WO2018076595A1 - 窄分布聚炔酯类化合物及其制备方法 - Google Patents

窄分布聚炔酯类化合物及其制备方法 Download PDF

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WO2018076595A1
WO2018076595A1 PCT/CN2017/076697 CN2017076697W WO2018076595A1 WO 2018076595 A1 WO2018076595 A1 WO 2018076595A1 CN 2017076697 W CN2017076697 W CN 2017076697W WO 2018076595 A1 WO2018076595 A1 WO 2018076595A1
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ester compound
narrow
polyalkynyl
monomer
distributed
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French (fr)
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唐本忠
宋波
秦安军
赵祖金
胡蓉蓉
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South China University of Technology SCUT
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Definitions

  • the invention belongs to the technical field of organic synthesis, and in particular relates to a narrow distribution polyacetylene ester compound and a preparation method thereof.
  • Carbon dioxide has now attracted widespread attention around the world, as the continued growth of carbon dioxide in the atmosphere has caused many climate problems. There are two ways to reduce the concentration of carbon dioxide in the atmosphere, one is to store it physically, and the other is to chemically convert it. It is well known that carbon dioxide is a rich, inexpensive, non-toxic and renewable C1 monomer, so converting carbon dioxide into some useful materials is a more advocated practice. However, due to the lower reactivity of carbon dioxide, its application in the field of chemical synthesis has been greatly limited. At present, there are only a few highly efficient polymerizations using carbon dioxide. The most famous one, which is the most widely studied in the world, is the copolymerization of carbon dioxide and epoxy compounds.
  • alkynes are one of the readily available or easily synthesized chemical materials.
  • the use of alkyne to construct functional polymers has important academic and technical significance and has attracted wide attention of scientists. However, there have been few reports on the copolymerization of alkynes and carbon dioxide.
  • the preparation method can be carried out under an atmospheric carbon dioxide atmosphere, and carbon dioxide participates as a monomer in the formation of a polymer, and the reaction is green, efficient, and easy to handle.
  • Another object of the present invention is to provide a narrow-distributed polyalkyn ester compound which is produced by the above method.
  • a method for preparing a narrow distribution polyalkyn ester compound comprising the following steps:
  • a bifunctional acetylenic monomer, carbon dioxide, and a dihalogen monomer are polymerized by an action of a catalyst and a base in an organic solvent;
  • the bifunctional acetylenic monomer has the structural formula of formula (II) as follows:
  • the dihalogen monomer has the structural formula of formula (III) as follows:
  • R 1 is any one of the following 1 to 26; and R 2 is any one of the following 27 to 29;
  • m, h, and k are integers of 1 to 20; X is selected from N, P, O, S, or Si elements; and * represents a substitution position.
  • the organic solvent in the step (1) is selected from the group consisting of tetrahydrofuran, dichloromethane, chloroform, toluene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N- At least one of dimethylacetamide, acetonitrile, ethanol, N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.
  • the organic solvent is selected from the group consisting of N,N-dimethylacetamide, and in this case, the obtained narrowly distributed polyacetylene ester compound has better solubility, yield and The molecular weight is also high, which is convenient for the next application.
  • the concentration of the reactive monomer may affect the yield of the reaction.
  • the concentration of the bifunctional acetylenic monomer and the dihalogen monomer in the organic solvent in the polymerization reaction in the step (1) is 0.05 to 0.05. 5 mol/L, further preferably, the amount of the substance of the difunctional acetylenic monomer in the organic solvent is 0.20 mol/L, and the molar ratio of the difunctional acetylenic monomer to the dihalogen monomer is 1: 1.
  • the type and amount of the reaction catalyst may affect the reaction time and the yield and molecular weight of the product.
  • the catalyst in the step (1) is silver tungstate, silver iodide, silver nitrate, silver tetrafluoroborate, silver chloride, At least one of silver bromide, silver oxide, silver acetate, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, the amount of the catalyst is a bifunctional acetylene single 1 mol% to 40 mol% of the body; further preferably, the catalyst is silver tungstate, and the catalyst is used in an amount of 10 mol% of the difunctional acetylenic monomer.
  • the type and amount of the reaction base may affect the reaction time and the yield and molecular weight of the product.
  • the base in the step (1) is cesium carbonate, potassium carbonate, potassium hydroxide, sodium hydroxide, cesium fluoride, At least one of potassium fluoride, potassium t-butoxide, sodium t-butoxide, lithium t-butoxide, 1,5,7-triazabicyclo[4.4.0]non-5-ene, and cesium acetate.
  • the base is used in an amount of from 100 mol% to 1000 mol% of the difunctional acetylenic monomer; more preferably, the base is cesium carbonate, and the base is used in an amount of from 300 mol% to 600 mol% of the difunctional acetylenic monomer.
  • the temperature of the polymerization reaction in the step (1) is from 0 to 200 ° C for a period of from 0.25 to 72 hours.
  • the temperature of the polymerization reaction is further preferably 80 ° C, and the time is preferably 12 hours from the viewpoint of energy saving and high speed and high efficiency in view of the yield of the polymerization reaction and the molecular weight of the product obtained by polymerization and the distribution thereof.
  • the precipitating agent described in the step (2) is methanol or n-hexane.
  • n is an integer of 0 to 200 and n is not 0, and R 1 and R 2 are an organic group.
  • R 1 is any one of the following 1 to 26;
  • R 2 is any one of the following 27 to 29;
  • m, h, and k are integers of 1 to 20; X is selected from N, P, O, S, or Si elements; and * represents a substitution position.
  • the narrow distribution polyalkynyl ester compound is prepared by the above method, and has a molecular weight distribution coefficient (PDI) of 1.00 to 2.00.
  • PDI molecular weight distribution coefficient
  • the preparation method of the present invention can be carried out under an atmospheric carbon dioxide atmosphere, and carbon dioxide is involved as a monomer in the formation of a polymer;
  • the preparation method of the invention is simple in operation, the reaction raw materials and the catalyst are easily available, and can be directly purchased or prepared by a simple reaction; the polymerization reaction condition is mild, and energy is saved; one monomer in the polymerization reaction is carbon dioxide, the cost is low, and the environment is green. ;
  • the preparation method of the invention has good functional group tolerance, and various functional groups can be introduced; the functionalized narrow-distribution polyalkynyl ester compound obtained has a narrow molecular weight distribution and good thermal stability. Excellent processability and extraordinary degradation properties, due to the introduction of aggregation-induced luminescent groups, some polymers exhibit typical aggregation-induced luminescence properties.
