An organic polymer for rapid detection and degradation of mercury ions and a preparation method and application thereof

Abstract

The application relates to an organic polymer for rapid detection and degradation of mercury ions, and belongs to the technical field of preparation and application of organic functional materials. The structural formula of the organic polymer is shown as formula (IV); the luminescence performance of the polymer is derived from a conjugated organic polymer skeleton, and the recognition function for mercury ions is derived from a sulfur hydrocarbon chain embedded in the organic polymer skeleton. The polymer has high chemical stability and thermal stability, and can be repeatedly used for multiple cycles. The organic polymer is used for detecting and degrading mercury ions, and has the advantages of simple operation, low cost, short detection and degradation time, real-time detection, field detection and the like, and is easy to popularize and apply.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation and application of organic functional materials, and particularly relates to an organic polymer for rapid detection and degradation of mercury ions, and a preparation method and application thereof. Background Art

[0002] Water pollution is one of the most serious forms of pollution, as all life depends on water. Among the many types of water pollution, mercury ion pollution is the most difficult to control and poses the greatest threat to human health. Mercury ions released into water primarily come from unregulated mining and metallurgical operations. Even extremely low concentrations of mercury can be extremely toxic to organisms.

[0003] According to relevant reports, inorganic mercury concentrations reaching 5 ppb can produce harmful effects. Organic mercury is more toxic than inorganic mercury, and inorganic mercury is easily converted into highly toxic methylmercury by bacteria and microorganisms in the environment, causing extremely serious damage to the ecological environment. Mercury in wastewater can seep into the soil and be ingested by crops and livestock. Once in vivo, mercury can accumulate and accumulate in organisms over long periods of time, participating in the food chain and ultimately entering the human body, causing a range of serious diseases in humans, such as central nervous system damage, decreased brain, liver, and kidney function, and even gene mutations. Therefore, the detection and degradation of mercury ions are of vital importance for environmental protection and human health. To date, a number of methods have been developed to detect mercury ion content, such as inductively coupled plasma atomic emission spectrometry, atomic absorption spectrophotometry, and atomic fluorescence spectrometry. However, these methods generally require expensive instrumentation and specialized technical operators, and the establishment of standard curves is time-consuming and labor-intensive. Furthermore, they are difficult to implement in the field and face challenges in real-time detection. Therefore, overcoming the shortcomings of existing technologies is an urgent challenge in the field of organic functional material preparation and application technology. Summary of the Invention

[0004] The present invention aims to address the deficiencies of the prior art by providing an organic polymer for the rapid detection and degradation of mercury ions, as well as its preparation method and application. The polymer of the present invention can be used to prepare a sensing material for the rapid detection of mercury ions. Its molecular structure consists of a conjugated organic polymer backbone and specific mercury ion recognition sites. The conjugated organic polymer backbone is a triphenylamine-pyrrolopyrrole diketo skeleton, which provides a chromogenic function. Furthermore, the sulfide chains embedded in the triphenylamine-pyrrolopyrrole diketo skeleton serve as recognition groups, providing specific recognition of mercury ions. The organic polymer of the present invention can achieve functional regeneration through interaction with sodium sulfide.

[0005] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] An organic polymer for rapid detection and degradation of mercury ions, having a structural formula as shown in formula (IV);

[0007]

[0008] The molecular formula of the compound is (C 18 H 15 N) 2n (C 28 H 32 N2O2S2) 3n , (n is a positive integer), the relative molecular mass is about 196600-294900 (the degree of polymerization is about 100-150), and it is named poly(3,6-bis(4-bromophenyl)-2,5-bis(3-(ethylthio)propyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione)-(tris(4-boronic acid pinnesol ester benzyl)amine).

[0009] The present invention also provides a method for preparing the organic polymer for rapid detection and degradation of mercury ions, comprising the following steps:

[0010] The pyrrolopyrrole diketo derivative represented by formula (I) is generated by reacting p-bromobenzonitrile with diisopropyl succinate to form a ring; the reaction formula is shown below:

[0011]

[0012] A pyrrolopyrrole dione derivative represented by formula (I) is subjected to a substitution reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate to generate a fat-soluble pyrrolopyrrole dione derivative represented by formula (II) in which the lactam hydrogen is replaced by a thioether chain. The reaction formula is shown below:

[0013]

[0014] Tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III); the reaction formula is shown below:

[0015]

[0016] Tris(4-boronic acid pinesyl ester benzyl)amine and the compound represented by formula (II) are reacted by Suzuki polymerization to produce an organic polymer represented by formula (IV); the reaction formula is as follows:

[0017]

[0018] Furthermore, preferably, when 4-bromobenzonitrile and diisopropyl succinate are reacted to form a ring, the reaction temperature is 110°C.

