WO2021031818A1 - 聚乙烯基硫醚酯及其制备方法与应用 - Google Patents

聚乙烯基硫醚酯及其制备方法与应用 Download PDF

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WO2021031818A1
WO2021031818A1 PCT/CN2020/105645 CN2020105645W WO2021031818A1 WO 2021031818 A1 WO2021031818 A1 WO 2021031818A1 CN 2020105645 W CN2020105645 W CN 2020105645W WO 2021031818 A1 WO2021031818 A1 WO 2021031818A1
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monomer
dibasic
ester
acetylenic
groups
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French (fr)
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李红坤
杜军
李永舫
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苏州大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0227—Polyarylenethioethers derived from monomers containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0236—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups
    • C08G75/024—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups containing carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N2021/6417—Spectrofluorimetric devices

Definitions

  • the invention belongs to the field of polymer chemistry and material science, and specifically relates to a polyvinyl sulfide ester and a preparation method and application thereof.
  • Bowman and others in the United States used ultraviolet light-induced terminal alkynes to react with sulfhydryl groups, that is, one alkynyl group adds two sulfhydryl groups to prepare a cross-linked polysulfide; Alkali-catalyzed polymerization of active end alkynes and mercaptans prepared soluble polyvinyl sulfide. Subsequently, they used rhodium-catalyzed polymerization of dibasic end alkynes and dibasic thiophenol to prepare stereoregularity adjustable Recently, they used potassium phosphate to catalyze this type of polymerization reaction to prepare all-cis polyalkenyl sulfide with anti-Markov addition.
  • acetylenic monomers used in the above-mentioned polymerization reactions are all terminal acetylenic compounds, and the polymerization reaction based on internal acetylenes and sulfhydryl monomers is rarely reported, and the reaction requires the use of catalysts.
  • organic and polymer light-emitting materials with a planar molecular structure usually emit strong light in a dilute solution state, but at a high concentration or aggregation state, the light emission is weakened, or even no light. The quenching effect caused by this concentration or aggregation limits the application range of such luminescent materials.
  • aggregation-induced luminescence (AIE) materials have been widely used in display, chemical detection, and biosensing fields because of their higher luminous efficiency in the aggregate state than in the solution state ( Chem. Rev. 2015 , 115: 11718–11940) .
  • polymer materials often have better processing properties. For example, large-area thin films can be prepared by simple spin coating or casting methods. Therefore, the development of new structured AIE polymer materials has important application value.
  • the present invention provides a polyvinyl sulfide ester, and provides a preparation method and application of the polymer, such as the application in the detection of polynitroaromatic hydrocarbons.
  • the present invention provides a polyvinyl sulfide ester, and provides a preparation method and application of the polymer, such as the application in the detection of polynitroaromatic hydrocarbons.
  • the present invention also discloses a preparation method of the above-mentioned polyvinyl sulfide ester.
  • the polyvinyl sulfide ester is obtained by solution polymerization using dibasic acetylenic acid ester internal acetylenic monomer and dibasic mercapto monomer as raw materials.
  • the invention also discloses a method for detecting nitro aromatic hydrocarbon explosives, which comprises the following steps.
  • polyvinyl sulfide ester is obtained through solution polymerization.
  • the nitroaromatic hydrocarbon explosive is picric acid (PA);
  • the solvent in the polyvinyl sulfide ester solution is a mixture of tetrahydrofuran and water. More preferably, the volume fraction of water in the mixture of tetrahydrofuran and water is 90%; the concentration of the polyvinyl sulfide ester solution is 10 -5 mol/L; compare the detection fluorescence spectrum with the reference fluorescence spectrum, if the spectrum does not change, the system to be detected does not contain nitroaromatic hydrocarbon explosives, if the spectrum fluorescence If the strength is weakened, the system to be detected contains nitro aromatic hydrocarbon explosives; the polyvinyl sulfide ester of the present invention can qualitatively or quantitatively detect nitro aromatic hydrocarbon explosives.
  • the process of detecting PA in the present invention can be exemplified as follows: firstly prepare 10 -5 mol/L polyvinyl sulfide ester tetrahydrofuran aqueous solution (the volume fraction of water is 90%), test the fluorescence spectrum, and then add different amounts of detected ⁇ PA, test the fluorescence spectrum. The results found that: when PA is not added, the fluorescence of the test substance is very strong; when PA is added, the fluorescence is weakened, and as the content of PA is added, the fluorescence decreases sequentially, indicating that the polyvinyl sulfide ester of the present invention can be used as The sensor is used to detect nitro aromatic hydrocarbon explosives.
  • the solution polymerization reaction is carried out in a nitrogen atmosphere without a catalyst; the temperature of the solution polymerization reaction is 30 to 120 °C, preferably 60 to 100 °C, and the time is 3 to 36 hours, preferably 12 to 24 hour.
  • the dibasic acetylenic acid ester internal acetylene monomer, the dibasic mercapto group monomer and the solvent are mixed to obtain a mixed liquid, and then the polyvinyl sulfide ester is obtained through solution polymerization;
  • the molar ratio of similar monomer and dibasic mercapto monomer is 1:1; in the mixed solution, the monomer concentration is 0.05-1 mol/L, preferably 0.5-1 mol/L; the monomer concentration is dibasic acetylenic acid ester The concentration of internal acetylenic monomers or di-mercapto monomers.
  • the solvent can be a conventional high boiling point solvent, such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) , Toluene.
  • DMF N,N-dimethylformamide
  • DMAc N,N-dimethylacetamide
  • DMSO dimethylsulfoxide
  • the polymer solution is obtained after the solution polymerization reaction is completed, and the polyvinyl sulfide ester is obtained by post-treatment; preferably, the post-treatment is that the polymer solution is diluted with chloroform and dropped into n-hexane to precipitate to obtain polyethylene ⁇ thioether ester.