  • Example 1 is a comparison of nuclear magnetic resonance spectra of a narrow-distributed polyalkyn ester compound (D) prepared in Example 1 of the present invention with its monomers 1a (A), 2a (B) and a model compound (C) in CD 2 Cl 2 And a nuclear magnetic resonance carbon spectrum comparison chart of the narrowly distributed polyalkyn ester compound (H) and its monomers 1a (E), 2a (F) and model compound (G) in CD 2 Cl 2 (* represents a solvent peak);
  • FIG. 2 is a comparison diagram of infrared absorption spectra of a narrow-distributed polyalkyn ester compound (C) prepared in Example 1 of the present invention and a monomer 1a (A) and a model compound (B);
  • FIG. 3 is a comparison of nuclear magnetic resonance spectra of a narrow-distributed polyalkyn ester compound (D) prepared in Example 2 of the present invention with its monomers 1a (A), 2b (B) and a model compound (C) in CD 2 Cl 2 ; And a nuclear magnetic resonance carbon spectrum comparison chart of the narrowly distributed polyalkyn ester compound (H) and its monomers 1a (E), 2b (F) and model compound (G) in CD 2 Cl 2 (* represents a solvent peak);
  • FIG. 4 is a comparison diagram of infrared absorption spectra of a narrow-distributed polyalkyn ester compound (C) prepared in Example 2 of the present invention and a monomer 1a (A) and a model compound (B);
  • Figure 5 is a comparison of nuclear magnetic resonance spectra of a narrow-distributed polyalkynyl ester compound (D) prepared in Example 3 of the present invention with its monomers 1a (A), 2c (B) and model compound (C) in CD 2 Cl 2 And a comparison chart of the nuclear magnetic resonance carbon spectra of the narrowly distributed polyalkyn ester compound (H) and its monomers 1a (E), 2c (F) and model compound (G) in CD 2 Cl 2 (* represents a solvent peak);
  • FIG. 6 is a comparison diagram of infrared absorption spectra of a narrow-distributed polyalkyn ester compound (C) prepared in Example 3 of the present invention and a monomer 1a (A) and a model compound (B);
  • Figure 7 is a comparison chart of the nuclear magnetic resonance spectrum of the narrow-distributed polyalkyn ester compound (C) prepared in Example 4 of the present invention and its monomers 1c (A) and 2a (B) in CD 2 Cl 2 and a narrow distribution polyalkynyl ester Comparison of nuclear magnetic resonance carbon spectra of compound (F) with its monomers 1c (D) and 2a (E) in CD 2 Cl 2 (* represents solvent peak);
  • Figure 8 is a comparison diagram of infrared absorption spectra of a narrow-distributed polyalkynyl ester compound (B) prepared in Example 4 of the present invention and its monomer 1c (A);
  • Figure 9 is a comparison chart of a nuclear magnetic resonance spectrum of a narrow-distributed polyalkynyl ester compound (C) prepared in Example 5 of the present invention with its monomers 1d (A) and 2a (B) in CD 2 Cl 2 and a narrow-distribution polyalkynyl ester Comparison of nuclear magnetic resonance carbon spectra of compound (F) with its monomers 1d(D) and 2a(E) in CD 2 Cl 2 (* represents solvent peak);
  • Figure 10 is a comparison chart of infrared absorption spectra of a narrow-distributed polyalkynyl ester compound (B) prepared in Example 5 of the present invention and its monomer 1d (A);
  • Figure 11 is a comparative view of a nuclear magnetic resonance spectrum of a narrow-distributed polyalkynyl ester compound (C) prepared in Example 6 of the present invention and its monomers 1e (A) and 2a (B) in CD 2 Cl 2 and a narrow-distribution polyalkynyl ester Comparison of nuclear magnetic resonance carbon spectra of compound (F) with its monomers 1e (D) and 2a (E) in CD 2 Cl 2 (* represents solvent peak);
  • Figure 12 is a comparison chart of infrared absorption spectra of a narrow-distributed polyalkyn ester compound (B) prepared in Example 6 of the present invention and its monomer 1e (A);
  • Figure 13 is a graph showing the thermal weight loss curves of the narrow-distributed polyalkyn ester compounds prepared in Examples 1 to 6 of the present invention.
  • Figure 14 is a graph showing changes in weight average molecular weight of a narrow-distributed polyalkynyl ester compound prepared in Example 1 of the present invention in a mixed solution of NaOH water and tetrahydrofuran with hydrolysis time.
  • a narrow distribution polyalkyn ester compound P1a/2a/CO 2 of this embodiment has the following structural formula:
  • the above narrowly distributed polyalkynyl ester compound is prepared by polymerization of a bifunctional acetylenic monomer, carbon dioxide and a dihalogen monomer, and the reaction equation is as follows:
  • the synthesis method of the monomer M1a can be carried out according to the applicant's published literature (Chan, CYK et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules Synthetic method synthesis of 46, 3246–3256 (2013).
  • M1a (76.1 mg, 0.2 mmol), M2a (43.2 mg, 0.2 mmol), Ag 2 WO 4 (9.3 mg, 0.02 mmol), Cs 2 CO 3 (390.0 mg, 1.2 mmol) was added to a dry Schlenk tube. ), evacuate for 0.5 hour, pour a balloon filled with carbon dioxide, add 1 mL of N,N-dimethylacetamide (DMAc), react at 80 ° C for 12 hours, then cool to room temperature, then take 4 mL of the solution after the reaction.
  • DMAc N,N-dimethylacetamide
  • the tetrahydrofuran was diluted and then added dropwise to a conical flask containing 200 mL of methanol solution through a cotton filter device, with vigorous stirring, placed for 12 h, filtered, rinsed with methanol solution, and then dried under vacuum.
  • the box was dried at 40 ° C until the weight did not change again, resulting in a narrow distribution of the polyalkyn ester compound P1a/2a/CO 2 .
  • the results of gel permeation chromatography (GPC) showed a weight average molecular weight (M w ) of 13 600 and a molecular weight distribution (PDI) of 1.37.
  • the nuclear magnetic resonance carbon spectrum shows that the resonance absorption peak representing the ester-based carbon appears in the chemical shift.
  • the resonance absorption peak representing the methylene carbon near the ester group appears at a chemical shift of 65.77.
  • the above data prove that we have obtained the target polymer.
  • the narrowly distributed polyalkynyl ester compound is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide at room temperature, indicating excellent processability.
  • thermogravimetric curve of the narrow-distributed polyalkyn ester compound prepared in Example 1 is shown in Fig. 13, and the test conditions were as follows: the heating rate was 20 ° C / min under a nitrogen atmosphere; the narrow-distributed polyalkyn ester compound prepared in Example 1
  • the change in weight average molecular weight with hydrolysis time in a mixed solution of NaOH water and tetrahydrofuran is shown in FIG.
  • the narrow-distributed polyalkyn ester compound has good thermal stability.
  • the polymer exhibited typical aggregation-induced luminescence by the test solution and the absolute quantum yield in the solid state.
  • the narrow distribution polyalkyn ester compound is mixed with water of NaOH and tetrahydrofuran. In the solution, it has a rapid degradation rate, which is faster than the general linear polyester, and has potential application value in the field of drug release.
  • a narrow distribution polyalkyn ester compound P1a/2b/CO 2 of the present embodiment has the following structural formula:
  • the above narrowly distributed polyalkynyl ester compound is prepared by polymerization of a bifunctional acetylenic monomer, carbon dioxide and a dihalogen monomer, and the reaction equation is as follows:
  • the synthesis method of the monomer M1a can be carried out according to the applicant's published literature (Chan, CYK et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules Synthetic method synthesis of 46, 3246–3256 (2013).
  • M1a (76.1 mg, 0.2 mmol), M2b (48.8 mg, 0.2 mmol), Ag 2 WO 4 (9.3 mg, 0.02 mmol), Cs 2 CO 3 (390.0 mg, 1.2 mmol) was added to a dry Schlenk tube. ), evacuate for 0.5 hour, pour a balloon filled with carbon dioxide, add 1 mL of N,N-dimethylacetamide (DMAc), react at 80 ° C for 12 hours, then cool to room temperature, then take 4 mL of the solution after the reaction.
  • DMAc N,N-dimethylacetamide
  • the tetrahydrofuran was diluted and then added dropwise via a cotton filter to an Erlenmeyer flask containing 200 mL of methanol solution, placed with vigorous stirring for 12 h, filtered, rinsed with methanol solution, and then dried in a vacuum oven. Drying to constant weight at 40 ° C gave a product narrowly distributed polyalkyn ester compound P1a/2b/CO 2 .
