CN109705344B - Method for preparing 1, 5-stereoregular polytriazole by catalysis of nickel complex - Google Patents
Method for preparing 1, 5-stereoregular polytriazole by catalysis of nickel complex Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer chemistry, and discloses a method for preparing 1, 5-stereoregular polytriazole by catalysis of a nickel complex. The method comprises the following steps: in the presence of alkaline environment and organic phosphine ligand, binary alkynyl compound and binary azido compoundClick polymerization is carried out in an organic solvent under the catalytic action of a nickel complex, and subsequent treatment is carried out to obtain the 1, 5-stereoregular polytriazole, wherein the structure of the polytriazole is shown in a formula (I). The method has the advantages of mild conditions, high reaction efficiency, good atom economy and very high regioselectivity. The polytriazole prepared by the method is 1, 5-stereoregular polytriazole, and has the advantages of high regioregularity, high yield, excellent processability and very good thermal stability.
Description
Technical Field
The invention relates to the field of polymer chemistry and material science, in particular to a method for preparing 1, 5-stereoregular polytriazole by using nickel complex-catalyzed azide-alkyne click polymerization.
Background
In the field of polymer science, the development of efficient and selective polymerization reactions is crucial for the preparation of functional polymers with defined structures and unique properties. The click polymerization has gained wide attention by virtue of the advantages of high reaction efficiency, mild conditions, good atom economy, good regioselectivity and the like, and is widely applied to the fields of biological materials, photoelectric materials, self-repairing materials and the like. However, the current research focus is mainly on copper (I) -catalyzed azide-alkyne click polymerization, and the research on other metal-catalyzed azide-alkyne click polymerization is very rare. In addition, considering that only 1, 4-stereoregular polytriazole can be prepared by catalyzing azide-alkyne click polymerization through copper (I), the development of new azide-alkyne click polymerization capable of providing 1, 5-stereoregular polytriazole can not only provide a new method for preparing polytriazole, but also enrich the types of click polymerization, and has important significance for further development and wider application of click polymerization.
For the preparation of 1, 5-stereoregular polytriazoles, a few reports have been made at present. In 2008, Tang Benzhou subject group disclosed a method for preparing 1, 5-stereoregular polytriazole by catalyzing azide-alkyne click polymerization through ruthenium complex (Hyperbr)(iii) achandpolysytriazoles: Click polymerization, regioisomeric structure, light emission, and fluoro emission patterning. macromolecules 2008,41, 3808-; in 2015, the group reported that organic base tetramethylammonium hydroxide catalyzed azido-alkyne click polymerization for the preparation of 1, 5-stereoregular polytriazoles (Synthesis of 1,5-regioregular polytriazoles by effect NMe)4OH-media-azide-alkyl polymerization. Polymer. chem.2015,6, 5545-5549). However, both methods have limitations, the former requiring reaction at 60 ℃ for heating, and the latter being applicable only to aromatic acetylene monomers and aromatic azide monomers. Therefore, it is very necessary to develop azide-alkyne click polymerization which has milder conditions, wider substrate range and can provide 1, 5-stereoregular polytriazole.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing 1, 5-stereoregular polytriazole by using a nickel complex as a catalyst, which is mild in condition, efficient in reaction and capable of synthesizing a high-molecular-weight polymer.
The purpose of the invention is realized by the following technical scheme:
a method for preparing 1, 5-stereoregular polytriazole by catalysis of a nickel complex comprises the following steps:
under the conditions of alkaline environment and the existence of organic phosphine ligand, carrying out click polymerization on a binary alkynyl compound and a binary azido compound in an organic solvent under the catalytic action of a nickel complex, and carrying out subsequent treatment to obtain 1, 5-stereoregular polytriazole;
the structure of the 1, 5-stereoregular polytriazole is shown as a formula (I):
the structural formula of the binary alkynyl compound is shown as a formula (II):
the structural formula of the binary azido compound is shown as a formula (III):
in the formulas (I) to (III), n is an integer of 2 to 200, R1、R2Are identical or different organic radicals.
R in the formulae (I) and (II)1Is any one of the following chemical structural formulas 1-17:
wherein m, k and h are positive integers of 1-20; x is selected from N, O, P, S or Si; indicates the substitution position.
