Narrow-Range Polyacetylene Ester Compound and Preparation Method Therefor

Abstract

Provided herein is a narrow-range polyacetylene ester compound and a preparation method. The narrow-range polyacetylene ester compound has a structural formula as represented by formula (I). The method includes: in atmospheric carbon dioxide environment, a bifunctional alkyne monomer, carbon dioxide, and a dihalide monomer perform polymerization reaction by means of a combined action of a catalyzer and alkali, dissolve the product into an organic solvent, then add same to a precipitant for precipitation, collect precipitates, and dry same to the constant weight to obtain the narrow-range polyacetylene ester compound. The reaction is carried out in atmospheric carbon dioxide atmosphere, and carbon dioxide is involved as a monomer in the formation of a polymer. The obtained narrow-range polyacetylene ester compound has good thermal stability and excellent processability. Due to introduction of an aggregation-induced emission group, some polymers show a typical aggregation-induced emission performance.

##STR00001##

Claims

1. A narrow-range polyacetylene ester compound; comprising a structural formula as represented by a formula (I): ##STR00024## wherein n is an integer of 0-200 excluding 0, and R.sub.1 and R.sub.2 are an organic group.

2. The narrow-range polyacetylene ester compound according to claim 1, wherein R.sub.1 is any one of the following organic groups of 1 to 26, and R.sub.2 is a hydrogen atom or any one of the following organic groups of 27 to 29: ##STR00025## ##STR00026## and wherein m, h and k are an integer of 1-20; X is selected from the group consisting of the elements of N, P, O, S and Si; and*indicates a substitution location.

3. A method for preparing the narrow-range polyacetylene ester compound according to claim 1, wherein the method comprises: (1) in atmospheric carbon dioxide atmosphere, a bifunctional alkyne monomer, carbon dioxide, and a dihalide monomer are polymerized by means of a combined action of a catalyzer and alkali in an organic solvent; and (2) after the reaction is completed, the product is added to a precipitant for precipitation, and the precipitate is collected and dried to a constant weight to obtain a narrow-range polyacetylene ester compound; the bifunctional alkyne monomer has a structural formula as represented by formula ##STR00027## the dihalide monomer has a structural formula as represented by formula (III):
XR.sub.2X XCl, Br, I (III) wherein R.sub.1 and R.sub.2 are an organic group.

4. The method for preparing the narrow-range polyacetylene ester compound according to claim 3, wherein R.sub.1 is any one of the following organic groups of 1 to 26, and R.sub.2 is a hydrogen atom or any one of the following organic groups of 27 to 29: ##STR00028## ##STR00029## wherein m, h and k are an integer of 1-20; X is selected from the group consisting of the elements of N, P, O, S and Si; and*indicates a substitution location.

5. The method for preparing the narrow-range polyacetylene ester compound according to claim 3, wherein the organic solvent in step (1) is selected from the group consisting of tetrahydrofuran, dichloromethane, chloroform, toluene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, ethanol, N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and mixtures thereof: and the precipitant described in the step (2) is methanol or n-hexane.

6. The method for preparing the narrow-range polyacetylene ester compound according to claim 3, wherein the catalyzer in the step (1) is at least one of silver tungstate, silver iodide, silver nitrate, silver tetrafluoroborate, silver chloride, silver bromide, silver oxide, silver acetate, cuprous chloride, cuprous bromide, iodide copper, cuprous cyanide, or cuprous oxide; and the alkali in the step (1) is at least one of cesium carbonate, potassium carbonate, potassium hydroxide, sodium hydroxide, cesium fluoride, potassium fluoride, potassium t-butoxide, sodium t-butoxide, lithium t-butoxide, 1,5,7-triazabicyclo[4.4.0]non-5-ene, or hydrazine acetate.

7. The method for preparing the narrow-range polyacetylene ester compound according to claim 3, wherein the concentration of the bifunctional alkyne monomer and the dihalide monomer in the organic solvent in the polymerization in the step (1) is 0.05-5 mol/L.

8. The method for preparing the narrow-range polyacetylene ester compound according to claim 3, wherein the catalyzer is used in an amount of from 1% to 40% by mole of the difunctional alkyne monomer; and the alkali is used in an amount of from 100% to 1000% by mole of the difunctional alkyne monomer.

9. The method for preparing the narrow-range polyacetylene ester compound according to claim 3, wherein the polymerization is performed at a temperature of 0 C. to 200 C. for 0.25-72 h.

