POLYVINYL THIOETHER ESTER, PREPARATION METHOD THEREFOR AND USE THEREOF.
20220195120 · 2022-06-23
Inventors
Cpc classification
C08G75/045
CHEMISTRY; METALLURGY
C08G75/0227
CHEMISTRY; METALLURGY
International classification
Abstract
Disclosed are a polyvinyl thioether ester, a preparation method therefor and use thereof. The polyvinyl thioether ester is obtained by subjecting a binary acetylenic acid ester-based internal-alkyne monomer and a dithiol monomer as starting materials to a solution polymerization reaction. The staring materials of the polymerization reaction are easy to obtain, and no by-products are produced during the process of the polymerization reaction. The polymerization reaction has a wide substrate applicability and a good functional group compatibility, such that various functional groups can be conveniently introduced. No catalyst is used in the polymerization reaction, and, the influence of a catalyst residue on the optical and electrical properties and the biological properties of a polymer material can be eliminated. The prepared polyvinyl thioether ester has a good workability, a higher heat stability and aggregation-induced luminescence performance, and has application value in terms of optical plastics, biomedical materials, fluorescent sensing, etc.
Claims
1. A polyvinyl thioether ester, which has the following Formula I, ##STR00017## wherein, n is 2 to 200; R.sub.1 is one of Groups 1 to 20, R.sub.2 is Group 21 or Group 22, R.sub.3 is one of Groups 1 to 8, Group 23, and Group 24; and the structures of Groups 1 to 24 are: ##STR00018## ##STR00019## ##STR00020## ##STR00021## m is 1 to 18.
2. A method of preparing the polyvinyl thioether ester of claim 1, comprising: using an acetylenic acid ester monomer and a dithiol monomer as starting materials, and conducting a solution polymerization reaction to obtain the polyvinyl thioether ester, wherein the acetylenic acid ester monomer is: ##STR00022## R.sub.1 is one of Groups 1 to 20, and R.sub.2 is Group 21 or Group 22; Wherein the dithiol monomer is: ##STR00023## wherein R.sub.3 is one of Groups 1 to 8, Group 23, or Group 24.
3. The method of claim 2, wherein the solution polymerization reaction is conducted under a nitrogen atmosphere without a catalyst; a reaction temperature is from 30 to 120° C., and a reaction time is 3 to 36 hours.
4. The method of claim 3, wherein the reaction temperature is from 60 to 100° C., and the reaction time is for 12 to 24 hours.
5. The method of claim 2, further comprising: mixing the acetylenic acid ester monomer, the dithiol monomer, and a solvent to obtain a mixture; and subjecting the mixture to the solution polymerization to obtain the polyvinyl thioether ester, wherein a molar ratio of acetylenic acid ester monomer and the dithiol monomer is 1:1; and a concentration of either monomer in the mixture is from 0.05 to 1 mol/L.
6. The method of claim 5, wherein the concentration of either monomer is from 0.5 to 1 mol/L; the solvent is N,N-dimethylformamide (DMF), N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, or toluene.
7. The method of claim 2, wherein the acetylenic acid ester monomer is prepared by a esterification reaction of an acetylenic acid and a diol compound; the diol compound is: ##STR00024## the acetylenic acid is: ##STR00025## wherein R.sub.1 is one of Groups 1 to 20, and R.sub.2 is Group 21 or Group 22.
8. The method of claim 7, wherein the esterification reaction is conducted at room temperature for 12 to 36 hours in dichloromethane and in the presence of N,N′-bicyclichexylcarbimide, 4-dimethylaminopyridine, and P-toluenesulfonic acid monohydrate.
9. (canceled)
10. (canceled)
Description
DESCRIPTION OF FIGURES
[0033]
[0034]
[0035]
[0036]
[0037]
DETAILED DESCRIPTION
[0038] Hereinafter, the present invention will be described in detail in conjunction with examples, but the protection scope of the present invention is not limited to the following examples.
