CN114716659B - Method for preparing nitrogen-containing polymer through click polymerization without catalyst - Google Patents
Method for preparing nitrogen-containing polymer through click polymerization without catalyst Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 99
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 31
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002269 spontaneous effect Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000004072 triols Chemical group 0.000 claims description 2
- 125000002355 alkine group Chemical group 0.000 claims 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical group CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 229920001109 fluorescent polymer Polymers 0.000 abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 12
- 125000000304 alkynyl group Chemical group 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 229920005862 polyol Polymers 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 230000001419 dependent effect Effects 0.000 description 13
- 230000005284 excitation Effects 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 238000002270 exclusion chromatography Methods 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 150000001345 alkine derivatives Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- RZOTVHJYCPTNCM-UHFFFAOYSA-N 6-propanoyloxyhexyl propanoate Chemical compound CCC(=O)OCCCCCCOC(=O)CC RZOTVHJYCPTNCM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- UMNVUZRZKPVECS-UHFFFAOYSA-N 2-propanoyloxyethyl propanoate Chemical compound CCC(=O)OCCOC(=O)CC UMNVUZRZKPVECS-UHFFFAOYSA-N 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- -1 cyclic tertiary amine Chemical class 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 3
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 2
- ADGOOVVFTLKVKH-UHFFFAOYSA-N 4-propanoyloxybutyl propanoate Chemical compound CCC(=O)OCCCCOC(=O)CC ADGOOVVFTLKVKH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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Abstract
The invention relates to a method for preparing a nitrogen-containing polymer by click polymerization without a catalyst, belonging to the field of fluorescent polymer synthesis. The invention uses the di-alcohol or polyol containing tertiary amine as hydroxyl monomer, and prepares the linear and hyperbranched nitrogen-containing polymer with high yield, regular structure and higher molecular weight with the activated alkynyl monomer under the condition of no catalyst. The polymerization method disclosed by the invention has the advantages of no need of adding a catalyst, environment friendliness, mild reaction conditions, high reaction efficiency, high yield and the like, is suitable for large-scale production and application, and has a huge application prospect. The obtained polymer has the characteristics of regular structure, controllability, modification and stable autofluorescence performance, and is suitable for application in different fields.
Description
Technical Field
The invention belongs to the field of fluorescent polymer synthesis, and particularly relates to a method for preparing a nitrogen-containing polymer through click polymerization under the condition of no catalyst.
Background
Nitrogen-containing polymers are not only widely found in life bodies, but also play an important role in our production and life as one of the important classes of synthetic polymers. Furthermore, researchers have found that nitrogen-containing polymers also exhibit significant photoluminescent properties in the aggregate state, which are non-traditional fluorescent polymer materials. Compared with the traditional polymer photoluminescent material, the non-traditional fluorescent polymer has the advantages of easy preparation, good hydrophilicity and biocompatibility and the like, and has become an ideal candidate material for sensor, biological and medical application. Therefore, the development of new methods for synthesizing nitrogen-containing polymers is of great significance for enriching the types of fluorescent polymers and understanding the fluorescence mechanism.
Click polymerization is developed from click reaction, has the advantages of good selectivity, wide application range, mild condition, high efficiency, no byproducts, atom economy and the like, and is a method for efficiently synthesizing nitrogen-containing polymers. At present, researchers have realized that amine monomers with nucleophilicity and unsaturated bond monomers (double bonds or triple bonds) can be subjected to click polymerization at room temperature under the condition of no catalysis to prepare the nitrogen-containing polymer with high yield. Hydroxyl monomers, like amino monomers, are also a class of commonly available nucleophiles. Compared with amine, the alcohol monomer has the advantages of multiple types, wide sources, good stability, no toxicity and no pungent smell. However, since alcohol has no strong nucleophilicity, the current click polymerization based on hydroxy-alkyne generally has the defects of poor activity, reversible reaction, difficult stereoselectivity and the like. Although there have been few methods for preparing nitrogen-containing polymers based on the click polymerization of hydroxyl and unsaturated monomers, all polymerization systems currently require additional catalyst addition. Therefore, the development of a catalyst-system-free hydroxyl-alkyne click polymerization reaction for preparing a high-molecular-weight and structurally-controllable nitrogen-containing polymer is a very significant subject.