10. The method for preparing the narrow-range polyacetylene ester compound according to claim 3, wherein the narrow-range polyacetylene ester compound has a molecular weight distribution coefficient of 1.00-2.00.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 shows a comparison of nuclear magnetic resonance hydrogen spectra of a narrow-range polyacetylene ester compound (D) prepared in Example 1 of the present invention with those of its monomers 1a(A), 2a(B) and a model compound (C) in CD.sub.2Cl.sub.2, and a comparison of nuclear magnetic resonance carbon spectra of a narrow-range polyacetylene ester compound (H) with those of its monomers 1a(E), 2a(F) and a model compound (G) in CD.sub.2Cl.sub.2 (*represents a solvent peak);

[0029] FIG. 2 shows a comparison of infrared absorption spectra of a narrow-range polyacetylene ester compound (C) prepared in Example 1 of the present invention with those of its monomer 1a(A) and a model compound (B);

[0030] FIG. 3 shows a comparison of nuclear magnetic resonance hydrogen spectra of a narrow-range polyacetylene ester compound (D) prepared in Example 2 of the present invention with those of its monomers 1a(A), 2b(B) and a model compound (C) in CD.sub.2Cl.sub.2, and a comparison of nuclear magnetic resonance carbon spectra of a narrow-range polyacetylene ester compound (H) with those of its monomers 1a(E), 2b(F) and a model compound (G) in CD.sub.2Cl.sub.2 (*represents a solvent peak);

[0031] FIG. 4 shows a comparison of infrared absorption spectra of a narrow-range polyacetylene ester compound (C) prepared in Example 2 of the present invention with those of its monomer 1a(A) and a model compound (B);

[0032] FIG. 5 shows a comparison of nuclear magnetic resonance hydrogen spectra of a narrow-range polyacetylene ester compound (D) prepared in Example 3 of the present invention with those of its monomers 1a(A), 2c(B) and a model compound (C) in CD.sub.2Cl.sub.2, and a comparison of nuclear magnetic resonance carbon spectra of a narrow-range polyacetylene ester compound (H) with those of its monomers 1a(E), 2c(F) and a model compound (G) in CD.sub.2Cl.sub.2 (*represents a solvent peak);

[0033] FIG. 6 shows a comparison of infrared absorption spectra of a narrow-range polyacetylene ester compound (C) prepared in Example 3 of the present invention with those of its monomer 1a(A) and a model compound (B);

[0034] FIG. 7 shows a comparison of nuclear magnetic resonance hydrogen spectra of a narrow-range polyacetylene ester compound (C) prepared in Example 4 of the present invention with those of its monomers 1c(A) and 2a(B) in CD.sub.2Cl.sub.2, and a comparison of nuclear magnetic resonance carbon spectra of a narrow-range polyacetylene ester compound (F) with those of its monomers 1c(D) and 2a(E) in CD.sub.2Cl.sub.2 (*represents a solvent peak);

[0035] FIG. 8 shows a comparison of infrared absorption spectra of a narrow-range polyacetylene ester compound (B) prepared in Example 4 of the present invention with those of its monomer 1c(A);

[0036] FIG. 9 shows a comparison of nuclear magnetic resonance hydrogen spectra of a narrow-range polyacetylene ester compound (C) prepared in Example 5 of the present invention with those of its monomers 1d(A) and 2a(B) in CD.sub.2Cl.sub.2, and a comparison of nuclear magnetic resonance carbon spectra of a narrow-range polyacetylene ester compound (F) with those of its monomers 1d(D) and 2a(E) in CD.sub.2Cl.sub.2 (*represents a solvent peak);

[0037] FIG. 10 shows a comparison of infrared absorption spectra of a narrow-range polyacetylene ester compound (B) prepared in Example 5 of the present invention with those of its monomer 1d(A);

[0038] FIG. 11 shows a comparison of nuclear magnetic resonance hydrogen spectra of a narrow-range polyacetylene ester compound (C) prepared in Example 6 of the present invention with those of its monomers 1e(A) and 2a(B) in CD.sub.2Cl.sub.2, and a comparison of nuclear magnetic resonance carbon spectra of a narrow-range polyacetylene ester compound (F) with those of its monomers 1e(D) and 2a(E) in CD.sub.2Cl.sub.2 (*represents a solvent peak);

[0039] FIG. 12 shows a comparison of infrared absorption spectra of a narrow-range polyacetylene ester compound (B) prepared in Example 6 of the present invention with those of its monomer 1e(A);

[0040] FIG. 13 shows thermal weight loss graphs of the narrow-range polyacetylene ester compounds prepared in Examples 1-6 of the present invention; and

[0041] FIG. 14 is a graph showing changes in the weight average molecular weight of a narrow-range polyacetylene ester compound prepared in Example 1 of the present invention with the hydrolysis time in a mixed water and tetrahydrofuran solution of NaOH.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0042] The present invention will be further described in detail below with reference to examples and accompanying drawings, but the embodiments of the present invention are not limited thereto.