Example 1
[0039] ##STR00011##
Synthesis of the First Monomer: Butynoate Acid Ester Monomer
[0040] Into a 250 mL two-necked flask were added 2.3 g (10 mmol) of bisphenol A, 6.2 g (30 mmol) of N,N-dicyclohexylcarbimide (DCC), 0.5 g (4 mmol) of 4-(dimethylamino)pyridine (DMAP), and 0.8 g (4 mmol) of p-toluenesulfonic acid monohydrate (TsOH). The flask was evacuated and refilled with dry nitrogen three times. Freshly distilled DCM (80 mL) was injected, and the solution was cooled to 0° C. with an ice-water bath. Then 2.0 g (25 mmol) of 2-butynoic acid dissolved in 20 mL of dry DCM was added and drop it into the above reaction system with a constant pressure dropping funnel. The reaction mixture was stirred overnight, washed with DCM, and to obtain the crude product by rotary evaporation of the filtrate. The crude product was separated and purified by column chromatography and dried to a constant weight in vacuum, the first monomer:butynoate monomer was obtained in 72% yield (2.6 g) as a white solid. .sup.1H NMR (400 MHz, CDCl.sub.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).
[0041] The second monomer: 4-4′thiobisbenzenethiol was commercially available.
[0042] Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer: the butynoate monomer and 25.0 mg (0.1 mmol) of the second monomer: 4-4′thiobisbenzenethiol. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.2 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the target polymer was obtained. The prepared target polymer polyvinyl thioether ester is easily soluble in dichloromethane, 1,2-dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide at room temperature. Common organic solvents have good processability and film-forming properties. When the concentration is 25 mg/mL, the polyvinyl thioether ester tetrahydrofuran solution is clear.
[0043] Characterization data: 76% yield of the white solid. The result of GPC, M.sub.w is 44100, PDI is 2.3. .sup.1H NMR (400 MHz, CDCl.sub.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.
[0044] The comparison of the hydrogen nuclear magnetic resonance spectrum of the polymer and its corresponding monomer is shown in
Example 2
[0045] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 2 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 82% yield. The result of GPC, M.sub.w=13800, PDI=2.2. There is also a good solubility and thermal stability of the polymer. The temperature of 5% weight loss (T.sub.d) is at 298° C.
Example 3
[0046] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 1 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 77% yield. The result of GPC, M.sub.w=18600, PDI=2.3. There is also a good solubility and thermal stability of the polymer.
Example 4
[0047] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 82% yield. The result of GPC, M.sub.w=24700, PDI=2.4. There is also a good solubility and thermal stability of the polymer. With other conditions unchanged, if the reaction solvent (dry DMF) is changed to chloroform or dry DCE, there would not polymer have obtained.
Example 5
[0048] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.1 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 74% yield. The result of GPC, M.sub.w=27700, PDI=2.1. There is also a good solubility and thermal stability of the polymer.
Example 6
[0049] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 30° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 76% yield. The result of GPC, M.sub.w=11500, PDI=1.5. There is also a good solubility and thermal stability of the polymer. With other conditions unchanged, if the reaction solvent (dry DMF) is changed to dry THF, there would not polymer have obtained.
Example 7
[0050] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 80° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 53% yield. The result of GPC, M.sub.w=37700, PDI=2.4. There is also a good solubility and thermal stability of the polymer. With other conditions unchanged, if the reaction time is changed to 1 h, there would not polymer have obtained.
Example 8
[0051] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 100° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 76% yield. The result of GPC, M.sub.w=33800, PDI=2.5. There is also a good solubility and thermal stability of the polymer.
Example 9
[0052] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 120° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 82% yield. The result of GPC, M.sub.w=19600, PDI=2.0. There is also a good solubility and thermal stability of the polymer.
Example 10
[0053] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 3 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 66% yield. The result of GPC, M.sub.w=6400, PDI=1.7. There is also a good solubility and thermal stability of the polymer.
Example 11
[0054] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 6 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 80% yield. The result of GPC, M.sub.w=10000, PDI=1.9. There is also a good solubility and thermal stability of the polymer.
Example 12
[0055] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 12 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 75% yield. The result of GPC, M.sub.w=24200, PDI=1.9. There is also a good solubility and thermal stability of the polymer.
Example 13
[0056] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 36 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 74% yield. The result of GPC, M.sub.w=56000, PDI=2.5. There is also a good solubility and thermal stability of the polymer.