  • acetylenic acid and dibasic phenol compounds are used as raw materials to prepare dibasic acetylenic acid ester internal acetylenic monomers through esterification; preferably, the esterification reaction is carried out in dichloromethane, N,N'-bicyclic The reaction is carried out in the presence of hexylcarbimide, 4-dimethylaminopyridine and p-toluenesulfonic acid; the esterification reaction is at room temperature for 12 to 36 hours.
  • the structural formula of the binary phenol compound is as follows: ;
  • the structural formula of acetylenic acid is as follows: ;
  • the structural formula of the internal acetylenic monomer of the dibasic acetylenic ester is as Wherein; R 1 is selected from one of groups 1-20, and R 2 is one of groups 21 and 22.
  • the structural formula of the dibasic sulfhydryl monomer is as .
  • R 3 is selected from one of groups 1-8, 23, and 24.
  • n is an integer from 1 to 18; * represents the position of substitution.
  • the preparation method of the polyvinyl sulfide ester of the present invention can be as follows.
  • dibasic acetylenic acid ester monomers are prepared by esterification reaction.
  • the preparation process is: adding dibasic phenols in methylene chloride Compound, N,N'-dicyclohexylcarbimide (DCC), 4-dimethylaminopyridine (DMAP), p-toluenesulfonic acid; then add dropwise dichloromethane solution of acetylenic acid at 0 °C; add dropwise After completing the reaction at room temperature for 12 to 36 hours, the internal acetylenic monomer of dibasic acetylenic acid ester is obtained.
  • DCC N,N'-dicyclohexylcarbimide
  • DMAP 4-dimethylaminopyridine
  • p-toluenesulfonic acid then add dropwise dichloromethane solution of acetylenic acid at 0 °C
  • the prepared dibasic acetylenic acid ester internal acetylenic monomer and dibasic mercapto monomer are dissolved in a solvent, and polyvinyl sulfide ester is obtained by solution polymerization; specifically, polyvinyl sulfide ester is obtained by solution polymerization: Add the dibasic acetylenic acid ester internal acetylenic monomer and dibasic sulfhydryl monomer to the polymerization tube at a molar ratio of 1:1, vacuumize and change nitrogen 3 times, add a solvent to dissolve and prepare a monomer concentration of 0.05 to 1 mol /L, preferably 0.5 to 1 mol/L; start the polymerization, the polymerization temperature is 30 to 120 °C, preferably 60 to 100 °C, the time is 3 to 36 hours, preferably 12 to 24 hours, the reaction is complete The polymer solution is subjected to post-treatment to obtain the polyvinyl sulfide ester; the post-
  • the polyvinyl sulfide ester containing polyaryls and sulfur elements prepared by the present invention is expected to be used as optical plastics with high refractive index; the polyvinyl sulfide ester with AIE performance can be used as a fluorescence sensor, for example, it can be used to detect polynitroaromatic hydrocarbons.
  • Class explosives have important application prospects in preventing explosive attacks.
  • the present invention also discloses the application of the above-mentioned polyvinyl sulfide ester in the preparation of high refractive index optical plastics, luminescent patterns, and fluorescent sensors; at the same time, the present invention further discloses the above-mentioned polyvinyl sulfide ester in the detection of polynitroaromatic The application of similar compounds.
  • the polyvinyl sulfide ester prepared by the invention has good solubility and is soluble in common organic solvents at room temperature, such as dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide and dimethylsulfoxide Etc., high thermal stability, and can introduce functional groups to make it have special properties, such as AIE properties.
  • the method for preparing polyvinyl sulfide ester by using catalyst-free polymerization reaction of the present invention has easy-to-obtain reaction raw materials and can be directly purchased or synthesized through simple reaction; no by-products are generated during the polymerization reaction, which conforms to atomic economy;
  • the reaction has wide substrate applicability and good functional group compatibility, and can easily introduce a variety of functional groups; the polymerization reaction does not use catalysts, which can eliminate the influence of catalyst residues on the biological and photoelectric properties of polymer materials. Therefore, the polymerization reaction has important scientific significance and application value in polymer synthesis and polymer functional materials.
  • Figure 1 is a solution diagram of the polyvinyl sulfide ester of the present invention, and the numbers indicate the concentration.
  • Fig. 2 is a hydrogen NMR spectrum of the polyvinyl sulfide ester and its corresponding monomer prepared in Example 1 in CDCl 3.
  • Fig. 3 is a graph of the thermal weight loss curve of the polyvinyl sulfide ester prepared in Example 1, and the test condition is: in a nitrogen atmosphere, the heating rate is 10 o C/min.
  • Figure 4 shows the fluorescence spectra of the polyvinyl sulfide ester prepared in Example 16 in the solution state and the aggregate state.
  • Fig. 5 is a fluorescence spectrum of picric acid in the aggregation state of the polyvinyl sulfide ester prepared in Example 16.
  • FIG. 1 is a general structural diagram of polyvinyl sulfide ester in the present invention.
  • Example one .
  • the second monomer binary thiophenol, is a commercial chemical and can be purchased directly.
  • the prepared target polymer polyvinyl sulfide ester is easily soluble in dichloromethane, 1,2-dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide and dimethylsulfoxide at room temperature Common organic solvents have good processability and film-forming properties. When the concentration is 25mg/mL, the polyvinyl sulfide ester tetrahydrofuran solution is clear.
  • the polymer is polyvinyl sulfide ester, and the binary thiophenol monomer has resonance at ⁇ 3.45. Absorption peak, the peak disappeared in the polymer, and two new peaks ⁇ 6.08 (a), 5.46 (b) appeared, which proved that the polymerization reaction took place and there were two isomers A and B in the polymer . According to the integral area of a and b in the polymer spectrum, the content of isomers A and B in the polymer is 72% and 28%, respectively, indicating that the polymerization reaction has a certain degree of stereoregularity.
  • the 5% thermal weight loss temperature of polyvinyl sulfide ester polymer is 300 °C (see Figure 3), indicating that it has high thermal stability.