EXAMPLE 1

[0043] A narrow-range polyacetylene ester compound P1a/2a/CO.sub.2 of this example has the following structural formula:

##STR00011##

[0044] The above narrow-range polyacetylene ester compound is prepared by polymerization of a bifunctional alkyne monomer, carbon dioxide and a dihalide monomer, with the reaction equation as follows:

##STR00012##

[0045] Wherein the monomer M1a can be synthesized according to the synthesis method disclosed in the applicant's literature (Chan, C. Y. K. et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules 46, 3246-3256 (2013)).

[0046] The specific preparation steps of the narrow-range polyacetylene ester compound described in this example are as follows:

[0047] To a dry Schlenk tube were added M1a (76.1 mg, 0.2 mmol), M2a (43.2 mg, 0.2 mmol), Ag.sub.2WO.sub.4 (9.3 mg, 0.02 mmol) and Cs.sub.2CO.sub.3 (390.0 mg, 1.2 mmol); the Schlenk tube was vacuumed for 0.5 h, and then pricked into a balloon filled with carbon dioxide; 1 mL of N,N-dimethylacetamide (DMAc) was added, a reaction went on at 80 C. for 12 h, and then the temperature was reduced to room temperature; the solution after the reaction was diluted with 4 mL of tetrahydrofuran, and then added dropwise to a conical flask containing 200 mL of methanol solution through a cotton filter device with strong stirring; the precipitate was allowed to stand for 12 h, and then filtered, rinsed with a methanol solution, and dried in a vacuum oven at 40 C. to a constant weight, thus resulting in a narrow-range polyacetylene ester compound P1a/2a/CO.sub.2.

[0048] Characterization data of the narrow-range polyacetylene ester compound P1a/2a/CO.sub.2: a yellow solid at a yield of 88%. The results of gel permeation chromatography (GPC) show a weight average molecular weight (M.sub.w) of 13,600 and a molecular weight distribution (PDI) of 1.37.

[0049] In order to characterize the structure of the narrow-range polyacetylene ester compound, a model reaction was performed and a model compound 3 obtained, with the reaction equation as follows:

##STR00013##

[0050] The comparison of the nuclear magnetic resonance spectra of the narrow-range polyacetylene ester compound obtained in this example with those of its corresponding monomer and the model compound (*represents the solvent peak) is shown in FIG. 1, and the infrared absorption spectra are shown in FIG. 2.

[0051] It can be seen from the nuclear magnetic resonance spectra of FIG. 1 that the resonance absorption peak of the alkyne hydrogen in the monomer M1a (i.e., the monomer 1a) at a chemical shift of 3.09 has completely disappeared in the model compound 3 (the model compound) and the narrow-ranged polyacetylene ester compound (the polymer P1a/2a/CO.sub.2); while in the hydrogen spectra of the model compound 3 (the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2a/CO.sub.2), a new resonance absorption peak representing a methylene hydrogen near the ester group appears at a chemical shift of 4.23.

[0052] It can be seen from the nuclear magnetic resonance carbon spectra of the model compound 3 (the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2a/CO.sub.2) in FIG. 1 that the resonance absorption peak representing an ester-based carbon appears at a chemical shift of 154.17 and the resonance absorption peak representing a methylene carbon near the ester group appears at a chemical shift of 65.77.

[0053] It can be seen from FIG. 2 that the stretching vibration absorption peak at 3293 cm.sup.1 of CH in M1a (i.e., the monomer 1a) has completely disappeared in the infrared absorption spectra of the model compound 3 (the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2a/CO.sub.2); while in the infrared absorption spectra of the model compound 3 (the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2a/CO.sub.2), a new strong absorption peak representing the CO stretching vibration appears at 1712 cm.sup.1.

[0054] The above data prove that we have obtained the target polymer. The narrow-range polyacetylene ester compound is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide at room temperature, indicating excellent processability.