[0019] Furthermore, preferably, when tri(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tri(4-boronic acid pinacol ester benzyl)amine represented by formula (III), [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride is used as a catalyst and the reaction temperature is 100°C.

[0020] Furthermore, preferably, when tris(4-boronic acid pinesyl ester benzyl)amine and the compound represented by formula (II) are reacted by Suzuki polymerization to produce the organic polymer represented by formula (IV), tetrakis(triphenylphosphine)palladium is used as a catalyst.

[0021] The present invention also provides the use of the organic polymer for rapid detection and degradation of mercury ions in the detection of mercury ions.

[0022] The present invention also provides the application of the organic polymer for rapid detection and degradation of mercury ions as a sensor for preparing mercury ion detection.

[0023] This invention designs an organic polymer based on a triphenylamine-dione pyrrolopyrrole backbone that exhibits high sensitivity, specific recognition, and degradation capabilities for mercury ions. The polymer's luminescence properties are derived from the conjugated organic polymer backbone, while its mercury ion recognition function stems from the sulfide chains embedded within the organic polymer backbone. The polymer also exhibits high chemical and thermal stability, enabling repeated reuse.

[0024] The fluorescence emission function of the polymer of the present invention is achieved by a conjugated triphenylamine-pyrrolopyrrole diketo organic polymer backbone. The recognition group for specific mercury ion recognition is a sulfide hydrocarbon chain embedded in the triphenylamine-pyrrolopyrrole diketo organic backbone. This group achieves specific recognition of mercury ions by complexing the sulfur atoms with mercury ions, transferring electrons from the π-conjugated backbone to the unoccupied orbitals of the mercury ions, resulting in fluorescence quenching. The polymer is used for mercury ion detection, and after fluorescence quenching, the mercury ion detection function can be regenerated by rinsing the material with a sodium sulfide aqueous solution, thereby enabling the repeated use of the sensing material.

[0025] Specifically, the polymer is used for mercury ion detection, and after its fluorescence is quenched, the mercury ion detection function of the material can be regenerated by washing the material with a 0.1M sodium sulfide aqueous solution, thereby achieving repeated recycling of the sensing material.

[0026] Considering that organic polymer fluorescent sensors have garnered widespread attention in recent years due to their high sensitivity, low detection limit, strong specificity, and low cost, the inventors designed an organic polymer based on a triphenylamine-dionepyrrolopyrrole backbone. This polymer exhibits high sensitivity, specific recognition, and degradation capabilities for mercury ions. The polymer's luminescence properties are derived from the conjugated organic polymer backbone, while its recognition of mercury ions stems from the sulfide chains embedded within the organic polymer backbone. The polymer also exhibits high chemical and thermal stability, enabling repeated reuse.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention designs an organic polymer based on a triphenylamine-dionepyrrolopyrrole backbone, which exhibits high sensitivity, specific recognition, and degradation capabilities for mercury ions. The polymer's luminescence properties derive from the conjugated organic polymer backbone, while its recognition of mercury ions stems from the sulfide chains embedded within the organic polymer backbone. The polymer exhibits high chemical and thermal stability, enabling repeated recycling. Using this organic polymer for the detection and degradation of mercury ions is simple, low-cost, and quick in detection and degradation times, enabling both real-time and field testing.

[0029] Prior to this invention, the main methods for detecting mercury ions included inductively coupled plasma atomic emission spectrometry, flame atomic absorption spectrometry, and atomic fluorescence spectrometry. However, these detection methods all required expensive equipment (for example, an atomic fluorescence spectrometer can cost over 400,000 RMB), involved complex detection procedures (e.g., the preparation of standard solutions), required high professional standards for detection personnel, and were difficult to move, making on-site and real-time detection difficult. The fluorescent probes of the present invention offer low cost, a simple detection process, and portable fluorescent probe materials, making on-site and real-time detection easy to implement. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a structural diagram of the organic polymer used for rapid detection and degradation of mercury ions in the present invention. DETAILED DESCRIPTION

[0031] The present invention is described in further detail below with reference to the embodiments.