R in the formulae (I) and (III)2Is any one of the following chemical structural formulas 1-18:
wherein m, k and h are positive integers of 1-20; x is selected from N, O, P, S or Si; indicates the substitution position.
The alkaline environment is provided by at least one of cesium carbonate, cesium pivalate, sodium hydroxide, sodium ascorbate, potassium phosphate, potassium hydroxide, sodium carbonate, sodium phosphate, potassium carbonate.
The nickel complex is at least one of nickelocene, bis (methylcyclopentadienyl) nickel and bis (tetramethylcyclopentadienyl) nickel; the organic phosphine ligand is 4, 5-bis (diphenylphosphino) -9, 9-dimethyl xanthene or bis (2-diphenylphosphinophenyl) ether.
The reaction temperature of the click polymerization is 15-35 ℃.
The reaction time of the click polymerization is 0.1-12 hours.
The molar ratio of the binary alkynyl compound to the binary azido compound is 1: (1-1.1), wherein the concentration of the binary alkynyl compound in the organic solvent is 0.05-1 mol/L;
the organic solvent is at least one of toluene, tetrahydrofuran, dichloromethane, chloroform, 1, 4-dioxane, dimethyl sulfoxide and N, N-dimethylformamide.
The dosage of the nickel complex is 5-30 mol% of the binary alkynyl compound (5-30% of the molar dosage of the binary alkynyl compound); the dosage of the organic phosphine ligand is 5mol percent to 30mol percent of the binary alkynyl compound (5 mol percent to 30mol percent of the binary alkynyl compound).
The click polymerization of the present invention can be carried out in an inert atmosphere as well as in air.
And the subsequent treatment is to dissolve the product in an organic solvent after the reaction is finished, then dropwise add the product into a precipitator for precipitation, collect the precipitate, and dry the precipitate to constant weight to obtain the 1, 5-stereoregular polytriazole.
The precipitant is methanol or n-hexane.
The organic solvent is at least one of toluene, tetrahydrofuran, dichloromethane, chloroform, 1, 4-dioxane, dimethyl sulfoxide and N, N-dimethylformamide.
The 1, 5-stereoregular polytriazole is prepared by the method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the method of the present invention can provide 1, 5-stereoregular polytriazole with high regioregularity.
2. The method has mild condition, simple process and high polymerization efficiency, such as: the reaction is carried out for 30 minutes at room temperature to obtain the polymer with high molecular weight.
3. The polymerization process of the invention has no byproduct and accords with atom economy.
4. The method has the advantages of easily available reaction raw materials, direct purchase or simple reaction preparation.
Drawings
FIG. 1 is CD of 1, 5-stereoregular polytriazole P1 prepared in example 1 and the corresponding monomer and model molecule2Cl2/DMSO-d6Comparison of nuclear magnetic resonance hydrogen spectra in (volume ratio 1: 2); c is 1,4-disubstituted triazoles (model molecules), D is 1, 5-disubstituted triazoles (model molecules), E is 1, 5-stereoregular polytriazoles P1;
FIG. 2 shows the CDCl of 1, 5-stereoregular polytriazole P1 prepared in example 1 and its corresponding monomers and model molecules3Nuclear magnetic resonance carbon spectrum contrast diagram; c is 1, 4-disubstituted triazole (model molecule), D is 1, 5-disubstituted triazole (model molecule), E is 1, 5-stereoregular polytriazole P1;
FIG. 3 is a graph showing the thermogravimetric curves of polytriazoles P1-P9 obtained in examples 1-9;
FIG. 4 shows the circular dichroism spectra (tetrahydrofuran solution, concentration: 10) of polytriazoles P5, P6, P8 and P9 and monomers M6 and M7 obtained in examples 5 to 6,8 and 9-5M)。
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Nickel complex catalysis M1 and M2 preparation of polytriazole P1:
wherein, the monomer M1 is synthesized according to the synthesis method disclosed in the published literature (Catalyst-free thiol-ene copolymerization: A power melt and surfactant tool for preparation of functional poly (vinyl sulfate) s. macromolecules 2014,47, 1325-1333); monomer M2 was synthesized according to a method disclosed in the literature (highly branched polyesters: Click polymerization, regioisomeric structure, light emission, and fluorescent patterning. macromolecules 2008,41, 3808-.