[0055] The thermal weight loss graph of the narrow-range polyacetylene ester compound prepared in Example 1 is shown in FIG. 13, wherein the test conditions were as follows: the test was performed in a nitrogen atmosphere, and the heating rate was 20 C/min; a graph showing changes in the weight average molecular weight of the narrow-range polyacetylene ester compound prepared in Example 1 with the hydrolysis time in a mixed water and tetrahydrofuran solution of NaOH is shown FIG. 14.

[0056] As can be seen from FIG. 13, the narrow-range polyacetylene ester compound has good thermal stability. The polymer exhibits typical aggregation-induced emission characteristic through testing of the solution and the absolute quantum yield in the solid state. As can be seen from FIG. 14, the narrow-range polyacetylene ester compound had a higher degradation rate in a mixed water and tetrahydrofuran solution of NaOH than a general linear polyester, having potential application value in the field of drug release and the like.

EXAMPLE 2

[0057] A narrow-range polyacetylene ester compound P1b/2b/CO.sub.2 of this example has the following structural formula:

##STR00014##

[0058] The above narrow-range polyacetylene ester compound is prepared by polymerization of a bifunctional alkyne monomer, carbon dioxide and a dihalide monomer, with the reaction equation as follows:

##STR00015##

[0059] Wherein the monomer M1a can be synthesized according to the synthesis method disclosed in the applicant's literature (Chan, C. Y. K. et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules 46, 3246-3256 (2013)).

[0060] The specific preparation steps of the narrow-range polyacetylene ester compound described in this example are as follows:

[0061] To a dry Schlenk tube were added M1a (76.1 mg, 0.2 mmol), M2b (48.8 mg, 0.2 mmol), Ag.sub.2WO.sub.4 (9.3 mg, 0.02 mmol) and Cs.sub.2CO.sub.3 (390.0 mg, 1.2 mmol); the Schlenk tube was vacuumed for 0.5 h, and then pricked into a balloon filled with carbon dioxide; 1 mL of N,N-dimethylacetamide (DMAc) was added, a reaction went on at 80 C. for 12 h, and then the temperature was reduced to room temperature; the solution after the reaction was diluted with 4 mL of tetrahydrofuran, and then added dropwise to a conical flask containing 200 mL of methanol solution through a cotton filter device with strong stirring; the precipitate was allowed to stand for 12 h, and then filtered, rinsed with a methanol solution, and dried in a vacuum oven at 40 C. to a constant weight, thus resulting in a narrow-range polyacetylene ester compound P1a/2b/CO.sub.2.

[0062] Characterization data of the narrow-range polyacetylene ester compound P1a/2b/CO.sub.2: a yellow solid at a yield of 90%. The results of gel permeation chromatography (GPC) show a weight average molecular weight (M.sub.w) of 20,500 and a molecular weight distribution (PDI) of 1.69.

[0063] In order to characterize the structure of the narrow-range polyacetylene ester compound, a model reaction was performed and a model compound 3 obtained, with the reaction equation as shown in (b) of Example 1.

[0064] The comparison of the nuclear magnetic resonance spectra of the narrow-range polyacetylene ester compound obtained in this example with those of its corresponding monomer and the model compound (*represents the solvent peak) is shown in FIG. 3, and the infrared absorption spectra are shown in FIG. 4.

[0065] It can be seen from the nuclear magnetic resonance hydrogen spectra of FIG. 3 that the resonance absorption peak of the alkyne hydrogen in the monomer M1a (i.e., the monomer 1a) at the chemical shift of 3.09 has completely disappeared in the model compound 3 (the model compound) and the narrow-ranged polyacetylene ester compound (the polymer P1a/2b/CO.sub.2); while in the hydrogen spectra of the model compound 3 (the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2b/CO.sub.2), a resonance absorption peak representing a methylene hydrogen near the ester group appears at a chemical shift of 4.18.

[0066] It can be seen from the nuclear magnetic resonance carbon spectra of the model compound 3 (the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2b/CO.sub.2) in FIG. 3 that the resonance absorption peak representing an ester-based carbon appears at a chemical shift of 154.27 and the resonance absorption peak representing a methylene carbon near the ester group appears at a chemical shift of 66.35.