Example 14
[0057] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry DMSO was injected to dissolve the monomers. The solution was stirred at 120° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 72% yield. The result of GPC, M.sub.w=12600, PDI=2.0. There is also a good solubility and thermal stability of the polymer.
Example 15
[0058] The butynoate monomer and the 4-4′thiobisbenzenethiol are the same as in Example 1. Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.5 mL of dry toluene was injected to dissolve the monomers. The solution was stirred at 100° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 75% yield. The result of GPC, M.sub.w=12600, PDI=2.0. There is also a good solubility and thermal stability of the polymer.
Example 16
[0059] ##STR00012##
Synthesis of the First Monomer: The Butynoate
[0060] Into a 250 mL two-necked flask were added 4 g (20 mmol) of 4-hydroxybenzophenone, 5.2 g (80 mmol) of zinc powder. The flask was evacuated and refilled with dry nitrogen three times. Dry tetrahydrofuran was injected and stirred to dissolve, the solution added 7.6 g (40 mmol) of titanium tetrachloride at 0° C. After the reaction keep it at 0° C. for half an hour to room temperature, and then reacted with heating and stirring at 75° C. overnight. After the reaction, the reaction was quenched with a potassium carbonate solution with a mass fraction of 20%, and dilute hydrochloric acid was added until no bubbles were generated. Extracted with dichloromethane and dried with anhydrous magnesium sulfate, filtered, and the filtrate was removed by rotary evaporation. Into a 250 mL two-necked flask were added all the residue, 6.2 g (30 mmol) of DCC, 0.5 g (4 mmol) of DMAP, 0.8 g (4 mmol) of TsOH. The flask was evacuated and refilled with dry nitrogen three times. Then the solution added 80 ml dry DCM to dissolve. Then 2.0 g (25 mmol) of 2-butynoic acid dissolved in 20 mL of dry DCM was added and drop it into the above reaction system with a constant pressure dropping funnel. The reaction mixture was stirred overnight, washed with DCM, and to obtain the crude product by rotary evaporation of the filtrate. The crude product was separated and purified by column chromatography and dried to a constant weight in vacuum, the first monomer:butynoate monomer was obtained in 50% yield (2.8 g) as a white solid. .sup.1H NMR (400 MHz, CDCl.sub.3): δ7.19-6.79 (m, 18H), 2.04 (s, 6H).
[0061] The second monomer: 4-4′thiobisbenzenethiol was the same as in Example 1.
[0062] Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 49.6 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.2 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 89% yield. The result of GPC, M.sub.w=18200, PDI=1.9. There is also a good solubility and thermal stability of the polymer. The photo of polyvinyl thioether ester tetrahydrofuran solution (25 mg/mL) as
[0063] The polymer has extremely weak luminescence in tetrahydrofuran solution, and the fluorescence is significantly enhanced after the addition of poor solvent (water), indicating that it has aggregation-induced luminescence properties, see
[0064] Application of polyvinyl thioether ester in the detection of nitroaromatic hydrocarbon explosives: picric acid (PA) is used as a model explosive, the process of detecting PA: first prepare a polyvinyl thioether ester tetrahydrofuran aqueous solution of 10.sup.−5 mol/L (the volume fraction of water is 90%), test the fluorescence spectrum, and then sequentially added in the range from 0 to 200 mg/mL (concentration gradient of 10 mg/mL) of the detected substance PA, test the fluorescence spectrum quickly. 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 increase, the fluorescence decreases respectively, see
[0065] Adjusted the amount of the above-mentioned first monomer and second monomer to 0.01 mmol, and the rest remain unchanged. The polymer yield was 63%. 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 of 2.5 mg/mL at least.
Example 17
[0066] ##STR00013##
[0067] The synthesis of the first monomer:butynoate was the same as in Example 1.
[0068] The second monomer: 1,2-ethanedithiol was commercially available.
[0069] Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 36.0 mg (0.1 mmol) of the first monomer and 9.4 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 2 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 71% yield. The result of GPC, M.sub.w=4900, PDI=1.6. There is also a good solubility and thermal stability of the polymer.
Example 18
[0070] ##STR00014##
[0071] The synthesis of the first monomer:butynoate was the same as in Example 16.