  • Example 2 The binary butynoate monomer and the divalent thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 2 mL of dry DMF. After the body is completely dissolved, react at 60°C for 24 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 82%.
  • the polymer also has good solubility and thermal stability, with a 5% weight loss temperature of 298 °C.
  • Example 3 The binary butynoate monomer and the divalent thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 1 mL of dry DMF. After the body is completely dissolved, react at 60°C for 24 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 77%.
  • the polymer also has good solubility and thermal stability.
  • Example 5 The binary butynoate monomer and the dibasic thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer into a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.1 mL of dry DMF. After the body is completely dissolved, react at 60°C for 24 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 74%.
  • the polymer also has good solubility and thermal stability.
  • Example 6 The binary butynoate monomer and the dibasic thiophenol monomer are the same as the first embodiment. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMF. After the body is completely dissolved, react at 30°C for 24 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer.
  • the rate is 76%.
  • the polymer also has good solubility and thermal stability. Keeping other conditions unchanged and changing the reaction solvent (dry DMF) to dry THF, no polymer was obtained.
  • Example 7 The binary butynoate monomer and the divalent thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMF. After the body is completely dissolved, react at 80°C for 24 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 53%.
  • the polymer also has good solubility and thermal stability. Keeping other conditions unchanged, the reaction time was modified to 1 hour, and no polymer was obtained.
  • Example 8 Binary butynoate monomer and dibasic thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMF. After the body is completely dissolved, react at 100°C for 24 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 76%.
  • the polymer also has good solubility and thermal stability.
  • Example 9 The binary butynoate monomer and the dibasic thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMF. After the body is completely dissolved, react at 120°C for 24 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 82%.
  • the polymer also has good solubility and thermal stability.
  • Example 10 The binary butynoate monomer and the dibasic thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMF. After the body is completely dissolved, react at 60°C for 3 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 66%.
  • the polymer also has good solubility and thermal stability.
  • Example 11 The binary butynoate monomer and the dibasic thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMF. After the body is completely dissolved, react at 60°C for 6 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 80%.
  • the polymer also has good solubility and thermal stability.
  • Example 12 The binary butynoate monomer and the dibasic thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMF. After the body is completely dissolved, react at 60°C for 12 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 75%.
  • the polymer also has good solubility and thermal stability.
  • Example 13 The binary butynoate monomer and the dibasic thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMF. After the body is completely dissolved, react at 60°C for 36 hours. After cooling to room temperature, it was diluted with 5 mL of chloroform, and the solution was added dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, left standing, filtered, and dried to constant weight to obtain a polymer. The rate is 74%.
  • the polymer also has good solubility and thermal stability.
  • Example 14 The binary butynoate monomer and the divalent thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer to a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry DMSO. After the body is completely dissolved, react at 120°C for 24 hours. After cooling to room temperature, dilute with 5 mL of chloroform, and add the solution dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, let stand, filter, and dry to constant weight, polymer, yield Is 72%.
  • the polymer also has good solubility and thermal stability.
  • Example 15 The binary butynoate monomer and the binary thiophenol monomer are the same as in Example 1. Add 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer into a 10 mL polymerization tube, vacuum and fill the system with nitrogen, repeat three times, and then add 0.5 mL of dry toluene. After the body is completely dissolved, react at 100°C for 24 hours. After cooling to room temperature, dilute with 5 mL of chloroform, and add the solution dropwise to 250 mL of vigorously stirred n-hexane through a cotton-plugged dropper, let stand, filter, and dry to constant weight, polymer, yield Is 75%.
  • the polymer also has good solubility and thermal stability.
  • Extract with dichloromethane dry with anhydrous magnesium sulfate, filter, and spin-evaporate to remove the filtrate, add all the residue to a 250 mL two-neck flask, and then add 6.2 g (30 mmol) N,N-dicyclohexylcarbonyl Imine (DCC), 0.5 g (4 mmol) 4-dimethylaminopyridine (DMAP), 0.8 g (4 mmol) p-toluenesulfonic acid hydrate, evacuated and filled with nitrogen three times. Add 80 mL of dry dichloromethane and stir to dissolve.
  • DCC N,N-dicyclohexylcarbonyl Imine
  • DMAP 4-dimethylaminopyridine
  • 0.8 g (4 mmol) p-toluenesulfonic acid hydrate evacuated and filled with nitrogen three times.
  • the second monomer dibasic thiophenol is the same as in Example 1.
  • the polymer also has good solubility and thermal stability.
  • the photo of the above-mentioned polyvinyl sulfide ester tetrahydrofuran solution (25mg/mL) is shown in Figure 1.
  • the polymer also has aggregation-induced luminescence properties and can be used for the detection of explosives. .
  • the polymer has extremely weak luminescence in the tetrahydrofuran solution, and the fluorescence is significantly enhanced after adding a poor solvent (water), indicating that it has aggregation-induced luminescence properties, see Figure 4.
  • the polymer has a low molecular weight and also has aggregation-induced luminescence properties, which can be used for the detection of explosives. With the above detection method, the polymer can detect PA at a minimum of 2.5 mg/mL.
  • Embodiment Seventeen .
  • the second monomer, 1,2-ethanedithiol is commercially available.
  • Embodiment 18 .
  • the second monomer, 1,2-ethanedithiol is commercially available.
  • the second monomer binary thiophenol monomer is commercially available.
  • Embodiment 20 .
  • the synthesis of the first monomer dibasic phenylpropiolate 4 g (20 mmol) 4-hydroxybenzophenone and 5.2 g (80 mmol) zinc powder were added to a 250 mL two-necked flask, and vacuumed and filled with nitrogen three times. Add dry tetrahydrofuran and stir to dissolve. Then, at 0°C, 7.6 g (40 mmol) of titanium tetrachloride was injected. After the end, keep it at 0°C for half an hour, return to room temperature, and react with heating and stirring at 75°C overnight. After the reaction, the reaction was quenched with 20% potassium carbonate solution, and diluted hydrochloric acid was added until no bubbles were generated. It was extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the filtrate was removed by rotary evaporation to obtain a crude product.