[0067] It can be seen from FIG. 4 that the stretching vibration absorption peak at 3293 cm.sup.1 of CH in M1a (i.e., the monomer 1a) has completely disappeared in the infrared absorption spectra of the model compound 3 (the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2b/CO.sub.2); while in the infrared absorption spectra of the model compound 3 (the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2b/CO.sub.2), a new strong absorption peak representing the CO stretching vibration appears at 1709 cm.sup.1. The above data prove that we have obtained the target polymer. The narrow-range polyacetylene ester compound is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide at room temperature, indicating excellent processability.

[0068] The thermal weight loss graph of the narrow-range polyacetylene ester compound prepared in Example 2 is shown in FIG. 13.

[0069] As can be seen from FIG. 13, the narrow-range polyacetylene ester compound has good thermal stability. The polymer exhibits typical aggregation-induced emission through testing of the solution and the absolute quantum yield in the solid state.

EXAMPLE 3

[0070] A narrow-range polyacetylene ester compound P1a/2c/CO.sub.2 of this example has the following structural formula:

##STR00016##

[0071] The above narrow-range polyacetylene ester compound is prepared by polymerization of a bifunctional alkyne monomer, carbon dioxide and a dihalide monomer, with the reaction equation as follows:

##STR00017##

[0072] Wherein the monomer M1a can be synthesized according to the synthesis method disclosed in the applicant's literature (Chan, C. Y. K. et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules 46,3246-3256 (2013)).

[0073] The specific preparation steps of the narrow-range polyacetylene ester compound described in this example are as follows:

[0074] To a dry Schlenk tube were added M1a (76.1 mg, 0.2 mmol), M2c (54.4 mg, 0.2 mmol), Ag.sub.2WO.sub.4 (9.3 mg, 0.02 mmol) and Cs.sub.2CO.sub.3 (390.0 mg, 1.2 mmol); the Schlenk tube was vacuumed for 0.5 h, and then pricked into a balloon filled with carbon dioxide; 1 mL of N,N-dimethylacetamide (DMAc) was added, the reaction went on at 80 C. for 12 h, and then the temperature was reduced to room temperature; the solution after the reaction was diluted with 4 mL of tetrahydrofuran, and then added dropwise to a conical flask containing 200 mL of methanol solution through a cotton filter device with strong stirring; the precipitate was allowed to stand for 12 h, and then filtered, rinsed with a methanol solution, and dried in a vacuum oven at 40 C. to a constant weight, thus resulting in a narrow-range polyacetylene ester compound P1a/2c/CO.sub.2.

[0075] Characterization data of the narrow-range polyacetylene ester compound P1a/2c/CO.sub.2: a yellow solid at a yield of 95%. The results of gel permeation chromatography (GPC) show a weight average molecular weight (M.sub.w) of 31,400 and a molecular weight distribution (PDI) of 1.86.

[0076] In order to characterize the structure of the narrow-range polyacetylene ester compound, a model reaction was performed and a model compound 3 (i.e., the model compound) obtained, with the reaction equation as shown in (b) of Example 1.

[0077] The comparison of the nuclear magnetic resonance spectra of the narrow-range polyacetylene ester compound obtained in this example with those of its corresponding monomer and the model compound (*represents the solvent peak) is shown in FIG. 5, and the infrared absorption spectra are shown in FIG. 6.

[0078] It can be seen from the nuclear magnetic resonance hydrogen spectra of the model compound 3 (i.e., the model compound) and the narrow-range polyacetylene ester compound (P1a/2c/CO.sub.2) in FIG. 5 that the resonance absorption peak of the alkyne hydrogen in the monomer M1a (i.e., the monomer 1a) at a chemical shift of 3.09 has completely disappeared in the model compound 3 (i.e., the model compound) and the narrow-range polyacetylene ester compound (P1a/2c/CO.sub.2); while in the hydrogen spectra of the model compound 3 and the narrow-range polyacetylene ester compound (the polymer P1a/2c/CO.sub.2), a resonance absorption peak representing a methylene hydrogen near the ester group appears at a chemical shift of 4.17.

[0079] It can be seen from the nuclear magnetic resonance carbon spectra of the model compound 3 (i.e., the model compound) and the narrow-range polyacetylene ester compound (the polymer P1a/2c/CO.sub.2) in FIG. 5 that the resonance absorption peak representing an ester-based carbon appears at a chemical shift of 154.28 and the resonance absorption peak representing a methylene carbon near the ester group appears at a chemical shift of 66.53.