[0072] The second monomer: 1,2-ethanedithiol was commercially available.
[0073] Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 49.6 mg (0.1 mmol) of the first monomer and 9.4 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 2 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 58% yield. The result of GPC, M.sub.w=4700, PDI=1.3. There is also a good solubility and thermal stability of the polymer. There are unique aggregation-induced luminescence properties, and can be used for the detection of explosives.
Example 19
[0074] ##STR00015##
[0075] Into a 250 mL two-necked flask were added 2.1 g (10 mmol) of 4,4′-dihydroxybenzophenone, 6.2 g (30 mmol) of DCC, 0.5 g (4 mmol) of DMAP, 0.8 g (4 mmol) of TsOH. The flask was evacuated and refilled with dry nitrogen three times. Then the solution added 80 ml dry DCM to dissolve. Then 3.7 g (25 mmol) of phenylpropynic acid dissolved in 20 mL of dry DCM was added and drop it into the above reaction system with a constant pressure dropping funnel. The reaction mixture was stirred overnight, washed with DCM, and to obtain the crude product by rotary evaporation of the filtrate. The crude product was separated and purified by column chromatography and dried to a constant weight in vacuum, the first monomer:butynoate monomer was obtained in 78% yield (3.8 g) as a white solid. .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.04-7.27 (m, 18H).
[0076] The second monomer:binary thiophenol monomer was commercially available.
[0077] Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 47.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.2 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 91% yield. The result of GPC, M.sub.w=15700, PDI=1.7. There is also a good solubility and thermal stability of the polymer.
Example 20
[0078] ##STR00016##
Synthesis of the First Monomer: The Phenylpropargyl Ester
[0079] Into a 250 mL two-necked flask were added 4 g (20 mmol) of 4-hydroxybenzophenone, 5.2 g (80 mmol) of zinc powder. The flask was evacuated and refilled with dry nitrogen three times. Dry tetrahydrofuran was injected and stirred to dissolve, the solution added 7.6 g (40 mmol) of titanium tetrachloride at 0° C. After the reaction keep it at 0° C. for half an hour to room temperature, and then reacted with heating and stirring at 75° C. overnight. After the reaction, the reaction was quenched with a potassium carbonate solution with a mass fraction of 20%, and dilute hydrochloric acid was added until no bubbles were generated. Extracted with dichloromethane and dried with anhydrous magnesium sulfate, filtered, and the filtrate was removed by rotary evaporation. Into a 250 mL two-necked flask were added all the residue, 6.2 g (30 mmol) of DCC, 0.5 g (4 mmol) of DMAP, 0.8 g (4 mmol) of TsOH. The flask was evacuated and refilled with dry nitrogen three times. Then the solution added 80 ml dry DCM to dissolve. Then 3.7 g (25 mmol) of phenylpropynic acid dissolved in 20 mL of dry DCM was added and drop it into the above reaction system with a constant pressure dropping funnel. The reaction mixture was stirred overnight, washed with DCM, and to obtain the crude product by rotary evaporation of the filtrate. The crude product was separated and purified by column chromatography and dried to a constant weight in vacuum, the first monomer:phenylpropargyl ester was obtained in 25% yield (1.5 g) as a white solid. .sup.1H NMR (400 MHz, CDCl.sub.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).
[0080] The second monomer: 4-4′-thiobisbenzenethiol was commercially available.
[0081] Into a 10 mL Schlenk tube with a stopcock in the side arm was placed 62.0 mg (0.1 mmol) of the first monomer and 25.0 mg (0.1 mmol) of the second monomer. The tube was evacuated and refilled with dry nitrogen three times through the side arm, and 0.2 mL of dry DMF was injected to dissolve the monomers. The solution was stirred at 60° C. for 24 h. After cooling to room temperature, the reaction mixture was diluted with 5 mL of chloroform and added dropwise into 250 mL of n-hexane under strong stirring through a cotton filter. After standing, filter and dried to a constant weight, the polymer was obtained in 85% yield. The result of GPC, M.sub.w=26800, PDI=2.1. There is also a good solubility and thermal stability of the polymer, and unique aggregation-induced luminescence properties, and can be used for the detection of explosives.