  • the second monomer dibasic thiophenol monomer can be commercially available.

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Abstract

一种聚乙烯基硫醚酯及其制备方法与应用，以二元炔酸酯内炔类单体与二元巯基单体为原料，通过溶液聚合反应得到聚乙烯基硫醚酯。该聚合反应的反应原料易得，聚合反应过程中无副产物生成；该聚合反应具有广泛的底物适用性及良好的官能团兼容性，可方便的引入多种功能性基团；该聚合反应没有用到催化剂，可消除催化剂残留对聚合物材料光电和生物学性能的影响。制备的聚乙烯基硫醚酯具有良好的可加工性、较高的热稳定性及聚集诱导发光性能，在光学塑料、生物医用材料、荧光传感等方面具有应用价值。

Description

聚乙烯基硫醚酯及其制备方法与应用 技术领域
本发明属于高分子化学和材料科学领域，具体涉及一种聚乙烯基硫醚酯及其制备方法与应用。
 背景技术
基于新型聚合反应制备新型结构的聚合物具有重要的研究意义和应用价值。其中利用炔类单体的聚合反应构筑功能性高分子成为近年来的一个研究热点。炔与硫醇的反应早在19世纪初期就有报道，但在当时并未引起过多的关注。2009年，美国的Bowman等人利用紫外光引发的末端炔与巯基反应，即一个炔基加成两个巯基，制备了交联网状的聚硫醚；2010年，香港科技大学Tang课题组利用有机碱催化的活性端炔与硫醇的聚合反应制备了可溶的聚乙烯基硫醚，随后，他们利用铑催化的二元末端炔与二元苯硫酚聚合反应制备了立构规整度可调的聚乙烯基苯硫醚，最近，他们利用磷酸钾催化该类聚合反应制备了反马氏加成的全顺式聚烯基硫醚。上述的聚合反应采用的炔类单体都是末端炔类化合物，而基于内炔与巯基类单体的聚合反应还很少有报道，并且反应都需采用催化剂。
另外，平面状分子结构的有机及高分子发光材料通常在稀溶液状态发光强烈，而在高浓度或聚集态下发光减弱、甚至不发光。这种浓度或聚集导致的猝灭效应限制了该类发光材料的应用范围。近年来，聚集诱导发光（AIE）材料由于在聚集态比溶液态具有更高的发光效率而广泛应用于显示、化学检测及生物传感等领域( Chem. Rev. 2015, 115: 11718–11940)。相对于有机小分子，高分子材料往往具有更好的加工性能，比如可通过简单的旋涂或浇筑的方法制备大面积薄膜。因此开发新型结构的AIE聚合物材料具有重要的应用价值。
技术问题
本发明提供了一种聚乙烯基硫醚酯，并提供了该聚合物的制备方法和应用，比如在多硝基芳烃类物质检测中的应用。
 技术解决方案
本发明提供了一种聚乙烯基硫醚酯，并提供了该聚合物的制备方法和应用，比如在多硝基芳烃类物质检测中的应用。
为实现上述目的，本发明所采取的技术方案如下。
一种聚乙烯基硫醚酯，具有式Ⅰ所示的结构：式Ⅰ
Figure 510020dest_path_image001
；其中， n为2～200；R 1选自基团1～20中的一种，R 2为基团21、22的一种，R 3选自基团1～8、23、24中的一种。
 本发明还公开了上述聚乙烯基硫醚酯的制备方法，以二元炔酸酯内炔类单体与二元巯基单体为原料，通过溶液聚合反应得到聚乙烯基硫醚酯。
本发明还公开了一种检测硝基芳烃类爆炸物的方法，包括以下步骤。
（1）以二元炔酸酯内炔类单体与二元巯基单体为原料，通过溶液聚合反应得到聚乙烯基硫醚酯。
（2）配置聚乙烯基硫醚酯溶液并测试荧光光谱，得到基准荧光光谱。
（3）将待检测体系加入聚乙烯基硫醚酯溶液中并测试荧光光谱，得到检测荧光光谱；比较检测荧光光谱与基准荧光光谱，完成硝基芳烃类爆炸物的检测。本发明公开了上述聚乙烯基硫醚酯在检测硝基芳烃类爆炸物中的应用。
优选的，硝基芳烃类爆炸物为苦味酸（picric acid, PA）；聚乙烯基硫醚酯溶液中溶剂为四氢呋喃与水的混合物，进一步优选，四氢呋喃与水的混合物中，水的体积分数为90%；聚乙烯基硫醚酯溶液的浓度为10 -5 mol/L；比较检测荧光光谱与基准荧光光谱，如果光谱没有变化，则待检测体系不含有硝基芳烃类爆炸物，如果光谱荧光强度减弱，则待检测体系含有硝基芳烃类爆炸物；本发明聚乙烯基硫醚酯可以定性或者定量的检测硝基芳烃类爆炸物。
本发明检测PA的过程可举例为：首先配制10 -5 mol/L的聚乙烯基硫醚酯的四氢呋喃水溶液（水的体积分数为90%），测试荧光光谱，然后依次加入不同量的被检测物PA，测试荧光光谱。结果发现：当不加PA时，检测物的荧光非常强；加入PA时，荧光减弱，并且随着加入PA含量的依次增大，荧光依次减弱，表明本发明的聚乙烯基硫醚酯可以作为传感器用检测硝基芳烃类爆炸物。
上述技术方案中，溶液聚合反应在氮气气氛中、无催化剂的条件下进行；溶液聚合反应的温度为30～120 ℃，优选为60～100 ℃，时间为3～36小时，优选为12～24小时。
上述技术方案中，将二元炔酸酯内炔类单体、二元巯基单体与溶剂混合，得到混合液，然后通过溶液聚合反应得到聚乙烯基硫醚酯；二元炔酸酯内炔类单体和二元巯基单体的摩尔比为1:1；混合液中，单体浓度为0.05～1 mol/L，优选为0.5～1 mol/L；单体浓度为二元炔酸酯内炔类单体或者二元巯基单体的浓度。
 上述技术方案中，所述溶剂可选用常规的高沸点溶剂，如N,N-二甲基甲酰胺（DMF）、N,N-二甲基乙酰胺（DMAc）、二甲亚砜（DMSO）、甲苯。
上述技术方案中，溶液聚合反应完毕得到聚合物溶液，再经后处理得到所述聚乙烯基硫醚酯；优选后处理为聚合物溶液经氯仿稀释后，滴入正己烷中，沉淀得到聚乙烯基硫醚酯。
本发明中，以炔酸、二元苯酚类化合物为原料，通过酯化反应制备二元炔酸酯内炔类单体；优选的，酯化反应在二氯甲烷、N,N'-二环己基碳酰亚胺、4-二甲氨基吡啶、对甲苯磺酸存在下进行；酯化反应为室温反应12～36小时。
本发明中：二元苯酚类化合物的结构式如：
Figure 786281dest_path_image002
；炔酸的结构式如：
Figure 19816dest_path_image003
；二元炔酸酯内炔类单体的结构式如：
Figure 381527dest_path_image005
；其中；R 1选自基团1～20中的一种，R 2为基团21、22的一种。