91.2mg (0.2mmol) of the monomer M1, 72mg (0.2mmol) of the monomer M2, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate were charged in a 10mL polymerization tube, and the mixture was evacuated and purged with nitrogen 3 times, and 0.5mL of ultra-dry N, N-dimethylformamide was injected by a syringe and reacted at room temperature for 30 minutes. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P1.
The final product, polytriazole P1, was determined to have a yield of 96.7%, a weight average molecular weight of 60100, and a molecular weight distribution of 1.69 (molecular weight and molecular weight distribution determined by an ultra efficient polymer chromatography system (APC) equipped with a diode array detector, THF as the mobile phase, a flow rate of 0.5mL/min, and single distribution linear Polystyrene (PS) as the standard for calibration).
FIG. 1 is CD of 1, 5-stereoregular polytriazole P1 prepared in example 1 and the corresponding monomer and model molecule2Cl2/DMSO-d6Comparison of nuclear magnetic resonance hydrogen spectra in (volume ratio 1: 2); c is 1, 4-disubstituted triazole (model molecule), D is 1, 5-disubstituted triazole (model molecule), E is 1, 5-stereoregular polytriazole P1; FIG. 2 shows the CDCl of 1, 5-stereoregular polytriazole P1 prepared in example 1 and its corresponding monomers and model molecules3Nuclear magnetic resonance carbon spectrum contrast diagram; c is 1, 4-disubstituted triazole (model molecule), D is 1, 5-disubstituted triazole (model molecule), and E is 1, 5-stereoregular polytriazole P1. The thermogravimetric plot of polytriazole P1 obtained in example 1 is shown in FIG. 3.
The nuclear magnetic resonance spectrum of polytriazole P1 and corresponding monomers and model molecules is shown in figures 1 and 2 (. beta. represents a solvent peak), as shown in figure 1, the nuclear magnetic resonance hydrogen spectrum of the polymer P1 has no alkyne hydrogen peak basically observed at a chemical shift of 3.98ppm, a very obvious characteristic peak corresponding to 1, 5-disubstituted triazolyl hydrogen appears at a chemical shift of 7.73ppm, and a very weak characteristic peak corresponding to 1, 4-disubstituted triazolyl hydrogen is observed at a chemical shift of 8.42 ppm; meanwhile, as shown in fig. 2, in the nuclear magnetic resonance carbon spectrum of the polymer P1, characteristic peaks corresponding to alkyne carbons were not observed at chemical shifts of 83.53ppm and 77.52ppm, while characteristic peaks corresponding to 1, 5-disubstituted triazolyl carbons were very clearly observed at chemical shifts of 138.84ppm and 133.25ppm, while characteristic peaks corresponding to 1, 4-disubstituted triazolyl carbons were not observed at chemical shifts of 147.88ppm and 119.60 ppm. These characterization results all show that the monomer has reacted completely and a 1, 5-stereoregular polytriazole product is obtained, and the 1, 5-stereoregularity of P1 can be calculated to be 95% by means of nuclear magnetic resonance hydrogen spectrum. The polytriazole can be dissolved in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide and the like at room temperature, and has excellent processability; as can be seen from FIG. 3 (test conditions: under nitrogen atmosphere, temperature rise rate of 10 ℃/min), the 5% thermal weight loss temperature of the polytriazole is 366.8 ℃, indicating that it has very good thermal stability.
The 1, 4-disubstituted triazole (model molecule) has the structure
The 1, 5-disubstituted triazole (model molecule) has the structure
When the reaction in example 1 was carried out in air, 1, 5-stereoregular polytriazole having a similar structure was likewise obtained, and it was found that the yield was 94.9%, the weight average molecular weight was 21250, the molecular weight distribution was 1.55 and the 1, 5-tacticity was 93.6%, according to measurement and analysis.