  • Narrow distribution polyalkynyl ester compound P1a/2b/CO 2 characterization data yellow solid, yield 90%.
  • the results of gel permeation chromatography (GPC) showed a weight average molecular weight (M w ) of 20 500 and a molecular weight distribution (PDI) of 1.69.
  • the nuclear magnetic resonance carbon spectrum shows that the resonance absorption peak representing the ester-based carbon appears in the chemical shift.
  • the resonance absorption peak representing the methylene carbon near the ester group appears at a chemical shift of 66.35.
  • thermogravimetric curve of the narrow-distributed polyalkyn ester compound prepared in Example 2 is shown in FIG.
  • the narrow-distributed polyalkyn ester compound has good thermal stability.
  • the polymer exhibited typical aggregation-induced luminescence by the test solution and the absolute quantum yield in the solid state.
  • a narrow distribution polyalkyn ester compound P1a/2c/CO 2 of this embodiment has the following structural formula:
  • the above narrowly distributed polyalkynyl ester compound is prepared by polymerization of a bifunctional acetylenic monomer, carbon dioxide and a dihalogen monomer, and the reaction equation is as follows:
  • the synthesis method of the monomer M1a can be carried out according to the applicant's published literature (Chan, CYK et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules Synthetic method synthesis of 46, 3246–3256 (2013).
  • M1a (76.1 mg, 0.2 mmol), M2c (54.4 mg, 0.2 mmol), Ag 2 WO 4 (9.3 mg, 0.02 mmol), Cs 2 CO 3 (390.0 mg, 1.2 mmol) was added to a dry Schlenk tube. ), evacuate for 0.5 hour, pour a balloon filled with carbon dioxide, add 1 mL of N,N-dimethylacetamide (DMAc), react at 80 ° C for 12 hours, then cool to room temperature, then take 4 mL of the solution after the reaction.
  • DMAc N,N-dimethylacetamide
  • the tetrahydrofuran was diluted and then added dropwise via a cotton filter to an Erlenmeyer flask containing 200 mL of methanol solution, placed with vigorous stirring for 12 h, filtered, rinsed with methanol solution, and then dried in a vacuum oven. Drying to constant weight at 40 ° C gave a product narrowly distributed polyalkyn ester compound P1a/2c/CO 2 .
  • model compound 3 i.e., a model compound
  • reaction equation is as shown in (b) of Example 1.
  • thermogravimetric curve of the narrowly distributed polyalkyn ester compound prepared in Example 3 is shown in FIG. As can be seen from Fig. 13, the narrow-distributed polyalkyn ester compound has good thermal stability. The polymer exhibited typical aggregation-induced luminescence by the test solution and the absolute quantum yield in the solid state.
  • a narrow distribution polyalkyn ester compound P1c/2a/CO 2 of this embodiment has the following structural formula:
  • the above narrowly distributed polyalkynyl ester compound is prepared by polymerization of a bifunctional acetylenic monomer, carbon dioxide and a dihalogen monomer, and the reaction equation is as follows:
  • the synthesis method of the monomer M1c can be carried out according to the applicant's published literature (Chan, CYK et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules Synthetic method synthesis of 46, 3246–3256 (2013).
  • M1c (58.7 mg, 0.2 mmol), M2a (43.2 mg, 0.2 mmol), Ag 2 WO 4 (9.3 mg, 0.02 mmol), Cs 2 CO 3 (390.0 mg, 1.2 mmol) was added to a dry Schlenk tube. ), evacuate for 0.5 hour, pour a balloon filled with carbon dioxide, add 1 mL of N,N-dimethylacetamide (DMAc), react at 80 ° C for 12 hours, then cool to room temperature, then take 4 mL of the solution after the reaction.
  • DMAc N,N-dimethylacetamide
  • the tetrahydrofuran was diluted and then added dropwise via a cotton filter to an Erlenmeyer flask containing 200 mL of methanol solution, placed with vigorous stirring for 12 h, filtered, rinsed with methanol solution, and then dried in a vacuum oven. Drying to constant weight at 40 ° C gave a product narrowly distributed polyalkyn ester compound P1c/2a/CO 2 .
  • Narrow distribution polyalkynyl ester compound P1c/2a/CO 2 characterization data yellow solid, yield 83%.
  • the results of gel permeation chromatography (GPC) showed a weight average molecular weight (M w ) of 12 100 and a molecular weight distribution (PDI) of 1.70.
  • the nuclear magnetic resonance spectrum comparison chart (* represents the solvent peak) of the narrow-distributed polyalkynyl ester compound obtained in this example and its corresponding monomer is shown in Fig. 7, and the infrared absorption spectrum is shown in Fig. 8.
  • thermogravimetric curve of the narrowly distributed polyalkyn ester compound prepared in Example 4 is shown in FIG. As can be seen from Fig. 13, the narrow-distributed polyalkyn ester compound has good thermal stability.
  • a narrow distribution polyalkyn ester compound P1d/2a/CO 2 of the present embodiment has the following structural formula:
  • the above narrowly distributed polyalkynyl ester compound is prepared by polymerization of a bifunctional acetylenic monomer, carbon dioxide and a dihalogen monomer, and the reaction equation is as follows:
  • the synthesis method of the monomer M1d can be in accordance with the applicant's published literature (Chan, CYK et al. Construction of Functional Macromolecules with Well-Defined Structures by Indium-Catalyzed Three-Component Polycoupling of Alkynes, Aldehydes, and Amines. Macromolecules Synthetic method synthesis of 46, 3246–3256 (2013).
  • M1d (92.5 mg, 0.2 mmol), M2a (43.2 mg, 0.2 mmol), Ag 2 WO 4 (9.3 mg, 0.02 mmol), Cs 2 CO 3 (390.0 mg, 1.2 mmol) was added to a dry Schlenk tube. ), evacuate for 0.5 hour, pour a balloon filled with carbon dioxide, add 1 mL of N,N-dimethylacetamide (DMAc), react at 80 ° C for 12 hours, then cool to room temperature, then take 4 mL of the solution after the reaction.
  • DMAc N,N-dimethylacetamide
  • the tetrahydrofuran was diluted and then added dropwise via a cotton filter to an Erlenmeyer flask containing 200 mL of methanol solution, placed with vigorous stirring for 12 h, filtered, rinsed with methanol solution, and then dried in a vacuum oven. Drying to constant weight at 40 ° C gave a product narrowly distributed polyalkyn ester compound P1d/2a/CO 2 .
  • a comparative NMR spectrum of the narrow-distributed polyalkynyl ester compound obtained in the present example and its corresponding monomer (* represents a solvent peak) is shown in Fig. 9, and an infrared absorption spectrum is shown in Fig. 10.
  • the graph of the thermogravimetric curve of the narrow-distributed polyalkyn ester compound prepared in Example 5 is shown in FIG. As can be seen from Fig. 13, the narrow-distributed polyalkyn ester compound has good thermal stability. The polymer exhibited typical aggregation-induced luminescence by the test solution and the absolute quantum yield in the solid state.
  • a narrow distribution polyalkyn ester compound P1e/2a/CO 2 of this embodiment has the following structural formula:
  • the above narrowly distributed polyalkynyl ester compound is prepared by polymerization of a bifunctional acetylenic monomer, carbon dioxide and a dihalogen monomer, and the reaction equation is as follows:
  • the synthesis method of the monomer M1e can be carried out according to the applicant's published literature (Li, W. et al. Catalyst-Free, Atom-Economic, Multicomponent Polymerizations of Aromatic Diynes, Elemental Sulfur, and Aliphatic Diamines toward Luminescent Polythioamides. Macromolecules). 48,7747–7754 (2015).) Synthesis of synthetic methods.