[0032] Those skilled in the art will understand that the following examples are intended to illustrate the present invention only and should not be construed as limiting the scope of the present invention. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in the art or in the product specifications were used. Materials or equipment used without manufacturer identification are commercially available conventional products.

[0033] Example 1

[0034] An organic polymer for rapid detection and degradation of mercury ions, having a structural formula as shown in formula (IV);

[0035]

[0036] The method for preparing the organic polymer for rapid detection and degradation of mercury ions comprises the following steps:

[0037] The pyrrolopyrrole diketo derivative represented by formula (I) is generated by reacting p-bromobenzonitrile with diisopropyl succinate to form a ring; the reaction formula is shown below:

[0038]

[0039] A pyrrolopyrrole dione derivative represented by formula (I) is subjected to a substitution reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate to generate a fat-soluble pyrrolopyrrole dione derivative represented by formula (II) in which the lactam hydrogen is replaced by a thioether chain. The reaction formula is shown below:

[0040]

[0041] Tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III); the reaction formula is shown below:

[0042]

[0043] Tris(4-boronic acid pinesyl ester benzyl)amine and the compound represented by formula (II) are reacted by Suzuki polymerization to produce an organic polymer represented by formula (IV); the reaction formula is as follows:

[0044]

[0045] Example 2

[0046] An organic polymer for rapid detection and degradation of mercury ions, having a structural formula as shown in formula (IV);

[0047]

[0048] The method for preparing the organic polymer for rapid detection and degradation of mercury ions comprises the following steps:

[0049] The pyrrolopyrrole diketo derivative represented by formula (I) is generated by reacting p-bromobenzonitrile with diisopropyl succinate to form a ring; the reaction formula is shown below:

[0050]

[0051] A pyrrolopyrrole dione derivative represented by formula (I) is subjected to a substitution reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate to generate a fat-soluble pyrrolopyrrole dione derivative represented by formula (II) in which the lactam hydrogen is replaced by a thioether chain. The reaction formula is shown below:

[0052]

[0053] Tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III); the reaction formula is shown below:

[0054]

[0055] Tris(4-boronic acid pinesyl ester benzyl)amine and the compound represented by formula (II) are reacted by Suzuki polymerization to produce an organic polymer represented by formula (IV); the reaction formula is as follows:

[0056]

[0057] When p-bromobenzonitrile and diisopropyl succinate are reacted to form a ring, the reaction temperature is 110°C.

[0058] When tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is used as a catalyst, and the reaction temperature is 100°C.

[0059] The organic polymer represented by formula (IV) is prepared by Suzuki polymerization of tris(4-boronic acid pinesyl ester benzyl)amine and a compound represented by formula (II). Tetrakis(triphenylphosphine)palladium is used as a catalyst.

[0060] Application of the organic polymer for rapid detection and degradation of mercury ions in the detection of mercury ions.

[0061] The organic polymer for rapid detection and degradation of mercury ions is used to prepare a sensor for mercury ion detection.

[0062] Example 3

[0063] An organic polymer for rapid detection and degradation of mercury ions, having a structural formula as shown in formula (IV);

[0064]

[0065] The method for preparing the organic polymer for rapid detection and degradation of mercury ions comprises the following steps:

[0066] The pyrrolopyrrole diketo derivative represented by formula (I) is generated by reacting p-bromobenzonitrile with diisopropyl succinate to form a ring; the reaction formula is shown below:

[0067]

[0068] The reaction solvent is tert-amyl alcohol;

[0069] During the reaction, the strong reducing property of sodium particles is used to convert tert-amyl alcohol into sodium tert-amyl alcohol, forming a strong alkaline reaction environment; during the reaction, ferric chloride is used as a catalyst to accelerate the formation of sodium tert-amyl alcohol;

[0070] The dosage ratio of sodium particles, ferric chloride, tert-amyl alcohol, p-bromobenzonitrile, and diisopropyl succinate is 108.695 mmol: 0.030 mmol: 28.726 mL: 9.890 mmol: 49.70 mmol;

[0071] Before adding the raw materials, diisopropyl succinate was dissolved in a portion of tert-amyl alcohol to prepare a tert-amyl alcohol solution of diisopropyl succinate with a concentration of 1.988 mg / mL and then the raw materials were added.

[0072] The reaction temperature was 95°C.