Example 2
Nickel complex catalysis M1 and M3 preparation of polytriazole P2:
wherein, the monomer M1 is synthesized according to the synthesis method disclosed in the published literature (Catalyst-free thiol-ene copolymerization: A power melt and surfactant tool for preparation of functional poly (vinyl sulfate) s. macromolecules 2014,47, 1325-1333); monomer M3 was synthesized according to the published literature (A recycled and reusable Cu (I) catalyzed azide-alkyl polymerization. Sci. Rep.2014,4,5107).
91.2mg (0.2mmol) of the monomer M1, 95.6mg (0.2mmol) of the monomer M3, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate were charged in a 10mL polymerization tube, and the reaction was carried out by changing the nitrogen gas by evacuation 3 times, injecting 0.5mL of ultra-dry N, N-dimethylformamide by means of a syringe and reacting at room temperature for 30 minutes. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P2.
The final product, polytriazole P2, was found to have a yield of 94.3%, a weight average molecular weight of 60000 and a molecular weight distribution of 1.78, as determined by assay analysis. The 1, 5-tacticity of P2 was calculated to be 96% by NMR spectroscopy. The polytriazole is soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and N, N-dimethylformamide at room temperature, and has excellent processability.
The thermogravimetric plot of polytriazole P2 obtained in example 2 is shown in FIG. 3. As can be seen from FIG. 3, the 5% thermal weight loss temperature of the polytriazole is 372.3 ℃, indicating that it has very good thermal stability.
Example 3
Nickel complex catalysis M1 and M4 preparation of polytriazole P3:
wherein, the monomer M1 is synthesized according to the synthesis method disclosed in the published literature (Catalyst-free thiol-ene copolymerization: A power melt and surfactant tool for preparation of functional poly (vinyl sulfate) s. macromolecules 2014,47, 1325-1333); monomer M4 was synthesized according to the published literature (A recycled and reusable Cu (I) catalyzed azide-alkyl polymerization. Sci. Rep.2014,4,5107).
91.2mg (0.2mmol) of the monomer M1, 122.8mg (0.2mmol) of the monomer M4, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate were charged in a 10mL polymerization tube, and the reaction was carried out by changing the nitrogen gas by evacuation 3 times, injecting 0.5mL of ultra-dry N, N-dimethylformamide by means of a syringe and reacting at room temperature for 30 minutes. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P3.
The final product, polytriazole P3, was determined to have a yield of 96.4%, a weight average molecular weight of 67900 and a molecular weight distribution of 1.92. The 1, 5-tacticity of P3 was calculated to be 95% by NMR spectroscopy. The polytriazole is soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and N, N-dimethylformamide at room temperature, and has excellent processability. The thermogravimetric plot of polytriazole P3 obtained in example 3 is shown in FIG. 3. As can be seen from FIG. 3, the 5% thermal weight loss temperature of the polytriazole is 368.7 deg.C, indicating that it has very good thermal stability.
Example 4
Nickel complex catalysis M1 and M5 preparation of polytriazole P4:
wherein, the monomer M1 is synthesized according to the synthesis method disclosed in the published literature (Catalyst-free thiol-ene copolymerization: A power melt and surfactant tool for preparation of functional poly (vinyl sulfate) s. macromolecules 2014,47, 1325-1333); monomer M5 was synthesized according to the published literature (Synthesis by gel polymerization and application activity cheminsors. macromolecules 2009,42, 1421-1424).
91.2mg (0.2mmol) of the monomer M1, 88.4mg (0.2mmol) of the monomer M5, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate were charged in a 10mL polymerization tube, and the reaction was carried out by changing the nitrogen gas by evacuation 3 times, injecting 0.5mL of ultra-dry N, N-dimethylformamide by means of a syringe and reacting at room temperature for 30 minutes. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P4.
The final product, polytriazole P4, was determined to have a yield of 93.3%, a weight average molecular weight of 29800 and a molecular weight distribution of 1.68. The 1, 5-tacticity of P4 was calculated to be 92.5% by NMR spectroscopy. The polytriazole is soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and N, N-dimethylformamide at room temperature, and has excellent processability. The thermogravimetric plot of polytriazole P4 obtained in example 4 is shown in FIG. 3. As can be seen from FIG. 3, the 5% thermal weight loss temperature of the polytriazole is 368.6 deg.C, indicating that it has very good thermal stability.