  • M1e (63.7 mg, 0.2 mmol), M2a (43.2 mg, 0.2 mmol), Ag 2 WO 4 (9.3 mg, 0.02 mmol), Cs 2 CO 3 (390.0 mg, 1.2 mmol) was added to a dry Schlenk tube. ), evacuate for 0.5 hour, pour a balloon filled with carbon dioxide, add 1 mL of N,N-dimethylacetamide (DMAc), react at 80 ° C for 12 hours, then cool to room temperature, then take 4 mL of the solution after the reaction.
  • DMAc N,N-dimethylacetamide
  • the tetrahydrofuran was diluted and then added dropwise via a cotton filter to an Erlenmeyer flask containing 200 mL of methanol solution, placed with vigorous stirring for 12 h, filtered, rinsed with methanol solution, and then dried in a vacuum oven. Drying to constant weight at 40 ° C gave a product narrowly distributed polyalkynyl ester compound P1e/2a/CO 2 .
  • Narrow distribution polyalkynyl ester compound P1e/2a/CO 2 Characterization data light gray solid, yield 78%.
  • Gel permeation chromatography (GPC) showed a weight average molecular weight (M w ) of 20 600 and a molecular weight distribution (PDI) of 2.00.
  • a comparative NMR spectrum of the narrow-distributed polyalkynyl ester compound obtained in the present example and its corresponding monomer (* represents a solvent peak) is shown in Fig. 11, and an infrared absorption spectrum is shown in Fig. 12.
  • thermogravimetric curve of the narrow-distributed polyalkyn ester compound prepared in Example 6 is shown in Fig. 13. As can be seen from Fig. 13, the narrow-distributed polyalkyn ester compound has good thermal stability.

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Abstract

一种窄分布聚炔酯类化合物及其制备方法。所述窄分布聚炔酯类化合物具有式（1）所示的结构通式。所述制备方法为：在常压二氧化碳环境下，双官能团炔类单体，二氧化碳和二卤代物单体在有机溶剂中通过催化剂和碱共同作用进行聚合反应，将产物溶解在有机溶剂中，然后加入到沉淀剂中进行沉淀，收集沉淀物，干燥至恒重，得到窄分布聚炔酯类化合物。所述聚炔酯类化合物的制备方法在常压二氧化碳环境下进行，并且二氧化碳作为一种单体参与聚合物的形成；所得窄分布聚炔酯类化合物具有较好的热稳定性和优异的可加工性，由于聚集诱导发光基团的引入，部分聚合物表现出典型的聚集诱导发光性能。

Description

[根据细则37.2由ISA制定的发明名称]　窄分布聚炔酯类化合物及其制备方法 技术领域
本发明属于有机合成技术领域，具体涉及一种窄分布聚炔酯类化合物及其制备方法。
背景技术
二氧化碳如今已经引起了全世界的广泛关注，因为大气中持续增长的二氧化碳已经造成了很多气候问题。现如今有两种方法降低大气中的二氧化碳浓度，一种是通过物理方法储存它，另外一种则是通过化学方法对其进行转化。众所周知的是二氧化碳是一种丰富，廉价，无毒并且可再生的C1单体，所以将二氧化碳转化为一些有用的材料是一种更加被提倡的做法。然而，由于二氧化碳较低的反应活性使其在化学合成领域的应用受到了很大的限制。目前只有很少的高效利用二氧化碳的聚合反应，其中最著名，也是被全世界最广泛研究的一个就是二氧化碳和环氧类化合物的共聚合，虽然其反应活性很高，但也有很多不可避免的缺点，例如苛刻的反应条件，复杂的催化剂以及单体设计的不灵活性从而不能实现聚合物多种多样的性质。其他例如二氧化碳和二元醇共聚，二氧化碳，二元醇以及二卤化物共聚等等都没有很高的反应活性。
发展基于炔烃的新聚合反应对于高分子材料科学来说是非常重要的。炔烃是易得或易合成的化学原料之一，利用炔烃构建功能性高分子具有重要的学术意义和技术意义，已经吸引了科学家们的广泛关注。然而炔烃和二氧化碳的共聚报道还很少。
发明内容
为了解决以上现有技术的缺点和不足之处，本发明的首要目的在于提供一种窄分布聚炔酯类化合物及其制备方法。该制备方法可以在常压二氧化碳环境下进行，并且二氧化碳作为一种单体参与聚合物的形成，反应绿色、高效、容易操作。
本发明的另一目的在于提供一种通过上述方法制备得到的窄分布聚炔酯类化合物。
本发明目的通过以下技术方案实现：
一种窄分布聚炔酯类化合物的制备方法，包括如下步骤：
(1)在常压二氧化碳环境下，双官能团炔类单体、二氧化碳以及二卤代物单体在有机溶剂中通过催化剂和碱的共同作用进行聚合反应；
(2)反应完毕后，将产物加入到沉淀剂中进行沉淀，收集沉淀物，干燥至恒重，得到窄分布聚炔酯类化合物；
所述双官能团炔类单体的结构通式为式(Ⅱ)，如下：
Figure PCTCN2017076697-appb-000001
所述的二卤代物单体的结构通式为式(III)，如下：
X-R2-X X＝Cl，Br，I(III)；其中R1，R2为有机基团。
优选的，R1为以下1～26中的任意一种有机基团；R2为以下27～29中任意一种有机基团；
Figure PCTCN2017076697-appb-000002
其中，m、h、k为1～20的整数；X选自N、P、O、S或Si元素；*表示取代位置。
步骤(1)中所述有机溶剂选自四氢呋喃、二氯甲烷、氯仿、甲苯、1,4-二氧六环、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙腈、乙醇、N-甲基吡咯烷酮、碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯中的至少一种。从溶剂的对聚合反应的影响程度考虑，进一步优选，所述的有机溶剂选自N,N-二甲基乙酰胺，此时，得到的窄分布聚炔酯类化合物溶解度较好，产率和分子量也较高，便于下一步应用。