Disclosure of Invention
Based on the defect that the catalyst is additionally added in all the prior clicking polymerization reactions of hydroxyl and alkyne, the invention provides a method for preparing nitrogen-containing polymers with different topological structures (linear or branched) by the clicking polymerization reactions of hydroxyl and alkyne without adding the catalyst. The polymerization does not need to additionally add a catalyst, has the advantages of mild reaction condition, high reaction yield, regular polymer structure and the like, has the intrinsic luminescence property, and is an economic and environment-friendly method for preparing fluorescent polymers with different topological structures.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing polymer by click polymerization without catalyst is based on polymerization of hydroxyl and alkynyl monomers, which is to prepare linear or branched nitrogen-containing polymer with regular structure and higher molecular weight by tertiary amine-containing alcohol and activated alkyne monomers under mild condition.
Further, the tertiary amine-containing alcoholic hydroxyl monomer is an aliphatic tertiary amine structure-containing diol or triol monomer or a cyclic tertiary amine-containing diol or triol monomer. While aromatic tertiary amine-containing monomers cannot spontaneously react under the conditions of the present invention. The spontaneous reaction can be ensured under the condition of simultaneously having the hydroxyl monomer of the specific tertiary amine and the activated alkyne monomer.
The structure of the dihydric alcohol containing tertiary amine is as follows:n is 1-5; r is methyl, butyl or alicyclic group;
tertiary amine-containing triols of structureR1 is hydrogen or methyl;
the structure of the cycloaliphatic tertiary amine-containing dihydric alcohol is as follows:
examples of tertiary amine-containing alcoholic hydroxyl monomers include N-methyldiethanolamine, N-bis (2-hydroxyethyl) piperazine, triethanolamine, and the like.
Further, the activated alkyne monomer is a difunctional activated terminal alkyne monomer or a polyfunctional activated terminal alkyne monomer.
Wherein, the difunctional activated terminal alkyne monomer has the structural formula:
n is 1-4, m is 1-3.
The structural formula of the polyfunctional ester group activated terminal alkyne monomer is as follows:
further, the activated terminal alkyne monomer includes 1, 6-hexanediol dipropionate, 1, 4-butanediol dipropionate, ethylene glycol dipropionate, etc.
The molar ratio of the tertiary amine-containing alcoholic hydroxyl monomer to the activated alkyne monomer can be any ratio. As preferable: when the difunctional monomer is polymerized to obtain a linear polymer, the molar ratio of hydroxyl groups to alkynyl groups in the monomer is 1:1, which is advantageous for obtaining polymers with larger molecular weights.
Further, the reaction scheme of the partially linear nitrogen-containing polymer is as follows:
wherein R is methyl, butyl, alicyclic hydrocarbon or CH 2 CH 2 OH。
Further, the reaction scheme of the partially branched nitrogen-containing polymer is as follows:
further, the mild polymerization conditions are a wide range of polymer temperatures: the polymerization environment is unlimited at the temperature of 25 ℃ below zero to 60 ℃, and the reaction can be carried out spontaneously under the conditions of nitrogen or air and solvent or no solvent, and the reaction time is within 24 hours. The high yield is more than 80 percent after the reaction; contains more than 97% of nitrogen-containing polymer with E configuration.
Further, the nitrogen-containing polymer synthesized by the invention has intrinsic fluorescence properties and exhibits concentration-enhanced fluorescence and excitation-dependent wavelength fluorescence characteristics. Further, the nitrogen-containing polymer can be imaged in cells, and is a potential biomedical fluorescent material.
Compared with the prior art, the invention has the beneficial effects that: the invention uses the di-alcohol or polyol containing tertiary amine as hydroxyl monomer, and prepares the linear and hyperbranched nitrogen-containing polymer with high yield, regular structure and higher molecular weight with the activated alkynyl monomer under the condition of no catalyst. The polymerization method disclosed by the invention has the advantages of no need of adding a catalyst, environment friendliness, mild reaction conditions, high reaction efficiency, high yield and the like, is suitable for large-scale production and application, and has a huge application prospect. The obtained polymer has the characteristics of regular structure, controllability, modification and stable autofluorescence performance, and has wide application prospects in the fields of sensors, biology, medicine and the like.