[0073] A pyrrolopyrrole dione derivative represented by formula (I) is subjected to a substitution reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate to generate a fat-soluble pyrrolopyrrole dione derivative represented by formula (II) in which the lactam hydrogen is replaced by a thioether chain. The reaction formula is shown below:

[0074]

[0075] The reaction solvent used was DMF;

[0076] The usage ratio of compound (I), K2CO3, DMF, and 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate is 9.977 mmol: 21.7390 mmol: 39 mL: 21.897 mmol;

[0077] The reaction temperature was 115°C.

[0078] Tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III); the reaction formula is shown below:

[0079]

[0080] The reaction solvent used was anhydrous dioxane;

[0081] The reaction uses [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride as a catalyst;

[0082] The usage ratio of tris(4-bromophenyl)amine, pinacol diboron, potassium acetate, [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and anhydrous dioxane is 8.298 mmol: 33.464 mmol: 65.102 mmol: 0.3279 mmol: 95 mL;

[0083] The reaction temperature was 95°C.

[0084] Tris(4-boronic acid pinesyl ester benzyl)amine and the compound represented by formula (II) are reacted by Suzuki polymerization to produce an organic polymer represented by formula (IV); the reaction formula is as follows:

[0085]

[0086] Toluene was used as the reaction solvent;

[0087] The usage ratio of compound (II), compound (III), tetrakistriphenylphosphine palladium, hexadecyltrimethylammonium bromide, anhydrous potassium carbonate, and toluene is 2.900 mmol: 2.006 mmol: 0.021 mmol: 82.313 mmol: 39.000 mmol: 19.00 mL;

[0088] Before adding the raw materials, cetyltrimethylammonium bromide was dissolved in water to prepare a cetyltrimethylammonium bromide solution with a concentration of 0.137 mol / L, and then the raw materials were added.

[0089] Before adding the raw materials, anhydrous potassium carbonate was dissolved in water to prepare a potassium carbonate solution with a concentration of 4 mol / L and then the raw materials were added.

[0090] The reaction temperature was 75°C.

[0091] Example 4

[0092] An organic polymer for rapid detection and degradation of mercury ions, having a structural formula as shown in formula (IV);

[0093]

[0094] The method for preparing the organic polymer for rapid detection and degradation of mercury ions comprises the following steps:

[0095] The pyrrolopyrrole diketo derivative represented by formula (I) is generated by reacting p-bromobenzonitrile with diisopropyl succinate to form a ring; the reaction formula is shown below:

[0096]

[0097] The reaction solvent is tert-amyl alcohol;

[0098] During the reaction, the strong reducing property of sodium particles is used to convert tert-amyl alcohol into sodium tert-amyl alcohol, forming a strong alkaline reaction environment; during the reaction, ferric chloride is used as a catalyst to accelerate the formation of sodium tert-amyl alcohol;

[0099] The dosage ratio of sodium particles, ferric chloride, tert-amyl alcohol, p-bromobenzonitrile, and diisopropyl succinate is 108.696 mmol: 0.031 mmol: 28.727 mL: 9.891 mmol: 49.71 mmol;

[0100] Before adding the raw materials, diisopropyl succinate was dissolved in a portion of tert-amyl alcohol to prepare a tert-amyl alcohol solution of diisopropyl succinate with a concentration of 1.989 mg / mL, and then the raw materials were added.

[0101] The reaction temperature was 110°C.

[0102] A pyrrolopyrrole dione derivative represented by formula (I) is subjected to a substitution reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate to generate a fat-soluble pyrrolopyrrole dione derivative represented by formula (II) in which the lactam hydrogen is replaced by a thioether chain. The reaction formula is shown below:

[0103]

[0104] The reaction solvent used was DMF;

[0105] The usage ratio of compound (I), K2CO3, DMF, and 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate is 9.978 mmol: 21.740 mmol: 41 mL: 21.898 mmol;

[0106] The reaction temperature was 125°C.

[0107] Tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III); the reaction formula is shown below:

[0108]

[0109] The reaction solvent used was anhydrous dioxane;

[0110] The reaction uses [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride as a catalyst;

[0111] The usage ratio of tris(4-bromophenyl)amine, pinacol diboron, potassium acetate, [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and anhydrous dioxane is 8.299 mmol: 33.465 mmol: 65.103 mmol: 0.3280 mmol: 105 mL;

[0112] The reaction temperature was 105°C.