反应单体的浓度会对反应的产率产生影响，作为优选，步骤(1)所述聚合反应中双官能团炔类单体和二卤代物单体在有机溶剂中的物质的量浓度为0.05～5mol/L，进一步优选，所述双官能团炔类单体在有机溶剂中的物质的量浓度为0.20mol/L，所述双官能团炔类单体和二卤代物单体的摩尔比为1:1。
反应催化剂的种类和用量会对反应的时间和产物的产率和分子量产生影响，作为优选，步骤(1)所述催化剂为钨酸银、碘化银、硝酸银、四氟硼酸银、氯化银、溴化银、氧化银、醋酸银、氯化亚铜、溴化亚铜、碘化亚铜、氰化亚铜、氧化亚铜中的至少一种，所述催化剂的用量为双官能团炔类单体的1mol％～40mol％；进一步优选，所述催化剂为钨酸银，所述催化剂的用量为双官能团炔类单体的10mol％。
反应碱的种类和用量会对反应的时间和产物的产率和分子量产生影响，作为优选，步骤(1)所述碱为碳酸铯、碳酸钾、氢氧化钾、氢氧化钠、氟化铯、氟化钾、叔丁醇钾、叔丁醇钠、叔丁醇锂、1,5,7-三氮杂二环[4.4.0]癸-5-烯、醋酸铯中的至少一种。所述碱的用量为双官能团炔类单体的100mol％～1000mol％；进一步优选，所述碱为碳酸铯，所述碱的用量为双官能团炔类单体的300mol％～600mol％。
作为优选，步骤(1)所述聚合反应的温度为0～200℃，时间为0.25～72小时。考虑到聚合反应的产率和聚合所得产物的分子量及其分布，同时从节省能源和高速高效的角度出发，将所述的聚合反应的温度进一步优选为80℃，时间优选为12小时。
步骤(2)中所述沉淀剂为甲醇或正己烷。
一种窄分布聚炔酯类化合物，所述窄分布聚炔酯类化合物具有式(I)所示的结构通式：
Figure PCTCN2017076697-appb-000003
式中，n为0～200的整数且n不为0，R1，R2为有机基团。
优选地，所述R1为以下1～26中的任意一种有机基团；R2为以下27～29中任意一种有机基团；
Figure PCTCN2017076697-appb-000004
其中，m、h、k为1～20的整数；X选自N、P、O、S或Si元素；*表示取代位置。
所述窄分布聚炔酯类化合物通过上述方法制备得到，分子量分布系数(PDI)为1.00～2.00。
本发明的制备方法及所得到的产物具有如下优点及有益效果：
(1)本发明的制备方法可以在常压二氧化碳环境下进行，并且二氧化碳作为一种单体参与聚合物的形成；
(2)本发明的制备方法操作简单，反应原料和催化剂易得，可直接购买或通过简单的反应制备；聚合反应条件温和，节约能源；聚合反应其中一个单体为二氧化碳，成本低，绿色环保；
(3)本发明的制备方法具有良好的官能团耐受性，可以引入多种功能性基团；制得的功能化窄分布聚炔酯类化合物具有窄的分子量分布，较好的热稳定性，优异的可加工性以及非凡的降解性能，由于聚集诱导发光基团的引入，部分聚合物表现出典型的聚集诱导发光性能。
附图说明
图1为本发明实施例1制备的窄分布聚炔酯类化合物(D)与其单体1a(A)、2a(B)和模型化合物(C)在CD2Cl2中核磁共振氢谱对比图以及窄分布聚炔酯类化合物(H)与其单体1a(E)、2a(F)和模型化合物(G)在CD2Cl2中核磁共振碳谱对比图(*代表溶剂峰)；
图2为本发明实施例1制备的窄分布聚炔酯类化合物(C)与其单体1a(A)和模型化合物(B)的红外吸收光谱对比图；
图3为本发明实施例2制备的窄分布聚炔酯类化合物(D)与其单体1a(A)、2b(B)和模型化合物(C)在CD2Cl2中核磁共振氢谱对比图以及窄分布聚炔酯类化合物(H)与其单体1a(E)、2b(F)和模型化合物(G)在CD2Cl2中核磁共振碳谱对比图(*代表溶剂峰)；
图4为本发明实施例2制备的窄分布聚炔酯类化合物(C)与其单体1a(A)和模型化合物(B)的红外吸收光谱对比图；
图5为本发明实施例3制备的窄分布聚炔酯类化合物(D)与其单体1a(A)、2c(B)和模型化合物(C)在CD2Cl2中核磁共振氢谱对比图以及窄分布聚炔酯类化合物(H)与其单体1a(E)、2c(F)和模型化合物(G)在CD2Cl2中核磁 共振碳谱对比图(*代表溶剂峰)；
图6为本发明实施例3制备的窄分布聚炔酯类化合物(C)与其单体1a(A)和模型化合物(B)的红外吸收光谱对比图；
图7为本发明实施例4制备的窄分布聚炔酯类化合物(C)与其单体1c(A)、2a(B)在CD2Cl2中核磁共振氢谱对比图以及窄分布聚炔酯类化合物(F)与其单体1c(D)、2a(E)在CD2Cl2中核磁共振碳谱对比图(*代表溶剂峰)；
图8为本发明实施例4制备的窄分布聚炔酯类化合物(B)与其单体1c(A)的红外吸收光谱对比图；
图9为本发明实施例5制备的窄分布聚炔酯类化合物(C)与其单体1d(A)、2a(B)在CD2Cl2中核磁共振氢谱对比图以及窄分布聚炔酯类化合物(F)与其单体1d(D)、2a(E)在CD2Cl2中核磁共振碳谱对比图(*代表溶剂峰)；
图10为本发明实施例5制备的窄分布聚炔酯类化合物(B)与其单体1d(A)的红外吸收光谱对比图；
图11为本发明实施例6制备的窄分布聚炔酯类化合物(C)与其单体1e(A)、2a(B)在CD2Cl2中核磁共振氢谱对比图以及窄分布聚炔酯类化合物(F)与其单体1e(D)、2a(E)在CD2Cl2中核磁共振碳谱对比图(*代表溶剂峰)；
图12为本发明实施例6制备的窄分布聚炔酯类化合物(B)与其单体1e(A)的红外吸收光谱对比图；
图13为本发明实施例1～6制备的窄分布聚炔酯类化合物的热失重曲线图；
图14为本发明实施例1制备的窄分布聚炔酯类化合物在NaOH的水和四氢呋喃混合溶液中重均分子量随水解时间的变化图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
本实施例的一种窄分布聚炔酯类化合物P1a/2a/CO2，其结构式如下：
Figure PCTCN2017076697-appb-000005
Figure PCTCN2017076697-appb-000006
上述窄分布聚炔酯类化合物通过双官能团炔类单体，二氧化碳以及二卤代物单体聚合反应进行制备，反应方程式如下：
Figure PCTCN2017076697-appb-000007
其中，单体M1a的合成方法可按照申请人在已公开文献中(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).)的合成方法合成。
本实施例所述的窄分布聚炔酯类化合物的具体制备步骤如下：
在一个干燥的施伦克管中加入M1a(76.1mg,0.2mmol)，M2a(43.2mg，0.2mmol),Ag2WO4(9.3mg,0.02mmol),Cs2CO3(390.0mg,1.2mmol)，抽真空0.5小时，扎入一个充满二氧化碳的气球，加N,N-二甲基乙酰胺(DMAc)1mL，在80℃反应12小时，然后冷却至室温，反应完之后的溶液先拿4mL的四氢呋喃进行稀释，然后通过一个棉花过滤装置，逐滴滴加到装有200mL甲醇溶液的锥形瓶中，并伴随有强烈的搅拌，放置12h沉淀，过滤，用甲醇溶液冲洗，然后在真空干燥箱40℃干燥到重量不会再发生变化，得到产物窄分布聚炔酯类化合物P1a/2a/CO2。
窄分布聚炔酯类化合物P1a/2a/CO2表征数据：黄色固体，产率88％。凝胶渗透色谱(GPC)结果显示：重均分子量(Mw)为13 600，分子量分布(PDI)为1.37。
为了表征窄分布聚炔酯类化合物结构，我们做了模型反应，拿到了模型化合物3，反应方程式如下：
Figure PCTCN2017076697-appb-000008
本实施例所得窄分布聚炔酯类化合物与其相应单体以及模型化合物的核磁共振谱对比图(*代表溶剂峰)见图1，红外吸收光谱图见图2。