Drawings
FIG. 1 nuclear magnetic resonance hydrogen spectra of the polymer obtained in example 1 and the corresponding monomer.
FIG. 2 shows nuclear magnetic resonance hydrogen spectra of the polymers obtained in examples 2,3 and 4.
FIG. 3 is a graph showing fluorescence spectra of polymers and corresponding monomers obtained in examples 1,2,3 and 4.
FIG. 4 shows fluorescence spectra of the polymer obtained in example 1 at (A) different concentrations and (B) different excitation wavelengths.
FIG. 5 shows the nuclear magnetic resonance spectrum of (A) and the fluorescence spectrum of (C) at different concentrations and at different excitation wavelengths of the polymer obtained in example 6.
FIG. 6 shows the nuclear magnetic resonance spectrum of (A) and the fluorescence spectrum of (C) at different concentrations and at different excitation wavelengths of the polymer obtained in example 7.
FIG. 7 shows the nuclear magnetic resonance spectrum of the polymer (A) obtained in example 8 and the fluorescence spectrum of the polymer (C) at different concentrations of (B) and at different excitation wavelengths.
FIG. 8 shows the nuclear magnetic resonance spectrum of (A) and the fluorescence spectrum of (C) at different concentrations and at different excitation wavelengths of the polymer obtained in example 9.
FIG. 9 shows the nuclear magnetic resonance spectrum of (A) and the fluorescence spectrum of (C) at different concentrations and at different excitation wavelengths of the polymer obtained in example 11.
FIG. 10 shows an intracellular image of the polymer obtained in example 1.
Detailed Description
The method for preparing the polymer based on the catalyst-free hydroxyl-alkyne click polymerization reaction comprises the following steps: all of which are commercially available or readily synthesized.
For example wherein the ester alkyne monomer is activatedReference may be made to the synthesis of publication (Polymer Chemistry,2020,11 (14): 2568-2575).
Example 1:
n-methyldiethanolamine (0.119 g,1 equiv) and 1, 6-hexanediol dipropionate (0.222 g,1 equiv) were added to a 5mL single port polymerization flask and reacted under argon at 25℃with stirring for 24h. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a polymer (LP-1) having 97% yield and 100% E configuration, and the structure of the target polymer was confirmed by nuclear magnetic resonance hydrogen spectroscopy (FIG. 1). The polymer was characterized by volume exclusion chromatography with a weight average molecular weight of 21000g/mol and a molecular weight distribution of 2.28. The fluorescence properties of the polymers were characterized using a fluorescence spectrometer (fig. 3), exhibiting concentration-dependent enhancement and excitation wavelength-dependent fluorescence properties (fig. 4). The method is shown to be capable of realizing the spontaneous polymerization to prepare the linear fluorescent polymer with higher molecular weight and regular structure. Cell experiments show that the fluorescent polymer can be imaged in cells (figure 10), and is a fluorescent material for potential biomedical use.
Example 2:
n-methyldiethanolamine 0.119g,1 equiv) and 1, 6-hexanediol dipropionate (0.222 g,1 equiv) were added to a 5mL single-port polymerization flask, and reacted under stirring in air at-25℃for 24 hours. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a polymer (LP-2) having 90% yield and 98% e configuration, and the target polymer structure was confirmed by nuclear magnetic resonance hydrogen spectroscopy (fig. 2). Volume exclusion chromatography characterizes the polymer as having a weight average molecular weight of 9600g/mol and a molecular weight distribution of 1.94, and the fluorescence properties of the polymer were characterized using a fluorescence spectrometer (FIG. 3). The method is shown to be capable of realizing the spontaneous polymerization to prepare the linear fluorescent polymer with higher molecular weight and regular structure.