二元巯基单体的结构式如 
Figure 93131dest_path_image006
。
 其中R 3选自基团1～8、23、24中的一种。
本发明中，所述基团1～24的结构式如下。
 
Figure 348532dest_path_image007
。
其中，m为1～18的整数；*表示取代位置。
本发明聚乙烯基硫醚酯的制备方法可如下。
以2-烷基炔酸或者苯丙炔酸和二元苯酚类化合物为原料，通过酯化反应制备二元炔酸酯类单体，其制备过程为：在二氯甲烷中加入二元苯酚类化合物、N,N'-二环己基碳酰亚胺(DCC)、4-二甲氨基吡啶（DMAP）、对甲苯磺酸；然后在0 ℃下滴加炔酸的二氯甲烷溶液；滴加完成后室温反应12～36小时得到二元炔酸酯内炔类单体。
将制备的二元炔酸酯内炔类单体和二元巯基单体溶于溶剂中，通过溶液聚合反应得到聚乙烯基硫醚酯；具体通过溶液聚合反应得到聚乙烯基硫醚酯为：将二元炔酸酯内炔类单体和二元巯基单体以摩尔比为1:1加入到聚合管中，抽真空换氮气3次，加入溶剂溶解配制成单体浓度为0.05～1 mol/L的混合液，优选为0.5～1 mol/L；开始聚合，聚合温度为30～120 ℃，优选为60～100 ℃，时间为3～36小时，优选为12～24小时，反应完毕得到聚合物溶液，再经后处理得到所述的聚乙烯基硫醚酯；后处理为聚合物溶液经氯仿稀释后，滴入正己烷中，沉淀得到聚乙烯基硫醚酯。所述的溶剂可选用常规的高沸点溶剂，如N,N-二甲基甲酰胺（DMF）、N,N-二甲基乙酰胺（DMAc）、二甲亚砜（DMSO）、甲苯。
 本发明制备的含多芳基含硫元素的聚乙烯基硫醚酯有望作为高折光指数的光学塑料；具有AIE性能聚乙烯基硫醚酯，可作为荧光传感器，比如可用于检测多硝基芳烃类爆炸物，在防止爆炸袭击方面具有重要的应用前景。因此本发明还公开了上述聚乙烯基硫醚酯在制备高折光指数的光学塑料、发光图案、荧光传感器中的应用；同时本发明进一步公开了上述聚乙烯基硫醚酯在检测多硝基芳烃类化合物中的应用。
 上述反应通式为
Figure 752969dest_path_image008
。
本发明制备的聚乙烯基硫醚酯具有较好的溶解性，室温下可溶于常见的有机溶剂，如二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺和二甲亚砜等，较高的热稳定性，并能引入功能性基团使其具有特殊性能，如AIE性能。
 有益效果
本发明的利用无催化剂的聚合反应制备聚乙烯基硫醚酯的方法，反应原料易得，可以直接购买或通过简单的反应合成；聚合反应过程中无副产物生成，符合原子经济性；该聚合反应具有广泛的底物适用性及良好的官能团兼容性，可方便的引入多种功能性基团；该聚合反应没有用到催化剂，可消除催化剂残留对聚合物材料生物学和光电性能的影响。因此该聚合反应在高分子合成及聚合物功能材料方面具有重要的科学意义和应用价值。
 附图说明
图1为本发明聚乙烯基硫醚酯的溶液图，数字表示浓度。
图2为实施例一制备的聚乙烯基硫醚酯及其相应单体在CDCl 3中的核磁氢谱图。
图3为实施例一制备的聚乙烯基硫醚酯的热失重曲线图，测试条件：氮气气氛下，升温速率为10 oC/min。
图4 为实施例十六制备的聚乙烯基硫醚酯的溶液态和聚集态下的荧光光谱图。
图5 为实施例十六制备的聚乙烯基硫醚酯聚集态下检测苦味酸的荧光光谱图。
 本发明的实施方式
下面将结合实施例对本发明进行具体地描述，但本发明的保护范围不限于以下实施例，图1为本发明中聚乙烯基硫醚酯的结构通式图。
实施例一：
Figure 601976dest_path_image009
。
 第一单体二元丁炔酸酯类单体的合成：在250 mL双口烧瓶中加入2.3 g (10 mmol) 双酚A、6.2 g (30 mmol) N,N-二环己基碳酰亚胺（DCC）、0.5 g (4 mmol) 4-二甲氨基吡啶（DMAP）、0.8 g (4 mmol) 对甲苯磺酸水合物，抽真空充氮气三次，加入80 mL 干燥的二氯甲烷搅拌溶解，得到反应体系。然后在0℃条件下，将2.0 g (25 mmol) 丁炔酸溶于20 mL干燥的二氯甲烷，并通过恒压滴液漏斗滴入上述反应体系中，搅拌反应过夜，过滤，用二氯甲烷洗涤，将滤液旋干，得到粗产物，经用柱层析分离纯化，真空干燥至恒重，得到白色固体2.6 g （产率为72%），为第一单体二元丁炔酸苯酚酯单体。 1H NMR (400 MHz, CDCl 3) δ 7.24 (t, J = 9.6 Hz, 4H), 7.04 (t, J = 11.3 Hz, 4H), 2.05 (s, 6H), 1.64 (d, J = 10.3 Hz, 6H)。
第二单体二元苯硫酚单体为商业化化学药品，可以直接买到。
向带有侧臂的10 mL的聚合管中加入第一单体二元的丁炔酸苯酚酯单体36.0 mg (0.1 mmol)和第二单体二元苯硫酚单体25.0 mg (0.1 mmol)，通过侧臂对体系抽真空充氮气，重复三次，然后加入0.2 mL干燥的DMF，待单体完全溶解后，60℃反应24小时，冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到目标聚合物。所制备的目标聚合物聚乙烯基硫醚酯在室温下易溶于二氯甲烷、1,2-二氯乙烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺和二甲亚砜等常见的有机溶剂，具有良好的可加工性和成膜性，浓度为25mg/mL时，聚乙烯基硫醚酯四氢呋喃溶液澄清。
表征数据：白色固体，产率为76%。凝胶渗透色谱（GPC）结果显示：重均分子量（ M w）为44100，分子量分布（PDI）为2.3。 1H NMR (400 MHz, CDCl 3) δ7.65–7.25, 7.25–7.00, 6.88, 6.08, 5.51–5.28, 3.42–2.73, 2.98, 3.24–2.73, 2.07, 2.81–0.98, 2.28–0.98, 2.03–1.06, 1.86–1.06, 1.86–1.06, 1.42–1.06, 1.42–1.06。该聚合物与其相应的单体的核磁共振氢谱对比图见附图2，从图中可以确定该聚合物为聚乙烯基硫醚酯，其中二元苯硫酚单体在 δ 3.45处有共振吸收峰，在聚合物中该峰消失了，而出现了两个新峰 δ6.08 (a), 5.46 (b), 证明该聚合反应发生了，并且聚合物中存在两种异构体A和B。根据聚合物谱图中a和b的积分面积计算得到聚合物中异构体A和B的含量分别为72%和28%，表明该聚合反应具有一定的立构规整性。聚乙烯基硫醚酯聚合物5%热失重温度为300 ℃（见附图3），表明具有较高的热稳定性。