[0113] Tris(4-boronic acid pinesyl ester benzyl)amine and the compound represented by formula (II) are reacted by Suzuki polymerization to produce an organic polymer represented by formula (IV); the reaction formula is as follows:

[0114]

[0115] Toluene was used as the reaction solvent;

[0116] The usage ratio of compound (II), compound (III), tetrakistriphenylphosphine palladium, hexadecyltrimethylammonium bromide, anhydrous potassium carbonate, and toluene is 3.100 mmol: 2.007 mmol: 0.022 mmol: 82.314 mmol: 41.000 mmol: 21.00 mL;

[0117] Before adding the raw materials, cetyltrimethylammonium bromide was dissolved in water to prepare a cetyltrimethylammonium bromide solution with a concentration of 0.137 mol / L, and then the raw materials were added.

[0118] Before adding the raw materials, anhydrous potassium carbonate was dissolved in water to prepare a potassium carbonate solution with a concentration of 4 mol / L and then the raw materials were added.

[0119] The reaction temperature was 85°C.

[0120] Example 5

[0121] An organic polymer for rapid detection and degradation of mercury ions, having a structural formula as shown in formula (IV);

[0122]

[0123] The method for preparing the organic polymer for rapid detection and degradation of mercury ions comprises the following steps:

[0124] The pyrrolopyrrole diketo derivative represented by formula (I) is generated by reacting p-bromobenzonitrile with diisopropyl succinate to form a ring; the reaction formula is shown below:

[0125]

[0126] The reaction solvent is tert-amyl alcohol;

[0127] During the reaction, the strong reducing property of sodium particles is used to convert tert-amyl alcohol into sodium tert-amyl alcohol, forming a strong alkaline reaction environment; during the reaction, ferric chloride is used as a catalyst to accelerate the formation of sodium tert-amyl alcohol;

[0128] The dosage ratio of sodium particles, ferric chloride, tert-amyl alcohol, p-bromobenzonitrile, and diisopropyl succinate is 108.6955 mmol: 0.0305 mmol: 28.7265 mL: 9.8905 mmol: 49.705 mmol;

[0129] Before adding the raw materials, diisopropyl succinate was dissolved in a portion of tert-amyl alcohol to prepare a tert-amyl alcohol solution of diisopropyl succinate with a concentration of 1.9885 mg / mL, and then the raw materials were added.

[0130] The reaction temperature was 100°C.

[0131] A pyrrolopyrrole dione derivative represented by formula (I) is subjected to a substitution reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate to generate a fat-soluble pyrrolopyrrole dione derivative represented by formula (II) in which the lactam hydrogen is replaced by a thioether chain. The reaction formula is shown below:

[0132]

[0133] The reaction solvent used was DMF;

[0134] The usage ratio of compound (I), K2CO3, DMF, and 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate is 9.9775 mmol: 21.7395 mmol: 40 mL: 21.8975 mmol;

[0135] The reaction temperature was 120°C.

[0136] Tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III); the reaction formula is shown below:

[0137]

[0138] The reaction solvent used was anhydrous dioxane;

[0139] The reaction uses [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride as a catalyst;

[0140] The usage ratio of tris(4-bromophenyl)amine, pinacol diboron, potassium acetate, [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and anhydrous dioxane is 8.2985 mmol: 33.4645 mmol: 65.1024 mmol: 0.32795 mmol: 100 mL;

[0141] The reaction temperature was 100°C.

[0142] Tris(4-boronic acid pinesyl ester benzyl)amine and the compound represented by formula (II) are reacted by Suzuki polymerization to produce an organic polymer represented by formula (IV); the reaction formula is as follows:

[0143]

[0144] Toluene was used as the reaction solvent;

[0145] The usage ratio of compound (II), compound (III), tetrakistriphenylphosphine palladium, hexadecyltrimethylammonium bromide, anhydrous potassium carbonate, and toluene is 3.000 mmol: 2.0065 mmol: 0.0215 mmol: 82.313-5 mmol: 40.000 mmol: 20.00 mL;

[0146] Before adding the raw materials, cetyltrimethylammonium bromide was dissolved in water to prepare a cetyltrimethylammonium bromide solution with a concentration of 0.137 mol / L, and then the raw materials were added.

[0147] Before adding the raw materials, anhydrous potassium carbonate was dissolved in water to prepare a potassium carbonate solution with a concentration of 4 mol / L and then the raw materials were added.

[0148] The reaction temperature was 80°C.