[0080] It can be seen from FIG. 6 that the stretching vibration absorption peak at 3293 cm.sup.1 of CH in M1a (i.e., the monomer 1a) has completely disappeared in the infrared absorption spectra of the model compound 3 and the narrow-range polyacetylene ester compound(P1a/2c/CO.sub.2); while in the infrared absorption spectra of the model compound 3 and the narrow-range polyacetylene ester compound (P1a/2c/CO.sub.2), a new strong absorption peak representing the CO stretching vibration appears at 1709 cm.sup.1. The above data prove that we have obtained the target polymer. The narrow-range polyacetylene ester compound is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide at room temperature, indicating excellent processability.

[0081] The thermal weight loss graph of the narrow-range polyacetylene ester compound prepared in Example 3 is shown in FIG. 13. As can be seen from FIG. 13, the narrow-range polyacetylene ester compound has good thermal stability. The polymer exhibits typical aggregation-induced emission through testing of the solution and the absolute quantum yield in the solid state.

EXAMPLE 4

[0082] A narrow-range polyacetylene ester compound P1c/2a/CO.sub.2 of this example has the following structural formula:

##STR00018##

[0083] The above narrow-range polyacetylene ester compound is prepared by polymerization of a bifunctional alkyne monomer, carbon dioxide and a dihalide monomer, with the reaction equation as follows:

##STR00019##

[0084] Wherein the monomer M1c can be synthesized according to the synthesis method disclosed in the applicant's literature (Chan, C. Y. K. et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules 46, 3246-3256 (2013)).

[0085] The specific preparation steps of the narrow-range polyacetylene ester compound described in this example are as follows:

[0086] To a dry Schlenk tube were added M1c (58.7 mg, 0.2 mmol), M2a (43.2 mg, 0.2 mmol), Ag.sub.2WO.sub.4 (9.3 mg, 0.02 mmol) and Cs.sub.2CO.sub.3 (390.0 mg, 1.2 mmol); the Schlenk tube was vacuumed for 0.5 h, and then pricked into a balloon filled with carbon dioxide; 1 mL of N,N-dimethylacetamide (DMAc) was added, the reaction went on at 80 C. for 12 h, and then the temperature was reduced to room temperature; the solution after the reaction was diluted with 4 mL of tetrahydrofuran, and then added dropwise to a conical flask containing 200 mL of methanol solution through a cotton filter device with strong stirring; the precipitate was allowed to stand for 12 h, and then filtered, rinsed with a methanol solution, and dried in a vacuum oven at 40 C. to a constant weight, thus resulting in a narrow-range polyacetylene ester compound P1c/2a/CO.sub.2.

[0087] Characterization data of the narrow-range polyacetylene ester compound P1c/2a/CO.sub.2: a yellow solid at a yield of 83%. The results of gel permeation chromatography (GPC) show a weight average molecular weight (M.sub.w) of 12,100 and a molecular weight distribution (PDI) of 1.70.

[0088] The comparison of the nuclear magnetic resonance spectra of the narrow-range polyacetylene ester compound obtained in this example with those of its corresponding monomer (*represents the solvent peak) is shown in FIG. 7, and the infrared absorption spectra are shown in FIG. 8.

[0089] It can be seen from the nuclear magnetic resonance hydrogen spectra in FIG. 7 that the resonance absorption peak of the alkyne hydrogen in the monomer M1c (i.e., the monomer 1c) at a chemical shift of 3.09 has completely disappeared in the narrow-range polyacetylene ester compound (P1c/2a/CO.sub.2); while in the hydrogen spectra of the narrow-range polyacetylene ester compound (the polymer P1c/2a/CO.sub.2), a resonance absorption peak representing a methylene hydrogen near the ester group appears at a chemical shift of 4.25. It can be seen from the nuclear magnetic resonance carbon spectra of the narrow-range polyacetylene ester compound (the polymer P1c/2a/CO.sub.2) in FIG. 7 that the resonance absorption peak representing an ester-based carbon appears at a chemical shift of 154.38 and the resonance absorption peak representing a methylene carbon near the ester group appears at a chemical shift of 65.71.

[0090] It can be seen from FIG. 8 that the stretching vibration absorption peak at 3290 cm.sup.1 of Cin M1c (i.e., the monomer 1c) has completely disappeared in the infrared absorption spectra of the narrow-range polyacetylene ester compound (P1c/2a/CO.sub.2); while in the infrared absorption spectra of the narrow-range polyacetylene ester compound (P1c/2a/CO.sub.2), a strong absorption peak representing the CO stretching vibration appears at 1708 cm.sup.1. The above data prove that we have obtained the target polymer. The narrow-range polyacetylene ester compound is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide at room temperature, indicating excellent process ability.