实施例二：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入2 mL干燥的DMF，待单体完全溶解后，60 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为82%。GPC结果显示： M w = 13800, PDI = 2.2。该聚合物也具有较好的溶解性和热稳定性，5%热失重温度为298 ℃。
实施例三：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入1 mL干燥的DMF，待单体完全溶解后，60 ℃反应24 小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为77%。GPC结果显示： M w = 18600, PDI = 2.3。该聚合物也具有较好的溶解性和热稳定性。
实施例四：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，60 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为82%。GPC结果显示： M w = 24700, PDI = 2.4。该聚合物也具有较好的溶解性和热稳定性。保持其它条件不变，反应溶剂（干燥的DMF）改为氯仿或者干燥的DCE时，没有得到聚合物。
  实施例五：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.1 mL干燥的DMF，待单体完全溶解后，60 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为74%。GPC结果显示： M w = 27700, PDI = 2.1。该聚合物也具有较好的溶解性和热稳定性。
实施例六：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，30 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为76%。GPC结果显示： M w = 11500, PDI = 1.5。该聚合物也具有较好的溶解性和热稳定性。保持其它条件不变，反应溶剂（干燥的DMF）改为干燥的THF时，没有得到聚合物。
实施例七：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，80 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为53%。GPC结果显示： M w = 37700, PDI = 2.4。该聚合物也具有较好的溶解性和热稳定性。保持其它条件不变，反应时间修改为1小时，没有得到聚合物。
实施例八：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，100 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为76%。GPC结果显示： M w = 33800, PDI = 2.5。该聚合物也具有较好的溶解性和热稳定性。
实施例九：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，120 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为82%。GPC结果显示： M w = 19600, PDI = 2.0。该聚合物也具有较好的溶解性和热稳定性。
实施例十：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，60 ℃反应3小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为66%。GPC结果显示： M w = 6400, PDI = 1.7。该聚合物也具有较好的溶解性和热稳定性。
实施例十一：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，60 ℃反应6小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为80%。GPC结果显示： M w = 10000, PDI = 1.9。该聚合物也具有较好的溶解性和热稳定性。
实施例十二：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，60 ℃反应12小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为75%。GPC结果显示： M w = 24200, PDI = 1.9。该聚合物也具有较好的溶解性和热稳定性。
实施例十三：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMF，待单体完全溶解后，60 ℃反应36小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为74%。GPC结果显示： M w = 56000, PDI = 2.5。该聚合物也具有较好的溶解性和热稳定性。
实施例十四：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的DMSO，待单体完全溶解后，120 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，聚合物，产率为72%。GPC结果显示： M w = 12600, PDI = 2.0。该聚合物也具有较好的溶解性和热稳定性。