从图1的核磁共振氢谱可以看出，单体M1a(即单体1a)中炔氢在化学位移3.09处的共振吸收峰在模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2a/CO2)中已经完全消失，而在模型化合物3(模型化合物)和窄分布聚炔酯类化合物(聚合物P1a/2a/CO2)的氢谱图中，在化学位移4.23处新出现了代表着靠近酯基的亚甲基氢的共振吸收峰。
在图1的模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2a/CO2)核磁共振碳谱可以看出，代表着酯基碳的共振吸收峰出现在化学位移154.17处，代表靠近酯基的亚甲基碳的共振吸收峰出现在化学位移65.77处。
从图2中可以看出，M1a(即单体1a)中≡C-H在3293cm-1的伸缩振动吸收峰在模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2a/CO2)的红外吸收谱图中已经完全消失，而在模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2a/CO2)的红外吸收谱图中，在1712cm-1处新出现了一个代表着C＝O伸缩振动的强吸收峰。
以上数据都证明我们拿到了目标聚合物。该窄分布聚炔酯类化合物在室温下易溶于二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺等常见有机溶剂，表明具有优异的可加工性。
实施例1制备的窄分布聚炔酯类化合物的热失重曲线图如图13所示，测试条件：氮气气氛下，升温速率为20℃/min；实施例1制备的窄分布聚炔酯类化合物在NaOH的水和四氢呋喃混合溶液中重均分子量随水解时间的变化图如图14所示。
从图13可以看出，该窄分布聚炔酯类化合物有良好的热稳定性。通过测试溶液以及固态下的绝对量子产率，该聚合物表现出典型的聚集诱导发光现象。而从图14中可以看出，该窄分布聚炔酯类化合物在NaOH的水和四氢呋喃混合 溶液中，具有很快的降解速率，快于一般的线性聚酯，在药物释放等领域具有潜在的应用价值。
实施例2
本实施例的一种窄分布聚炔酯类化合物P1a/2b/CO2，其结构式如下：
Figure PCTCN2017076697-appb-000009
上述窄分布聚炔酯类化合物通过双官能团炔类单体，二氧化碳以及二卤代物单体聚合反应进行制备，反应方程式如下：
Figure PCTCN2017076697-appb-000010
其中，单体M1a的合成方法可按照申请人在已公开文献中(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).)的合成方法合成。
本实施例所述的窄分布聚炔酯类化合物的具体制备步骤如下：
在一个干燥的施伦克管中加入M1a(76.1mg,0.2mmol)，M2b(48.8mg，0.2mmol),Ag2WO4(9.3mg,0.02mmol),Cs2CO3(390.0mg,1.2mmol)，抽真空0.5小时，扎入一个充满二氧化碳的气球，加N,N-二甲基乙酰胺(DMAc)1mL，在80℃反应12小时，然后冷却至室温，反应完之后的溶液先拿4mL的四氢呋喃进行稀释，然后通过一个棉花过滤装置，逐滴滴加到装有200mL甲醇溶液的锥形瓶中，并伴随有强烈的搅拌，放置12h，过滤，用甲醇溶液冲洗，然后在真 空干燥箱40℃干燥至恒重，得到产物窄分布聚炔酯类化合物P1a/2b/CO2。
窄分布聚炔酯类化合物P1a/2b/CO2表征数据：黄色固体，产率90％。凝胶渗透色谱(GPC)结果显示：重均分子量(Mw)为20 500，分子量分布(PDI)为1.69。
为了表征窄分布聚炔酯类化合物结构，我们做了模型反应，拿到了模型化合物3，反应方程式如实施例1中的(二)所示。
本实施例所得窄分布聚炔酯类化合物与其相应单体以及模型化合物的核磁共振谱对比图(*代表溶剂峰)见图3，红外吸收光谱图见图4。
从图3核磁共振氢谱可以看出，单体M1a(即单体1a)中炔氢在化学位移3.09处的共振吸收峰在模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2b/CO2)中已经完全消失，而在模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2b/CO2)的氢谱图中，在化学位移4.18处出现了代表着靠近酯基的亚甲基氢的共振吸收峰。
在图3的模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2b/CO2)核磁共振碳谱可以看出，代表着酯基碳的共振吸收峰出现在化学位移154.27处，代表靠近酯基的亚甲基碳的共振吸收峰出现在化学位移66.35处。
从图4中可以看出，M1a(即单体1a)中≡C-H在3293cm-1的伸缩振动吸收峰在模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2b/CO2)的红外吸收谱图中已经完全消失，而在模型化合物3(模型化合物)以及窄分布聚炔酯类化合物(聚合物P1a/2b/CO2)的红外吸收谱图中，在1709cm-1处出现了一个代表着C＝O伸缩振动的强吸收峰。以上数据都证明我们拿到了目标聚合物。该窄分布聚炔酯类化合物在室温下易溶于二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺等常见有机溶剂，表明具有优异的可加工性。
实施例2制备的窄分布聚炔酯类化合物的热失重曲线图如图13所示。
从图13可以看出，该窄分布聚炔酯类化合物有良好的热稳定性。通过测试溶液以及固态下的绝对量子产率，该聚合物表现出典型的聚集诱导发光现象。
实施例3
本实施例的一种窄分布聚炔酯类化合物P1a/2c/CO2，其结构式如下：
Figure PCTCN2017076697-appb-000011
上述窄分布聚炔酯类化合物通过双官能团炔类单体，二氧化碳以及二卤代物单体聚合反应进行制备，反应方程式如下：
Figure PCTCN2017076697-appb-000012
其中，单体M1a的合成方法可按照申请人在已公开文献中(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).)的合成方法合成。
本实施例所述的窄分布聚炔酯类化合物的具体制备步骤如下：
在一个干燥的施伦克管中加入M1a(76.1mg,0.2mmol)，M2c(54.4mg，0.2mmol),Ag2WO4(9.3mg,0.02mmol),Cs2CO3(390.0mg,1.2mmol)，抽真空0.5小时，扎入一个充满二氧化碳的气球，加N,N-二甲基乙酰胺(DMAc)1mL，在80℃反应12小时，然后冷却至室温，反应完之后的溶液先拿4mL的四氢呋喃进行稀释，然后通过一个棉花过滤装置，逐滴滴加到装有200mL甲醇溶液的锥形瓶中，并伴随有强烈的搅拌，放置12h，过滤，用甲醇溶液冲洗，然后在真空干燥箱40℃干燥至恒重，得到产物窄分布聚炔酯类化合物P1a/2c/CO2。
窄分布聚炔酯类化合物P1a/2c/CO2表征数据：黄色固体，产率95％。凝胶渗透色谱(GPC)结果显示：重均分子量(Mw)为31 400，分子量分布(PDI) 为1.86。
为了表征窄分布聚炔酯类化合物结构，我们做了模型反应，拿到了模型化合物3(即模型化合物)，反应方程式如实施例1中的(二)所示。
本实施例所得窄分布聚炔酯类化合物与其相应单体以及模型化合物的核磁共振谱对比图(*代表溶剂峰)见图5，红外吸收光谱图见图6。