[0149] Application Examples

[0150] Figure 1 The structure diagram of the organic polymer used for rapid mercury ion detection is a molecular schematic diagram of the final product used for rapid mercury ion detection. The organic polymer in the present invention is composed of a triphenylamine-pyrrolopyrrole diketo conjugated organic basic skeleton and a sulfide chain recognition group. The sulfide chain is first embedded through the reaction of 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate with 3,6-bis(4-bromophenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, and the hydrogen on the 3,6-bis(4-bromophenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione lactam is replaced by 3-(thioethyl)-n-propyl. The triphenylamine-pyrrolopyrrole-dione conjugated organic basic skeleton is generated by tri(4-boronic acid pinesyl ester benzyl)amine and the 3,6-bis(4-bromophenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione derivative embedded with the sulfide chain through Suzuki polymerization. The detection mechanism of mercury ions by the organic polymer in the present invention is as follows: after the sulfur atoms on the sulfide chains embedded in the organic polymer skeleton are complexed with mercury ions, the electrons on the π-conjugated skeleton are transferred to the empty orbitals of the mercury ions, resulting in fluorescence quenching, thereby achieving specific recognition of mercury ions.

[0151] Specific synthesis method:

[0152] (1) p-Bromobenzonitrile and diisopropyl succinate are reacted to form a ring to generate a pyrrolopyrrole diketo derivative represented by formula (I); the reaction formula is as follows:

[0153]

[0154] The reaction solvent is preferably tert-amyl alcohol;

[0155] During the reaction, the strong reducing property of sodium particles is used to convert tert-amyl alcohol into sodium tert-amyl alcohol, forming a strong alkaline reaction environment;

[0156] During the reaction, ferric chloride is used as a catalyst to accelerate the formation of sodium tert-amyl alcohol;

[0157] The preferred usage ratio of sodium particles, ferric chloride, tert-amyl alcohol, p-bromobenzonitrile, and diisopropyl succinate is 108.695-108.696 mmol: 0.030-0.031 mmol: 28.726-28.727 mL: 9.890-9.891 mmol: 49.70-49.71 mmol;

[0158] Before adding the raw materials, diisopropyl succinate was dissolved in a portion of tert-amyl alcohol to prepare a tert-amyl alcohol solution of diisopropyl succinate with a concentration of 1.988 mg / mL-1.989 mg / mL, and then the raw materials were added.

[0159] The reaction temperature is preferably 95-110°C.

[0160] A specific example:

[0161] To a three-necked flask, add 3g of tert-amyl alcohol. While stirring, add 2.5g of sodium granules, and finally a trace amount of ferric chloride (5mg). Heat the mixture to 110°C and maintain for 2 hours. Cool the mixture to room temperature, add 1.8g of p-bromobenzonitrile, heat the mixture to 110°C, and then add a solution of diisopropyl succinate in tert-amyl alcohol (10mL of diisopropyl succinate and 25mL of tert-amyl alcohol) dropwise at a rate of 3 to 4 seconds per drop. After the additions are complete, maintain the reaction at 110°C for another 4 hours. After the reaction is complete, cool the reaction mixture to room temperature, adjust the pH to neutral with acetic acid, filter, and dry. Reflux the crude solid product with water at 95°C for 1 hour, filter, and dry. Reflux the crude solid product with N,N-dimethylformamide at 110°C for 1 hour, filter, and dry. Repeat the water and N,N-dimethylformamide reflux cycle twice. Compound (I) was obtained as a red solid.

[0162] (2) A pyrrolopyrrole diketo derivative represented by formula (I) is subjected to a substitution reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate to generate a fat-soluble pyrrolopyrrole diketo derivative represented by formula (II) in which the lactam hydrogen is replaced by a thioether chain. The reaction formula is as follows:

[0163]

[0164] The reaction solvent is preferably DMF;

[0165] During the reaction, the weak alkalinity of K2CO3 is used to react with the hydrogen on the lactam of compound (I), so that the lactam nitrogen of compound (I) is converted into a nitrogen anion, thereby achieving a reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate;

[0166] The preferred usage ratio of compound (I), K2CO3, DMF, and 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate is 9.977-9.978 mmol: 21.739-21.740 mmol: 39-41 mL: 21.897-21.898 mmol;

[0167] The reaction temperature is preferably 115-125°C.