实施例十五：二元的丁炔酸酯单体和二元硫酚单体同实施例一。在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.5 mL干燥的甲苯，待单体完全溶解后 100 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，聚合物，产率为75%。GPC结果显示： M w = 12600, PDI = 2.0。该聚合物也具有较好的溶解性和热稳定性。
实施例十六：  
Figure 117271dest_path_image010
。
第一单体二元丁炔酸酯的合成：在250 mL两口瓶中加入4 g （20 mmol）4-羟基二苯甲酮，5.2 g（80 mmol）锌粉，抽真空充氮气三次。加入干燥的四氢呋喃搅拌溶解。然后在0 ℃条件下，加入7.6 g（40 mmol）四氯化钛。结束后0 ℃保温半小时，恢复到室温，然后75 ℃加热搅拌反应过夜。反应结束后，用质量分数为20 %的碳酸钾溶液淬灭反应，加入稀盐酸直至无气泡产生。用二氯甲烷进行萃取，无水硫酸镁干燥，过滤，旋蒸除去滤液后，将全部剩余物加入250 mL双口烧瓶中，再加入6.2 g (30 mmol) N,N-二环己基碳酰亚胺（DCC）、0.5 g (4 mmol) 4-二甲氨基吡啶（DMAP）、0.8 g (4 mmol) 对甲苯磺酸水合物，抽真空充氮气三次。加入80 mL 干燥的二氯甲烷搅拌溶解。然后在0℃条件下，将2.0 g (25 mmol) 丁炔酸溶于20 mL干燥的二氯甲烷，并通过恒压滴液漏斗滴入反应体系中，搅拌反应过夜，过滤，用二氯甲烷洗涤，将滤液旋干，得到粗产物，经用柱层析分离纯化，真空干燥至恒重，得到白色固体2.8 g （产率为50%），为第一单体二元丁炔酸苯酚酯单体。 1H NMR (400 MHz, CDCl 3) : δ7.19–6.79 (m, 18H), 2.04 (s, 6H)。
第二单体二元硫酚同实施例一。
在10 mL的聚合管中加入第一单体49.6 mg (0.1 mmol)和第二单体25.0 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.2 mL干燥的DMF，待单体完全溶解后，60℃反应24 小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为89%。GPC结果显示： M w =18200, PDI = 1.9。该聚合物也具有较好的溶解性和热稳定性，上述聚乙烯基硫醚酯四氢呋喃溶液（25mg/mL）照片见图1，该聚合物也具有聚集诱导发光性能，可用于爆炸物的检测。
该聚合物在四氢呋喃溶液发光极其微弱，加入不良溶剂（水）后荧光显著增强，表明具有聚集诱导发光性能，见附图4。
聚乙烯基硫醚酯在硝基芳烃类爆炸物检测中的应用：以苦味酸（picric acid, PA）为模型爆炸物，检测PA的过程：首先配制10 -5 mol/L的聚乙烯基硫醚酯的四氢呋喃水溶液（水的体积分数为90%）作为检测物，依次加入0~200 mg/mL（浓度梯度为10 mg /mL）的被检测物PA, 快速测试荧光光谱。结果发现：当不加PA时，检测物的荧光非常强；加入PA时，荧光减弱，并且随着加入PA含量的依次增大，荧光依次减弱，见附图5，表明本发明的聚乙烯基硫醚酯可以作为传感器用检测硝基芳烃类爆炸物；而且进一步实验发现该聚合物可以检测0.5 mg /mL的PA，具有优异的灵敏度。
将上述第一单体、第二单体的用量都调整为0.01 mmol，其余不变，聚合物产率63%，该聚合物分子量较低也具有聚集诱导发光性能，可用于爆炸物的检测，根据上述检测方法，该聚合物最低检测2.5 m g/mL的PA。
实施例十七：
Figure 243490dest_path_image011
。
第一单体二元丁炔酸酯的合成同实施例一。
第二单体1,2-乙二硫醇可由市售得到。
在10 mL的聚合管中加入第一单体36.0 mg (0.1 mmol)和第二单体9.4 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.2 mL干燥的DMF，待单体完全溶解后，60℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为71%。GPC结果显示： M w =4900, PDI = 1.6。该聚合物也具有较好的溶解性和热稳定性。
实施例十八：
Figure 553249dest_path_image012
。
第一单体二元丁炔酸酚酯的合成同实施例十六。
第二单体1,2-乙二硫醇可由市售得到。
在10 mL的聚合管中加入第一单体49.6 mg (0.1 mmol)和第二单体9.4 mg (0.1 mmol)，对体系抽真空充氮气，重复三次，然后加入0.2 mL干燥的DMF，待单体完全溶解后，60 ℃反应24小时。冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为58%。GPC结果显示： M w =4700, PDI = 1.3。该聚合物也具有较好的溶解性和热稳定性，具有聚集诱导发光性能，可用于爆炸物的检测。
  实施例十九：
Figure 889552dest_path_image013
。
 第一单体二元苯丙炔酸酯类单体的合成：在250 mL双口烧瓶中加入2.1 g (10 mmol) 4,4’-二羟基二苯甲酮、6.2 g (30 mmol) N,N-二环己基碳酰亚胺（DCC）、0.5 g (4 mmol) 4-二甲氨基吡啶（DMAP）、0.8 g (4 mmol) 对甲苯磺酸，抽真空充氮气三次。加入80 mL干燥的二氯甲烷搅拌溶解。然后在0 ℃条件下，将3.7 g (25 mmol) 苯丙炔酸溶于20 mL干燥的二氯甲烷，并通过恒压滴液漏斗滴入反应体系中，搅拌反应过夜，过滤，用二氯甲烷洗涤，将滤液旋干，得到粗产物，经用柱层析分离纯化，真空干燥至恒重，得到白色固体3.7 g（产率为78%），为第一单体二元丁炔酸苯酚酯单体。 1H NMR (400 MHz, CDCl 3) δ 8.04–7.27 (m, 18H)。