Example 5
Nickel complex catalysis M1 and M6 preparation of polytriazole P5:
wherein, the monomer M1 is synthesized according to the synthesis method disclosed in the published literature (Catalyst-free thiol-ene copolymerization: A power melt and surfactant tool for preparation of functional poly (vinyl sulfate) s. macromolecules 2014,47, 1325-1333); monomer M6 was synthesized with reference to the synthesis of monomer M1.
91.2mg (0.2mmol) of the monomer M1, 107.2mg (0.2mmol) of the monomer M6, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate were charged in a 10mL polymerization tube, and the reaction was carried out by changing the nitrogen gas by evacuation 3 times, injecting 0.5mL of ultra-dry N, N-dimethylformamide by means of a syringe and reacting at room temperature for 30 minutes. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P5.
The final product, polytriazole P5, was found to have a yield of 89.8%, a weight average molecular weight of 47000 and a molecular weight distribution of 1.73. The 1, 5-position of P5 can be calculated by nuclear magnetic resonance hydrogen spectrumThe tacticity was 94%. The polytriazole is soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and N, N-dimethylformamide at room temperature, and has excellent processability. The thermogravimetric plot of polytriazole P5 obtained in example 5 is shown in FIG. 3. As can be seen from FIG. 3, the 5% thermal weight loss temperature of the polytriazole is 369.8 ℃, indicating that it has very good thermal stability. In addition, polytriazole P5 shows chirality consistent with that of monomer M6, due to the introduction of binaphthalene moieties having chiral axes (FIG. 4). Example 5 circular dichroism of Polytriazole P5 and monomer M6 (tetrahydrofuran solution, concentration: 10)-5M) is shown in fig. 4.
Example 6
Nickel complex catalysis M1 and M7 preparation of polytriazole P6:
wherein, the monomer M1 is synthesized according to the synthesis method disclosed in the published literature (Catalyst-free thiol-ene copolymerization: A power melt and surfactant tool for preparation of functional poly (vinyl sulfate) s. macromolecules 2014,47, 1325-1333); monomer M7 was synthesized with reference to the synthesis of monomer M1.
91.2mg (0.2mmol) of the monomer M1, 107.2mg (0.2mmol) of the monomer M7, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate were charged in a 10mL polymerization tube, and the reaction was carried out by changing the nitrogen gas by evacuation 3 times, injecting 0.5mL of ultra-dry N, N-dimethylformamide by means of a syringe and reacting at room temperature for 30 minutes. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P6.
The final product, polytriazole P6, was determined to have a yield of 90.4%, a weight average molecular weight of 53800 and a molecular weight distribution of 1.72. The 1, 5-tacticity of P6 was calculated to be 95.5% by NMR spectroscopy. The polytriazole is soluble in dichloromethane, chloroform and tetrahydro at room temperatureFuran, N-dimethylformamide and the like are commonly used organic solvents, indicating that they have excellent processability. The thermogravimetry of the polytriazole P6 obtained in example 6 is shown in FIG. 3. As can be seen from fig. 3, the 5% thermal weight loss temperature of the polytriazole is 371.3 ℃, indicating that it has very good thermal stability; in addition, polytriazole P6 shows chirality consistent with that of monomer M7, due to the introduction of binaphthalene moieties having chiral axes (FIG. 4). Example 6 circular dichroism of Polytriazole P6 and monomer M7 (tetrahydrofuran solution, concentration: 10)-5M) is shown in fig. 4.
Example 7
Nickel complex catalysis M8 and M2 preparation of polytriazole P7:
wherein, the monomer M8 is synthesized according to the synthesis method disclosed in the published literature (i.e., a small route to a preparation regio-regionalized monomer hyperbranched enes. Polymer. chem.2014,5, 5890-5894); monomer M2 was synthesized according to a method disclosed in the literature (highly branched polyesters: Click polymerization, regio-structural, light emission, and fluorescent patterning. macromolecules 2008,41, 3808-.