从图5的模型化合物3(即模型化合物)以及窄分布聚炔酯类化合物(P1a/2c/CO2)核磁共振氢谱可以看出，单体M1a(即单体1a)中炔氢在化学位移3.09处的共振吸收峰在模型化合物3(即模型化合物)以及窄分布聚炔酯类化合物(P1a/2c/CO2)中已经完全消失，而在模型化合物3以及窄分布聚炔酯类化合物(P1a/2c/CO2)的氢谱图中，在化学位移4.17处出现了代表着靠近酯基的亚甲基氢的共振吸收峰。
在图5的模型化合物3(即模型化合物)以及窄分布聚炔酯类化合物(P1a/2c/CO2)核磁共振碳谱可以看出，代表着酯基碳的共振吸收峰出现在化学位移154.28处，代表靠近酯基的亚甲基碳的共振吸收峰出现在化学位移66.53处。
从图6中可以看出，M1a(即单体1a)中≡C-H在3293cm-1的伸缩振动吸收峰在模型化合物3以及窄分布聚炔酯类化合物(P1a/2c/CO2)的红外吸收谱图中已经完全消失，而在模型化合物3以及窄分布聚炔酯类化合物(P1a/2c/CO2)的红外吸收谱图中，在1709cm-1处出现了一个代表着C＝O伸缩振动的强吸收峰。以上数据都证明我们拿到了目标聚合物。该窄分布聚炔酯类化合物在室温下易溶于二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺等常见有机溶剂，表明具有优异的可加工性。
实施例3制备的窄分布聚炔酯类化合物的热失重曲线图如图13所示。从图13可以看出，该窄分布聚炔酯类化合物有良好的热稳定性。通过测试溶液以及固态下的绝对量子产率，该聚合物表现出典型的聚集诱导发光现象。
实施例4
本实施例的一种窄分布聚炔酯类化合物P1c/2a/CO2，其结构式如下：
Figure PCTCN2017076697-appb-000013
Figure PCTCN2017076697-appb-000014
上述窄分布聚炔酯类化合物通过双官能团炔类单体，二氧化碳以及二卤代物单体聚合反应进行制备，反应方程式如下：
Figure PCTCN2017076697-appb-000015
其中，单体M1c的合成方法可按照申请人在已公开文献中(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).)的合成方法合成。
本实施例所述的窄分布聚炔酯类化合物的具体制备步骤如下：
在一个干燥的施伦克管中加入M1c(58.7mg,0.2mmol)，M2a(43.2mg，0.2mmol),Ag2WO4(9.3mg,0.02mmol),Cs2CO3(390.0mg,1.2mmol)，抽真空0.5小时，扎入一个充满二氧化碳的气球，加N,N-二甲基乙酰胺(DMAc)1mL，在80℃反应12小时，然后冷却至室温，反应完之后的溶液先拿4mL的四氢呋喃进行稀释，然后通过一个棉花过滤装置，逐滴滴加到装有200mL甲醇溶液的锥形瓶中，并伴随有强烈的搅拌，放置12h，过滤，用甲醇溶液冲洗，然后在真空干燥箱40℃干燥至恒重，得到产物窄分布聚炔酯类化合物P1c/2a/CO2。
窄分布聚炔酯类化合物P1c/2a/CO2表征数据：黄色固体，产率83％。凝胶渗透色谱(GPC)结果显示：重均分子量(Mw)为12 100，分子量分布(PDI)为1.70。
本实施例所得窄分布聚炔酯类化合物与其相应单体的核磁共振谱对比图(*代表溶剂峰)见图7，红外吸收光谱图见图8。
从图7核磁共振氢谱可以看出，单体M1c(即单体1c)中炔氢在化学位移3.09处的共振吸收峰在窄分布聚炔酯类化合物(P1c/2a/CO2)中已经完全消失，而在窄分布聚炔酯类化合物(P1c/2a/CO2)的氢谱图中，在化学位移4.25处出现了代表着靠近酯基的亚甲基氢的共振吸收峰；在图7的窄分布聚炔酯类化合 物(P1c/2a/CO2)核磁共振碳谱可以看出，代表着酯基碳的共振吸收峰出现在化学位移154.38处，代表靠近酯基的亚甲基碳的共振吸收峰出现在化学位移65.71处。
从图8中可以看出，M1c(即单体1c)中≡C-H在3290cm-1的伸缩振动吸收峰在窄分布聚炔酯类化合物(P1c/2a/CO2)的红外吸收谱图中已经完全消失，而在窄分布聚炔酯类化合物(P1c/2a/CO2)的红外吸收谱图中，在1708cm-1处出现了一个代表着C＝O伸缩振动的强吸收峰。以上数据都证明我们拿到了目标聚合物。该窄分布聚炔酯类化合物在室温下易溶于二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺等常见有机溶剂，表明具有优异的可加工性。
实施例4制备的窄分布聚炔酯类化合物的热失重曲线图如图13所示。从图13可以看出，该窄分布聚炔酯类化合物有良好的热稳定性。
实施例5
本实施例的一种窄分布聚炔酯类化合物P1d/2a/CO2，其结构式如下：
Figure PCTCN2017076697-appb-000016
上述窄分布聚炔酯类化合物通过双官能团炔类单体，二氧化碳以及二卤代物单体聚合反应进行制备，反应方程式如下：
Figure PCTCN2017076697-appb-000017
其中，单体M1d的合成方法可按照申请人在已公开文献中(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).)的合成方法合成。
本实施例所述的窄分布聚炔酯类化合物的具体制备步骤如下：
在一个干燥的施伦克管中加入M1d(92.5mg,0.2mmol)，M2a(43.2mg，0.2mmol),Ag2WO4(9.3mg,0.02mmol),Cs2CO3(390.0mg,1.2mmol)，抽真空0.5小时，扎入一个充满二氧化碳的气球，加N,N-二甲基乙酰胺(DMAc)1mL，在80℃反应12小时，然后冷却至室温，反应完之后的溶液先拿4mL的四氢呋喃进行稀释，然后通过一个棉花过滤装置，逐滴滴加到装有200mL甲醇溶液的锥形瓶中，并伴随有强烈的搅拌，放置12h，过滤，用甲醇溶液冲洗，然后在真空干燥箱40℃干燥至恒重，得到产物窄分布聚炔酯类化合物P1d/2a/CO2。
窄分布聚炔酯类化合物P1d/2a/CO2表征数据：黄色固体，产率85％。凝胶渗透色谱(GPC)结果显示：重均分子量(Mw)为13 200，分子量分布(PDI)为1.61。
为本实施例所得窄分布聚炔酯类化合物与其相应单体的核磁共振谱对比图(*代表溶剂峰)见图9，红外吸收光谱图见图10。
从图9的核磁共振氢谱可以看出，单体M1d(即单体1d)中炔氢在化学位移3.08处的共振吸收峰在窄分布聚炔酯类化合物P1d/2a/CO2中已经完全消失，而在窄分布聚炔酯类化合物P1d/2a/CO2的氢谱图中，在化学位移4.23处出现了代表着靠近酯基的亚甲基氢的共振吸收峰。
在图9的窄分布聚炔酯类化合物P1d/2a/CO2核磁共振碳谱可以看出，代表着酯基碳的共振吸收峰出现在化学位移154.28处，代表靠近酯基的亚甲基碳的共振吸收峰出现在化学位移65.73处。
从图10中可以看出，M1d(即单体1d)中≡C-H在3287cm-1的伸缩振动吸收峰在窄分布聚炔酯类化合物P1d/2a/CO2的红外吸收谱图中已经完全消失，而在窄分布聚炔酯类化合物P1d/2a/CO2的红外吸收谱图中，在1708cm-1处出现了一个代表着C＝O伸缩振动的强吸收峰。以上数据都证明我们拿到了目标聚合物。该窄分布聚炔酯类化合物在室温下易溶于二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺等常见有机溶剂，表明具有优异的可加工性。
实施例5制备的窄分布聚炔酯类化合物的热失重曲线图如图13所示。从图13可以看出，该窄分布聚炔酯类化合物有良好的热稳定性。通过测试溶液以及固态下的绝对量子产率，该聚合物表现出典型的聚集诱导发光现象。
