane to obtain a diluted polymer solution;

[0179] (2) Under stirring conditions (rotation speed of 450 rpm), the diluted polymer solution obtained in step (1) was added dropwise to 100 mL of methanol, and then allowed to stand (standing time of 12 h), the supernatant was poured out, the product was rinsed with 5 to 10 mL of methanol, and vacuum dried to constant weight (drying temperature of 50° C.) to obtain polysulfide P14.

[0180] The results of analysis showed that the yield of polysulfide P14 was 74%, the weight average molecular weight was 2500, and the molecular weight distribution was 1.15.

[0181] The DMF solution of P14 (water to DMF volume ratio 9:1) can be used for the detection of cations. By comparing 15 cations (K + , Na + , NH4 + , Ag + , Zn 2+ , Li + , Ni 2+ ,Cr 3+ , Cu 2+ , Fe 3+ ,Co 2+ , Ca 2+ , Sm 3+ , Ce 3+ , Lu 2+ ), it was found that the aggregated solution of P14 and Fe 3+ The effect was fluorescence quenching, while the other 14 cations had no obvious response. Figure 3 DMF / H2O mixed solvent (v / v, 9 / 1, 10 -3 mol / L) and the fluorescence intensity ratio of different cations. 3+ The specific fluorescence quenching showed that the polymer can be used as a Fe 3+ The prospects of fluorescent probes; Figure 4 DMF / H2O mixed solvent (v / v, 9 / 1, 10 -3 mol / L) and different concentrations of Fe 3+ The linear relationship between the two groups was good, and the detection limit was 9.15×10 -7 M; In addition, Figure 5 THF solvent for polysulfide P14 (10 -3 mol / L) with different cations. Through simple solvent regulation, the THF solution of the polymer showed weak or even no fluorescence, so it can be clearly observed that P14 has a strong affinity for Ag. + The specific fluorescence enhancement of + Application prospects of fluorescent probes; Figure 6THF solvent for polysulfide P14 and different concentrations of Ag + The linear relationship between the two groups was good, and the detection limit was 4.6×10 -7 M. The concentration of P14 above is 10 -3 M, cation concentration is 6×10 -3 M.

[0182] The polysulfide P14 has the structural formula:

[0183]

[0184] Test Case

[0185] Fluorescence detection

[0186] The polysulfide prepared in the example was prepared with 3 mL of dimethylformamide (DMF) solution (water to DMF volume ratio 9:1) and tetrahydrofuran (THF) solution, wherein the concentration of the polysulfide was 10 -3 mol / L; configurations each contain a single cation of 15 species (K + , Na + , NH4 + , Ag + , Zn 2+ , Li + , Ni 2+ ,Cr 3+ , Cu 2+ , Fe 3+ ,Co 2+ , Ca 2+ , Sm 3+ , Ce 3+ , Lu 2+ ) solution (ion detection concentration is 6mM). The fluorescence intensity changes of DMF solution and THF solution of polysulfide after interaction with different cations were tested. Under a certain wavelength fluorescence excitation (400nm), the DMF solution of polysulfide and Fe 3+ The effect was fluorescence quenching, while the other 14 cations had no obvious response, such as Figure 3 The DMF solution of P14 and Fe 3+ The effect is a fluorescence quenching diagram, and its detection limit (LOD) is as low as 9.15×10 -7 M(Detection limit test Fe 3+ The concentration is 0-1mM), such as Figure 4 As shown in (where Kq is the quenching constant fitted under fluorescence quenching conditions); under a certain wavelength fluorescence excitation (400nm), the THF solution of polysulfide exhibits weak emission, which can achieve Ag + The fluorescence detection of P14 showed obvious fluorescence enhancement, while the other 14 cations showed weak emission. The results of THF solution of P14 are as follows: Figure 5 As shown in Figure 2, its detection limit (LOD) is as low as 4.6×10 -7 M(Detection limit test Ag + The concentration is 0-10 μM), such as Figure 6 As shown (where Ksv is the linear relationship constant between fluorescence intensity and silver ion concentration under fluorescence enhancement conditions).