63.6mg (0.2mmol) of the monomer M8, 72mg (0.2mmol) of the monomer M2, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate were charged in a 10mL polymerization tube, and the mixture was evacuated and purged with nitrogen 3 times, and 0.5mL of ultra-dry N, N-dimethylformamide was injected by a syringe and reacted at room temperature for 30 minutes. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P7.
The final product, polytriazole P7, was determined to have a yield of 91.3%, a weight average molecular weight of 46900 and a molecular weight distribution of 1.70. The 1, 5-tacticity of P7 was calculated to be 97% by NMR. The polytriazole is soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and N, N-dimethylformamide at room temperature, and has excellent processability. The thermogravimetry of the polytriazole P7 obtained in example 7 is shown in FIG. 3. As can be seen from FIG. 3, the 5% thermal weight loss temperature of the polytriazole is 388.1 ℃, indicating that it has very good thermal stability.
Example 8
Nickel complex catalysis M9 and M6 preparation of polytriazole P8:
wherein, the monomer M9 is synthesized according to the synthesis method disclosed in the published literature (hybridization-induced emission and superamplified amplified detection. J. mater. chem.2011,21, 4056-; monomer M6 was synthesized with reference to the synthesis of monomer M1.
76mg (0.2mmol) of the monomer M9, 107.2mg (0.2mmol) of the monomer M6, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate were charged in a 10mL polymerization tube, and the mixture was evacuated and purged with nitrogen 3 times, and 0.5mL of ultra-dry N, N-dimethylformamide was injected by a syringe and reacted at room temperature for 30 minutes. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P8.
The final product, polytriazole P8, was found to have a yield of 85.9%, a weight average molecular weight of 47500 and a molecular weight distribution of 1.86 by assay analysis. The 1, 5-tacticity of P8 was found to be 94.5% by NMR spectroscopy. The polytriazole is soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and N, N-dimethylformamide at room temperature, and has excellent processability. The thermogravimetric plot of polytriazole P8 obtained in example 8 is shown in FIG. 3. As can be seen from FIG. 3, the 5% thermal weight loss temperature of the polytriazole is 385.6 deg.C, indicating that it has very good thermal propertiesStability; in addition, polytriazole P8 shows chirality consistent with that of monomer M6, due to the introduction of binaphthalene moieties having chiral axes (FIG. 4). Example 8 circular dichroism of Polytriazole P8 and monomer M6 (tetrahydrofuran solution, concentration: 10)-5M) is shown in fig. 4.
Example 9
Nickel complex catalysis M9 and M7 preparation of polytriazole P9:
wherein, the monomer M9 is synthesized according to the synthesis method disclosed in the published literature (hybridization-induced emission and superamplified amplified detection. J. mater. chem.2011,21, 4056-; monomer M7 was synthesized with reference to the synthesis of monomer M1.
76mg (0.2mmol) of monomer M9, 107.2mg (0.2mmol) of monomer M7, 7.6mg (0.04mmol) of nickelocene, 23.1mg (0.04mmol) of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene and 65.2mg (0.2mmol) of cesium carbonate (the amount of the substance providing the alkaline environment is 0.01-10 times of the molar amount of the binary alkynyl compound) are added into a 10mL polymerization tube, the vacuum pumping is carried out to exchange nitrogen for 3 times, 0.5mL of ultra-dry N, N-dimethylformamide is injected by a syringe, and the reaction is carried out for 30 minutes at room temperature. After the reaction, 4mL of dichloromethane was added to the polymerization tube for dilution, the resulting polymer solution was filtered through cotton and then added dropwise to 80mL of vigorously stirred methanol for precipitation, followed by standing, and the precipitate was collected and dried to obtain polytriazole P9.