实施例6
本实施例的一种窄分布聚炔酯类化合物P1e/2a/CO2，其结构式如下：
Figure PCTCN2017076697-appb-000018
上述窄分布聚炔酯类化合物通过双官能团炔类单体，二氧化碳以及二卤代物单体聚合反应进行制备，反应方程式如下：
Figure PCTCN2017076697-appb-000019
其中，单体M1e的合成方法可按照申请人在已公开文献中(Li,W.et al.Catalyst-Free,Atom-Economic,Multicomponent Polymerizations of Aromatic Diynes,Elemental Sulfur,and Aliphatic Diamines toward Luminescent Polythioamides.Macromolecules 48,7747–7754(2015).)的合成方法合成。
本实施例所述的窄分布聚炔酯类化合物的具体制备步骤如下：
在一个干燥的施伦克管中加入M1e(63.7mg,0.2mmol)，M2a(43.2mg，0.2mmol),Ag2WO4(9.3mg,0.02mmol),Cs2CO3(390.0mg,1.2mmol)，抽真空0.5小时，扎入一个充满二氧化碳的气球，加N,N-二甲基乙酰胺(DMAc)1mL，在80℃反应12小时，然后冷却至室温，反应完之后的溶液先拿4mL的四氢呋喃进行稀释，然后通过一个棉花过滤装置，逐滴滴加到装有200mL甲醇溶液的锥形瓶中，并伴随有强烈的搅拌，放置12h，过滤，用甲醇溶液冲洗，然后在真空干燥箱40℃干燥至恒重，得到产物窄分布聚炔酯类化合物P1e/2a/CO2。
窄分布聚炔酯类化合物P1e/2a/CO2表征数据：浅灰色固体，产率78％。凝 胶渗透色谱(GPC)结果显示：重均分子量(Mw)为20 600，分子量分布(PDI)为2.00。
为本实施例所得窄分布聚炔酯类化合物与其相应单体的核磁共振谱对比图(*代表溶剂峰)见图11，红外吸收光谱图见图12。
从图11核磁共振氢谱可以看出，单体M1e(即单体1e)中炔氢在化学位移3.03处的共振吸收峰在窄分布聚炔酯类化合物P1e/2a/CO2中已经完全消失，而在窄分布聚炔酯类化合物P1e/2a/CO2的氢谱图中，在化学位移4.24处出现了代表着靠近酯基的亚甲基氢的共振吸收峰；在图11的窄分布聚炔酯类化合物P1e/2a/CO2核磁共振碳谱可以看出，代表着酯基碳的共振吸收峰出现在化学位移154.48处，代表靠近酯基的亚甲基碳的共振吸收峰出现在化学位移65.64处。
从图12中可以看出，M1e(即单体1e)中≡C-H在3310cm-1的伸缩振动吸收峰在窄分布聚炔酯类化合物P1e/2a/CO2的红外吸收谱图中已经完全消失，而在窄分布聚炔酯类化合物P1e/2a/CO2的红外吸收谱图中，在1703cm-1处出现了一个代表着C＝O伸缩振动的强吸收峰。以上数据都证明我们拿到了目标聚合物。该窄分布聚炔酯类化合物在室温下易溶于二氯甲烷、氯仿、四氢呋喃、N,N-二甲基甲酰胺等常见有机溶剂，表明具有优异的可加工性。
实施例6制备的窄分布聚炔酯类化合物的热失重曲线图如图13所示。从图13可以看出，该窄分布聚炔酯类化合物有良好的热稳定性。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种窄分布聚炔酯类化合物，其特征在于：所述窄分布聚炔酯类化合物具有式(I)所示的结构通式；
    Figure PCTCN2017076697-appb-100001
    式中，n为0～200的整数且不为0，R1，R2为有机基团。
  2. 根据权利要求1所述窄分布聚炔酯类化合物，其特征在于：所述R1为以下1～26中的任意一种有机基团；R2为氢原子或以下27～29中任意一种有机基团；
    Figure PCTCN2017076697-appb-100002
    其中，m、h、k为1～20的整数；X选自N、P、O、S或Si元素；*表示取代位置。
  3. 根据权利要求1或2所述窄分布聚炔酯类化合物的制备方法，其特征在于包括如下步骤：
    (1)在常压二氧化碳环境下，双官能团炔类单体，二氧化碳和双卤代物单体在有机溶剂中通过催化剂和碱共同作用进行聚合反应；
    (2)反应完毕后，将产物加入到沉淀剂中进行沉淀，收集沉淀物，干燥至恒重，得到窄分布聚炔酯类化合物；
    所述的双官能团炔类单体的结构通式如式(Ⅱ)所示：
    Figure PCTCN2017076697-appb-100003
    所述的二卤代物单体的结构通式如式(III)所示：
    X-R2-X X＝Cl，Br，I     (III)，
    R1，R2为有机基团。
  4. 根据权利要求3所述窄分布聚炔酯类化合物的制备方法，其特征在于：所述R1为以下1～26中的任意一种有机基团；R2为氢原子或以下27～29中任意一种有机基团；
    Figure PCTCN2017076697-appb-100004
    Figure PCTCN2017076697-appb-100005
    其中，m、h、k为1～20的整数；X选自N、P、O、S或Si元素；*表示取代位置。
  5. 根据权利要求3所述窄分布聚炔酯类化合物的制备方法，其特征在于：
    步骤(1)中所述有机溶剂选自四氢呋喃、二氯甲烷、氯仿、甲苯、1,4-二氧六环、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙腈、乙醇、N-甲基吡咯烷酮、碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯中的至少一种；
    步骤(2)中所述沉淀剂为甲醇或正己烷。
  6. 根据权利要求3所述窄分布聚炔酯类化合物的制备方法，其特征在于：步骤(1)中所述催化剂为钨酸银、碘化银、硝酸银、四氟硼酸银、氯化银、溴化银、氧化银、醋酸银、氯化亚铜、溴化亚铜、碘化亚铜、氰化亚铜、氧化亚铜中的至少一种；
    步骤(1)中所述碱为碳酸铯、碳酸钾、氢氧化钾、氢氧化钠、氟化铯、氟化钾、叔丁醇钾、叔丁醇钠、叔丁醇锂、1,5,7-三氮杂二环[4.4.0]癸-5-烯、醋酸铯中的至少一种。
  7. 根据权利要求3所述窄分布聚炔酯类化合物的制备方法，其特征在于：
    步骤(1)所述聚合反应中双官能团炔类单体和二卤代物单体在有机溶剂中的物质的量浓度都为0.05～5mol/L。
  8. 根据权利要求3所述窄分布聚炔酯类化合物的制备方法，其特征在于：
    所述催化剂的用量为双官能团炔类单体摩尔用量的1％～40％；所述碱的用量为双官能团炔类单体摩尔用量的100％～1000％。
  9. 根据权利要求3所述窄分布聚炔酯类化合物的制备方法，其特征在于：所述聚合反应的温度为0～200℃，时间为0.25～72小时。
  10. 根据权利要求3所述窄分布聚炔酯类化合物的制备方法，其特征在于：所述窄分布聚炔酯类化合物的分子量分布系数为1.00～2.00。
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CN113683767B (zh) * 2021-07-23 2022-10-25 华南理工大学 一种聚烯醚类化合物及其制备方法与应用
CN116874796A (zh) * 2023-06-19 2023-10-13 华南理工大学 一类聚炔硒醚类聚合物及其制备方法和应用
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