[0091] The thermal weight loss graph of the narrow-range polyacetylene ester compound prepared in Example 4 is shown in FIG. 13. As can be seen from FIG. 13, the narrow-range polyacetylene ester compound has good thermal stability.

EXAMPLE 5

[0092] A narrow-range polyacetylene ester compound P1d/2a/CO.sub.2 of this example has the following structural formula:

##STR00020##

[0093] The above narrow-range polyacetylene ester compound is prepared by polymerization of a bifunctional alkyne monomer, carbon dioxide and a dihalide monomer, with the reaction equation as follows:

##STR00021##

[0094] Wherein the monomer M1d can be synthesized according to the synthesis method disclosed in the applicant's literature (Chan, C. Y. K. et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules 46, 3246-3256 (2013)).

[0095] The specific preparation steps of the narrow-range polyacetylene ester compound described in this example are as follows:

[0096] To a dry Schlenk tube were added M1d (92.5 mg, 0.2 mmol), M2a (43.2 mg, 0.2 mmol), Ag.sub.2WO.sub.4 (9.3 mg, 0.02 mmol) and C.sub.2CO.sub.3 (390.0 mg, 1.2 mmol); the Schlenk tube was vacuumed for 0.5 h, and then pricked into a balloon filled with carbon dioxide; 1 mL of N,N-dimethylacetamide (DMAc) was added, the reaction went on at 80 C. for 12 h, and then the temperature was reduced to room temperature; the solution after the reaction was diluted with 4 mL of tetrahydrofuran, and then added dropwise to a conical flask containing 200 mL of methanol solution through a cotton filter device with strong stirring; the precipitate was allowed to stand for 12 h, and then filtered, rinsed with a methanol solution, and dried in a vacuum oven at 40 C. to a constant weight, thus resulting in a narrow-range polyacetylene ester compound P1d/2a/CO.sub.2.

[0097] Characterization data of the narrow-range polyacetylene ester compound P1d/2a/CO.sub.2: a yellow solid at a yield of 85%. The results of gel permeation chromatography (GPC) show a weight average molecular weight (M.sub.w) of 13,200 and a molecular weight distribution (PDI) of 1.61.

[0098] The comparison of the nuclear magnetic resonance spectra of the narrow-range polyacetylene ester compound obtained in this example with those of its corresponding monomer (*represents the solvent peak) is shown in FIG. 9, and the infrared absorption spectra are shown in FIG. 10.

[0099] It can be seen from the nuclear magnetic resonance hydrogen spectra in FIG. 9 that the resonance absorption peak of the alkyne hydrogen in the monomer M1d (i.e., the monomer 1d) at a chemical shift of 3.08 has completely disappeared in the narrow-range polyacetylene ester compound (P1d/2a/CO.sub.2); while in the hydrogen spectra of the narrow-range polyacetylene ester compound (the polymer P1d/2a/CO.sub.2), a resonance absorption peak representing a methylene hydrogen near the ester group appears at a chemical shift of 4.23.

[0100] It can be seen from the nuclear magnetic resonance carbon spectra of the narrow-range polyacetylene ester compound (the polymer P1d/2a/CO.sub.2) in FIG. 9 that the resonance absorption peak representing an ester-based carbon appears at a chemical shift of 154.28 and the resonance absorption peak representing a methylene carbon near the ester group appears at a chemical shift of 65.73.

[0101] It can be seen from FIG. 10 that the stretching vibration absorption peak at 3287 cm.sup.1 of Cin M1d (i.e., the monomer 1d) has completely disappeared in the infrared absorption spectra of the narrow-range polyacetylene ester compound (P1d/2a/CO.sub.2); while in the infrared absorption spectra of the narrow-range polyacetylene ester compound (P1d/2a/CO.sub.2), a strong absorption peak representing the CO stretching vibration appears at 1708 cm.sup.1. The above data prove that we have obtained the target polymer. The narrow-range polyacetylene ester compound is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide at room temperature, indicating excellent proces s ability.

[0102] The thermal weight loss graph of the narrow-range polyacetylene ester compound prepared in Example 5 is shown in FIG. 13. As can be seen from FIG. 13, the narrow-range polyacetylene ester compound has good thermal stability. The polymer exhibits typical aggregation-induced emission through testing of the solution and the absolute quantum yield in the solid state.