第二单体二元苯硫酚单体可以通过市售得到。
向带有侧臂的10 mL的聚合管中加入第一单体二元的苯丙炔酸苯酚酯单体47.0 mg (0.1 mmol)和第二单体二元苯硫酚单体25.0 mg (0.1 mmol)，通过侧臂对体系抽真空充氮气，重复三次，然后加入0.2 mL干燥的DMF，待单体完全溶解后，60 ℃反应24小时，冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为91%。GPC结果显示： M w =15700, PDI = 1.7。该聚合物也具有较好的溶解性和热稳定性。
  实施例二十：
Figure 208538dest_path_image014
。
第一单体二元苯丙炔酸酯的合成：在250 mL两口瓶中加入4 g（20 mmol）4-羟基二苯甲酮，5.2 g（80 mmol）锌粉，抽真空充氮气三次。加入干燥的四氢呋喃搅拌溶解。然后在0℃条件下，打入7.6 g（40 mmol）四氯化钛。结束后0℃保温半小时，恢复到室温，75 ℃加热搅拌反应过夜。反应结束后，用质量分数为20%的碳酸钾溶液进行焠灭反应，加入稀盐酸直至无气泡产生。用二氯甲烷进行萃取，无水硫酸镁干燥，过滤，旋蒸除去滤液后，得到粗产物。
在250 mL双口烧瓶中加入上一步的粗产物、6.2 g (30 mmol) N,N-二环己基碳酰亚胺（DCC）、0.5 g (4 mmol) 4-二甲氨基吡啶（DMAP）、0.8 g (4 mmol) 对甲苯磺酸水合物，抽真空充氮气三次。加入80 mL 干燥的二氯甲烷搅拌溶解。然后在0 ℃条件下，将3.7 g (25 mmol) 苯丙炔酸溶于20 mL干燥的二氯甲烷，并通过恒压滴液漏斗滴入反应体系中，搅拌反应过夜，过滤，用二氯甲烷洗涤，将滤液旋干，得到粗产物，经用柱层析分离纯化，真空干燥至恒重，得到白色固体1.5 g （产率为25%），为第一单体二元苯丙炔酸苯酚酯单体。 1H NMR (400 MHz, CDCl 3): δ 7.62 (d, J = 7.0 Hz, 4H), 7.53–7.44 (m, 2H), 7.41 (t, J = 7.4 Hz, 4H), 7.19–6.89 (m, 18H)。
第二单体二元硫酚单体可以通过市售得到。
向带有侧臂的10 mL的聚合管中加入第一单体二元的苯丙炔酸苯酚酯单体62.0 mg (0.1 mmol)和第二单体二元苯硫酚单体25.0 mg (0.1 mmol)，通过侧臂对体系抽真空充氮气，重复三次，然后加入0.2 mL干燥的DMF，待单体完全溶解后，60℃反应24小时，冷却至室温后用5 mL的三氯甲烷稀释，并将溶液通过塞有棉花的滴管滴加到250 mL剧烈搅拌的正己烷中，静置，过滤，干燥至恒重，得到聚合物，产率为85%。GPC结果显示： M w = 26800, PDI = 2.1。该聚合物也具有较好的溶解性和热稳定性，该聚合物也具有聚集诱导发光性能，可用于爆炸物的检测。

Claims (10)

  1. 一种聚乙烯基硫醚酯，具有式Ⅰ所示的结构：
    式Ⅰ
    Figure 863611dest_path_image001
    其中， n为2～200；R 1选自基团1～20中的一种，R 2为基团21、22的一种，R 3选自基团1～8、23、24中的一种；所述基团1～24的结构式如下：
    Figure 391676dest_path_image002
    其中，m为1～18。
  2. 权利要求1所述聚乙烯基硫醚酯的制备方法，其特征在于：以二元炔酸酯内炔类单体与二元巯基单体为原料，通过溶液聚合反应得到聚乙烯基硫醚酯；二元炔酸酯内炔类单体的结构式如下：
    Figure 27056dest_path_image003
    其中；R 1选自基团1～20中的一种，R 2为基团21、22的一种；
    二元巯基单体的结构式如下：
    Figure 183231dest_path_image004
    其中R 3选自基团1～8、23、24中的一种。
  3. 根据权利要求2所述聚乙烯基硫醚酯的制备方法，其特征在于：溶液聚合反应在氮气气氛中、无催化剂的条件下进行；溶液聚合反应的温度为30～120 ℃，时间为3～36小时。
  4. 根据权利要求3所述聚乙烯基硫醚酯的制备方法，其特征在于：溶液聚合反应的温度为60～100 ℃，时间为12～24小时。
  5. 根据权利要求2所述二元酯类炔单体的制备方法，其特征在于：将二元炔酸酯内炔类单体、二元巯基单体与溶剂混合，得到混合液，然后通过溶液聚合反应得到聚乙烯基硫醚酯；二元炔酸酯内炔类单体和二元巯基单体的摩尔比为1:1；混合液中，单体浓度为0.05～1 mol/L。
  6. 根据权利要求5所述聚乙烯基硫醚酯的制备方法，其特征在于：混合液中，单体浓度为0.5～1mol/L；所述溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、六甲基磷酰胺或甲苯。
  7. 根据权利要求2所述聚乙烯基硫醚酯的制备方法，其特征在于：以炔酸、二元苯酚类化合物为原料，通过酯化反应制备二元炔酸酯内炔类单体；
    二元苯酚类化合物的结构式如下：
    Figure 980286dest_path_image005
    炔酸的结构式如下：
    Figure 854701dest_path_image006
    其中；R 1选自基团1～20中的一种，R 2为基团21、22的一种。
  8. 根据权利要求7所述聚乙烯基硫醚酯的制备方法，其特征在于：所述酯化反应温度为室温，时间为12～36小时；酯化反应在二氯甲烷、N,N'-二环己基碳酰亚胺、4-二甲氨基吡啶、对甲苯磺酸存在下进行。
  9. 权利要求1所述聚乙烯基硫醚酯在制备高折光指数的光学塑料、生物医用材料或者荧光传感器中的应用；或者权利要求1所述聚乙烯基硫醚酯在检测多硝基芳烃类化合物中的应用。
  10. 根据权利要求9所述的应用，其特征在于，多硝基芳烃类化合物为苦味酸。
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