[0168] A specific example:

[0169] 4.45 g of compound (I), 3 g of K₂CO₃, and 40 mL of DMF were added to a 100 mL three-necked flask. After reacting at 120°C for 30 minutes, 6 g of 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate was slowly added, and the mixture was stirred at 120°C for 2 hours. After the reaction ceased, 100 mL of water was added, and the mixture was extracted with 80 mL of ethyl acetate (3 times). The resulting organic phase was dried over Na₂SO₄ and vacuum-dried. The organic phase was then purified by 200-300 mesh silica gel column chromatography using a mixture of dichloromethane and petroleum ether (15:1, by volume) as the eluent to obtain compound (II). Preferably, during purification, a TLC plate was spotted, and the eluate that emitted orange-yellow fluorescence under a 365 nm UV lamp was concentrated.

[0170] (3) Tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III); the reaction formula is as follows:

[0171]

[0172] The reaction solvent is preferably anhydrous dioxane;

[0173] During the reaction, potassium acetate is used as a base to react with the addition product formed by aryl halide and palladium to generate a strongly electrophilic organic palladium intermediate;

[0174] The reaction uses [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride as a catalyst;

[0175] The preferred usage ratio of tris(4-bromophenyl)amine, pinacol diboron, potassium acetate, [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and anhydrous dioxane is 8.298-8.299 mmol: 33.464-33.465 mmol: 65.102-65.103 mmol: 0.3279-0.3280 mmol: 95-105 mL;

[0176] The reaction temperature is preferably 95-105°C.

[0177] A specific example:

[0178] Place 4 g of tris(4-bromophenyl)amine, 8.5 g of pinacol diboronate, and 6.38 g of potassium acetate in a reaction flask and deoxygenate under a nitrogen atmosphere for 15 minutes. Add 240 mg of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride to the flask and continue deoxygenating under a nitrogen atmosphere for another 15 minutes. Then, inject 100 mL of anhydrous dioxane into the mixture, and stir at 100°C for 10 hours. After the reaction, cool the reaction mixture to room temperature, pour it into ice water, and filter it using a Buchner funnel to collect the crude solid product. The solid crude product is then dried, mixed with 10 g of 300-400 mesh silica gel to prepare a dry sample, and the product is purified by dry loading and silica gel column chromatography using 200-300 mesh silica gel. The eluent is a mixture of dichloromethane and petroleum ether in a volume ratio of 1:5 to obtain tris(4-boronic acid pinesyl ester benzyl)amine represented by formula (III); preferably, during purification, a TLC plate is placed, and the eluate that emits deep blue fluorescence under a 365 nm ultraviolet lamp is concentrated.

[0179] (4) Tris(4-boronic acid pinesyl ester benzyl)amine represented by formula (III) and the compound represented by formula (II) are subjected to Suzuki polymerization reaction to produce an organic polymer represented by formula (IV); the reaction formula is shown below:

[0180]

[0181] Toluene is preferably used as the reaction solvent;

[0182] During the reaction, hexadecyltrimethylammonium bromide is used as a surfactant to form nanomicelles in water. The reaction of the compounds represented by formula (II) and formula (III) is carried out in the nanomicelles to control the size of the polymer represented by formula (IV) within the nanometer range.

[0183] Tetrakis(triphenylphosphine)palladium is used as a catalyst in the reaction;

[0184] During the reaction, anhydrous potassium carbonate is used as a base to react with the addition product formed by aryl halide and palladium to generate a strongly electrophilic organic palladium intermediate;

[0185] The preferred usage ratio of compound (II), compound (III), tetrakis(triphenylphosphine)palladium, hexadecyltrimethylammonium bromide, anhydrous potassium carbonate, and toluene is 2.900-3.100 mmol: 2.006-2.007 mmol: 0.021-0.022 mmol: 82.313-82.314 mmol: 39.000-41.000 mmol: 19.00-21.00 mL;

[0186] Before adding the raw materials, cetyltrimethylammonium bromide was dissolved in water to prepare a cetyltrimethylammonium bromide solution with a concentration of 0.137 mol / L, and then the raw materials were added.

[0187] Before adding the raw materials, anhydrous potassium carbonate was dissolved in water to prepare a potassium carbonate solution with a concentration of 4 mol / L and then the raw materials were added.

[0188] The reaction temperature is preferably 75-85°C.