[0187] Among them, M represents mol / L, mM represents mmol / L, and μM represents μmol / L.

[0188] Obviously, the above embodiments are merely examples for clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from them are still within the protection scope of the invention.

Claims

1. A method for preparing polysulfide, characterized in that: The following steps are involved: Polymerization reaction of polychalcone-derived olefin and mercapto compound is carried out in an organic solvent to obtain polysulfide.

2. The preparation method according to claim 1, characterized in that: The polychalcone-derived olefin has a structure as shown in the following formula (V) or (VI): The thiol compound has a structure as shown in the following formula (VII) or (VIII) or (IX): Preferably, R 1 , R 1’ , R 2 , R 2’ , R 3 , R 4 Each is independently selected from a substituted or unsubstituted C1-C60 aliphatic group or a substituted or unsubstituted C3-C60 aromatic group; Preferably, R 3’ , R 3” Each is independently selected from a substituted or unsubstituted C1-C60 aliphatic group; Among them, the substituents in the substituted C1-C60 aliphatic group and the substituted C3-C60 aromatic group are selected from any one or a combination of at least two of halogen, cyano, nitro, hydroxyl, amino, aldehyde, ester, C1-C30 straight or branched alkyl, C2-C10 alkenyl, C1-C30 alkoxy, C6-C60 aromatic, and C3-C60 heteroaromatic groups.

3. The preparation method according to claim 1 or 2, characterized in that: The polysulfide has the following structure: Among them, R 1 , R 1’ , R 2 , R 2’ , R 3 , R 3’ , R 3” , R 4 The definition is the same as that in claim 2, and n is an integer from 2 to 200.

4. The preparation method according to any one of claims 1 to 3, characterized in that R 1 , R 1’ , R 3 Each independently selected from the following groups: Wherein, h, i, j, k, l, and m are integers from 1 to 20, and X is selected from O or S elements; Preferably, R 3’ Independently selected from groups having the following structures; Preferably, R 3” A group independently selected from the following structures: Preferably, R 2 , R 2’ , R 4 Each independently selected from the following groups: Wherein, o, p, q are integers of 1 to 20, X is selected from O or S elements, and Y is selected from methoxy.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The organic solvent is selected from at least one of tetrahydrofuran, dichloromethane, chloroform, toluene, benzene, chlorobenzene, m-xylene, mesitylene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylacetamide and N,N-dimethylformamide; Preferably, the molar ratio of the vinyl group in the polychalcone-derived olefin to the thiol group in the thiol compound is (0.25-4):1 Preferably, the concentration of the polychalcone-derived olefin in the organic solvent is 0.05 to 5 mol / L.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The polymerization reaction temperature is 10 to 100° C.; the polymerization reaction time is 5 min to 36 h; Preferably, the polymerization reaction is carried out under air, oxygen, carbon dioxide, nitrogen or an inert atmosphere.

7. The preparation method according to any one of claims 1 to 6, characterized in that: After the polymerization reaction, there are also precipitation and drying processes.

8. The preparation method according to any one of claims 1 to 7, characterized in that: The precipitation process is to mix the system after the polymerization reaction with a precipitant and let it stand; Preferably, the standing time is 5-15h; Preferably, the precipitation process further includes a process of adding a diluent to dissolve before mixing with the precipitant and after the polymerization reaction is completed; Preferably, the diluent is selected from at least one of dichloromethane, chloroform and tetrahydrofuran; Preferably, the precipitant is selected from at least one of water, methanol, ethanol, n-hexane, petroleum ether, ether and acetone; Preferably, the addition ratio of the diluent to the polychalcone-derived olefin is (5-1000):(0.1-5), and the ratio unit is mL:mmol; Preferably, the drying is vacuum drying at a drying temperature of 25-80°C.

9. A polysulfide, characterized in that The preparation method is described in any one of claims 1 to 8.

10. Use of the polysulfide prepared by the preparation method according to any one of claims 1 to 8 or the polysulfide according to claim 9 in a fluorescent probe, characterized in that: The fluorescent probe is used to detect cations; Preferably, the cation includes Fe 3+ or Ag + .

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