EXAMPLE 6

[0103] A narrow-range polyacetylene ester compound P1e/2a/CO.sub.2 of this example has the following structural formula:

##STR00022##

[0104] The above narrow-range polyacetylene ester compound is prepared by polymerization of a bifunctional alkyne monomer, carbon dioxide and a dihalide monomer, with the reaction equation as follows:

##STR00023##

[0105] Wherein the monomer M1e can be synthesized according to the synthesis method disclosed in the applicant's literature (Li, W. et al. Catalyzer-Free, Atom-Economic, Multicomponent Polymerizations of Aromatic Diynes, Elemental Sulfur, and Aliphatic Diamines toward Luminescent Polythioamides. Macromolecules 48, 7747-7754 (2015)).

[0106] The specific preparation steps of the narrow-range polyacetylene ester compound described in this example are as follows:

[0107] To a dry Schlenk tube were added M1e (63.7 mg, 0.2 mmol), M2a (43.2 mg, 0.2 mmol), Ag.sub.2WO.sub.4 (9.3 mg, 0.02 mmol) and Cs.sub.2CO.sub.3 (390.0 mg, 1.2 mmol); the Schlenk tube was vacuumed for 0.5 h, and then pricked into a balloon filled with carbon dioxide; 1 mL of N,N-dimethylacetamide (DMAc) was added, the reaction went on at 80 C. for 12 h, and then the temperature was reduced to room temperature; the solution after the reaction was diluted with 4 mL of tetrahydrofuran, and then added dropwise to a conical flask containing 200 mL of methanol solution through a cotton filter device with strong stirring; the precipitate was allowed to stand for 12 h, and then filtered, rinsed with a methanol solution, and dried in a vacuum oven at 40 C. to a constant weight, thus resulting in a narrow-range polyacetylene ester compound P1e/2a/CO.sub.2.

[0108] Characterization data of the narrow-range polyacetylene ester compound P1e/2a/CO.sub.2: a light gray solid at a yield of 78%. The results of gel permeation chromatography (GPC) show a weight average molecular weight (M.sub.w) of 20,600 and a molecular weight distribution (PDI) of 2.00.

[0109] The comparison of the nuclear magnetic resonance spectra of the narrow-range polyacetylene ester compound obtained in this example with those of its corresponding monomer (*represents the solvent peak) is shown in FIG. 11, and the infrared absorption spectra are shown in FIG. 12.

[0110] It can be seen from the nuclear magnetic resonance hydrogen spectra in FIG. 11 that the resonance absorption peak of the alkyne hydrogen in the monomer M1e (i.e., the monomer 1e) at a chemical shift of 3.03 has completely disappeared in the narrow-range polyacetylene ester compound (P1e/2a/CO.sub.2); while in the hydrogen spectra of the narrow-range polyacetylene ester compound (the polymer P1e/2a/CO.sub.2), a resonance absorption peak representing a methylene hydrogen near the ester group appears at a chemical shift of 4.24. It can be seen from the nuclear magnetic resonance carbon spectra of the narrow-range polyacetylene ester compound (the polymer P1e/2a/CO.sub.2) in FIG. 11 that the resonance absorption peak representing an ester-based carbon appears at a chemical shift of 154.48 and the resonance absorption peak representing a methylene carbon near the ester group appears at a chemical shift of 65.64.

[0111] It can be seen from FIG. 12 that the stretching vibration absorption peak at 3310 cm.sup.1 of Cin M1e (i.e., the monomer le) has completely disappeared in the infrared absorption spectra of the narrow-range polyacetylene ester compound (P1e/2a/CO.sub.2); while in the infrared absorption spectra of the narrow-range polyacetylene ester compound (P1e/2a/CO.sub.2), a strong absorption peak representing the CO stretching vibration appears at 1703 cm.sup.1. The above data prove that we have obtained the target polymer. The narrow-range polyacetylene ester compound is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide at room temperature, indicating excellent process ability.

[0112] The thermal weight loss graph of the narrow-range polyacetylene ester compound prepared in Example 6 is shown in FIG. 13. As can be seen from FIG. 13, the narrow-range polyacetylene ester compound has good thermal stability.

[0113] The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited thereto, and any other alterations, modifications, substitutions, combinations and simplifications made without departing from the spirit and principle of the present invention should all be equivalent replacements and included in the scope of protection of the present invention.