[0189] A specific example:

[0190] At room temperature, dissolve 30 g of hexadecyltrimethylammonium bromide in 600 mL of deionized water and pour into a 1 L three-necked flask. Deoxygenate under nitrogen four times (2 minutes each time). Then, weigh 1.95 g of compound (II), 1.25 g of compound (III), and 25 mg of tetrakis(triphenylphosphine)palladium into a small flask. Add 20 mL of toluene and sonicate at room temperature to dissolve the solution. After dissolution, inject the solution into the aforementioned hexadecyltrimethylammonium bromide aqueous solution and alternately sonicate and stir at room temperature for a total of 30 minutes. 5.52 g of anhydrous potassium carbonate was weighed and dissolved in 10 mL of deionized water under ultrasound. After dissolution, 10 mL of 4 mol / L potassium carbonate was injected into the above mixed solution. The mixture was stirred at 80°C for 3 days. After the reaction was completed, the mixture was cooled to room temperature and poured into a large beaker. 200 mL each of methanol, dichloromethane, and tetrahydrofuran were added and stirred thoroughly. The lower organic phase was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure to obtain a paste residue. The paste residue was wrapped with filter paper and the target product in the residue was extracted using a Soxhlet extractor with methanol as the solvent at 80°C for 3 days. The filter paper was removed and dried to obtain a high molecular weight covalent organic polymer with compound (IV) as a repeating structural unit.

[0191] The solid-state nuclear magnetic resonance carbon spectrum test results of the compound represented by formula (IV) are: 145-125ppm (carbon vibration of benzene ring skeleton), 150ppm (carbon vibration in carbon-nitrogen bond), 180ppm (carbon vibration in carbon-sulfur bond); Fourier transform infrared spectroscopy analysis shows: 1488cm -1 、1593cm -1 (Benzene ring absorption signal).

[0192] The compound represented by formula (IV) exhibits high sensitivity and selectivity for mercury ions. Using a fluorescence spectrophotometer, the compound represented by formula (IV) emits fluorescence of varying intensities upon contact with varying concentrations of mercury ions, enabling quantitative detection of mercury ions using an external standard method (standard curve method). The test results indicate that the compound exhibits no change in fluorescence properties upon contact with other metal ions (including sodium, potassium, barium, cadmium, iron, copper, calcium, lead, cobalt, silver, and chromium). However, upon contact with mercury ions, the compound exhibits fluorescence quenching, enabling the detection of mercury ions with a detection limit of 32.8 μg / L.

[0193] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the foregoing embodiments. The foregoing embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention. Such changes and modifications are intended to fall within the scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims and their equivalents.

Claims

1. An organic polymer for rapid detection and degradation of mercury ions, characterized in that: The structural formula is shown in formula (IV); 2. The method for preparing an organic polymer for rapid detection and degradation of mercury ions according to claim 1, wherein: The steps include: The pyrrolopyrrole diketo derivative represented by formula (I) is generated by reacting p-bromobenzonitrile with diisopropyl succinate to form a ring; the reaction formula is shown below: A pyrrolopyrrole dione derivative represented by formula (I) is subjected to a substitution reaction with 3-(thioethyl)-n-propyl-4-methylbenzenesulfonate to generate a fat-soluble pyrrolopyrrole dione derivative represented by formula (II) in which the lactam hydrogen is replaced by a thioether chain. The reaction formula is shown below: Tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III); the reaction formula is shown below: Tris(4-boronic acid pinesyl ester benzyl)amine and the compound represented by formula (II) are reacted by Suzuki polymerization to produce an organic polymer represented by formula (IV); the reaction formula is as follows:

3. The method for preparing an organic polymer for rapid detection and degradation of mercury ions according to claim 2, wherein: When p-bromobenzonitrile and diisopropyl succinate are reacted to form a ring, the reaction temperature is 110°C.

4. The method for preparing an organic polymer for rapid detection and degradation of mercury ions according to claim 2, wherein: When tris(4-bromophenyl)amine and diboronic acid pinacol ester are reacted under an inert atmosphere to generate tris(4-boronic acid pinacol ester benzyl)amine represented by formula (III), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is used as a catalyst, and the reaction temperature is 100°C.

5. The method for preparing an organic polymer for rapid detection and degradation of mercury ions according to claim 2, characterized in that: The organic polymer represented by formula (IV) is prepared by Suzuki polymerization of tris(4-boronic acid pinesyl ester benzyl)amine and a compound represented by formula (II). Tetrakis(triphenylphosphine)palladium is used as a catalyst.

6. Use of the organic polymer for rapid detection and degradation of mercury ions according to claim 1 in detecting mercury ions.

7. The organic polymer for rapid detection and degradation of mercury ions according to claim 1 is used as a sensor for mercury ion detection.

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