The final product, polytriazole P9, was found to have a yield of 81.6%, a weight average molecular weight of 32000 and a molecular weight distribution of 1.75 by assay analysis. The 1, 5-tacticity of P9 was calculated to be 93.5% by NMR spectroscopy. The polytriazole is soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and N, N-dimethylformamide at room temperature, and has excellent processability. The thermogravimetry of the polytriazole P9 obtained in example 9 is shown in FIG. 3. As can be seen from FIG. 3, the 5% thermal weight loss temperature of the polytriazole is 388 ℃, which shows that it has very good propertiesThermal stability of (a); in addition, polytriazole P9 shows chirality consistent with that of monomer M7, due to the introduction of binaphthalene moieties having chiral axes (FIG. 4). Example 9 circular dichroism of Polytriazole P9 and monomer M7 (tetrahydrofuran solution, concentration: 10)-5M) is shown in fig. 4.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing 1, 5-stereoregular polytriazole by catalysis of a nickel complex is characterized by comprising the following steps: the method comprises the following steps: under the conditions of alkaline environment and the existence of organic phosphine ligand, carrying out click polymerization on a binary alkynyl compound and a binary azido compound in an organic solvent under the catalytic action of a nickel complex, and carrying out subsequent treatment to obtain 1, 5-stereoregular polytriazole;
the structure of the 1, 5-stereoregular polytriazole is shown as a formula (I):
the structural formula of the binary alkynyl compound is shown as a formula (II):
the structural formula of the binary azido compound is shown as a formula (III):
N3-R2-N3(III)
in the formulas (I) to (III), n is an integer of 2 to 200, R1、R2Are identical or different organic radicals; the nickel complex is at least one of nickelocene, bis (methylcyclopentadienyl) nickel and bis (tetramethylcyclopentadienyl) nickel.
2. The method for preparing 1, 5-stereoregular polytriazole under the catalysis of nickel complex according to claim 1, wherein: r in the formulae (I) and (II)1Is any one of the following chemical structural formulas 1-17:
wherein m, k and h are positive integers of 1-20; x is selected from O or S; indicates the substitution position.
3. The method for preparing 1, 5-stereoregular polytriazole under the catalysis of nickel complex according to claim 1, wherein: r in the formulae (I) and (III)2Is any one of the following chemical structural formulas 1-18:
wherein m, k and h are positive integers of 1-20; x is selected from O or S; indicates the substitution position.
4. The method for preparing 1, 5-stereoregular polytriazole under the catalysis of nickel complex according to claim 1, wherein: the organic phosphine ligand is 4, 5-bis (diphenylphosphino) -9, 9-dimethyl xanthene or bis (2-diphenylphosphinophenyl) ether.
5. The method for preparing 1, 5-stereoregular polytriazole under the catalysis of nickel complex according to claim 1, wherein: the alkaline environment is provided by at least one of cesium carbonate, cesium pivalate, sodium hydroxide, sodium ascorbate, potassium phosphate, potassium hydroxide, sodium carbonate, sodium phosphate, potassium carbonate.
6. The method for preparing 1, 5-stereoregular polytriazole under the catalysis of nickel complex according to claim 1, wherein: the reaction temperature of the click polymerization is 15-35 ℃;
the reaction time of the click polymerization is 0.1-12 hours;
the molar ratio of the binary alkynyl compound to the binary azido compound is 1: (1-1.1);
the dosage of the nickel complex is 5-30 mol% of the binary alkynyl compound; the dosage of the organic phosphine ligand is 5mol percent to 30mol percent of the binary alkynyl compound.
7. The method for preparing 1, 5-stereoregular polytriazole under the catalysis of nickel complex according to claim 1, wherein: the concentration of the binary alkynyl compound in the organic solvent is 0.05-1 mol/L;
the organic solvent is at least one of toluene, tetrahydrofuran, dichloromethane, chloroform, 1, 4-dioxane, dimethyl sulfoxide and N, N-dimethylformamide.
8. The method for preparing 1, 5-stereoregular polytriazole under the catalysis of nickel complex according to claim 1, wherein: and the subsequent treatment is to dissolve the product in an organic solvent after the reaction is finished, then dropwise add the product into a precipitator for precipitation, collect the precipitate, and dry the precipitate to constant weight to obtain the 1, 5-stereoregular polytriazole.
9. The process for preparing 1, 5-stereoregular polytriazole under the catalysis of nickel complexes according to claim 8, wherein: the precipitant is methanol or n-hexane;
the organic solvent is at least one of toluene, tetrahydrofuran, dichloromethane, chloroform, 1, 4-dioxane, dimethyl sulfoxide and N, N-dimethylformamide.
10. A 1, 5-stereoregular polytriazole prepared by a process according to any one of claims 1 to 9.
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