Example 3:
n-methyldiethanolamine (0.119 g,1 equiv) and 1, 6-hexanediol dipropionate (0.222 g,1 equiv) were added to a 5mL single port polymerization flask and reacted with stirring in air at 25℃for 24 hours. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a polymer (LP-3) of 96% yield and 100% E configuration, and the structure of the target polymer was confirmed by nuclear magnetic resonance hydrogen spectroscopy (FIG. 2). The polymer was characterized by volume exclusion chromatography with a weight average molecular weight of 26800g/mol and a molecular weight distribution of 2.35 and fluorescence properties (FIG. 3) by fluorescence spectroscopy. The method is shown to be capable of realizing the spontaneous polymerization to prepare the linear fluorescent polymer with higher molecular weight and regular structure.
Example 4:
n-methyldiethanolamine (0.119 g,1 equiv) and 1, 6-hexanediol dipropionate (0.222 g,1 equiv) were added to a 5mL single port polymerization flask and reacted under stirring in air at 60℃for 24 hours. After the reaction was completed, the mixture was precipitated by n-hexane to obtain a polymer in 99% yield. The polymer was characterized by volume exclusion chromatography with a weight average molecular weight of 71700g/mol and a molecular weight distribution of 2.75, confirming that the catalyst-free click polymerization of hydroxy-alkynes could proceed spontaneously by nuclear magnetic resonance hydrogen spectroscopy (FIG. 2), and yielded a linear polymer (LP-4) in the 100% E configuration. The fluorescence properties of the polymers were characterized using a fluorescence spectrometer (fig. 3). The method is shown to be capable of realizing the spontaneous polymerization to prepare the linear fluorescent polymer with higher molecular weight and regular structure.
Example 5:
n-butyldiethanolamine (0.119 g,1 equiv) and 1, 6-hexanediol dipropionate (0.222 g,1 equiv) were added to a 5mL single port polymerization flask and reacted under stirring in air at 25℃for 24 hours. After the reaction was completed, the mixture was precipitated by n-hexane to obtain a polymer in 96% yield. The polymer was characterized by volume exclusion chromatography with a weight average molecular weight of 14600g/mol and a molecular weight distribution of 2.33. The method can realize spontaneous polymerization to prepare the nitrogenous linear polymer with higher molecular weight.
Example 6:
n-methyldiethanolamine (0.119 g,1 equiv) and 1, 4-butanediol dipropionate (0.194, 1 equiv) were added to a 5mL single port polymerization flask and reacted under stirring in air at 25℃for 24 hours. After the reaction was completed, the mixture was precipitated by n-hexane to obtain a polymer in 85% yield. The polymer was characterized by volume exclusion chromatography with a weight average molecular weight of 20400g/mol and a molecular weight distribution of 1.96, and it was confirmed by nuclear magnetic resonance hydrogen spectroscopy that the catalyst-free click polymerization of hydroxy-alkynes could proceed spontaneously, and a linear polymer (LP-5) of 100% E configuration was obtained. The fluorescence properties of the polymers were characterized using a fluorescence spectrometer and exhibited concentration-dependent enhancement and excitation wavelength-dependent fluorescence properties (fig. 5). The method is shown to be capable of realizing the spontaneous polymerization to prepare the linear fluorescent polymer with higher molecular weight and regular structure.
Example 7:
n-methyldiethanolamine (0.119 g,1 equiv) and ethylene glycol dipropionate (0.166 g,1 equiv) were added to a 5mL single port polymerization flask and reacted under stirring in air at 45℃for 24 hours. After the reaction was completed, the mixture was precipitated by n-hexane to obtain a polymer in 80% yield. The polymer was characterized by volume exclusion chromatography with a weight average molecular weight of 18700g/mol and a molecular weight distribution of 1.75, and it was confirmed by nuclear magnetic resonance hydrogen spectroscopy that the catalyst-free click polymerization of hydroxy-alkynes could proceed spontaneously, and a linear polymer (LP-6) of 100% E configuration was obtained. The fluorescence properties of the polymers were characterized using a fluorescence spectrometer and exhibited concentration-dependent enhancement and excitation wavelength-dependent fluorescence properties (fig. 6). The method is shown to be capable of realizing the spontaneous polymerization to prepare the linear fluorescent polymer with higher molecular weight and regular structure.
Example 8:
n, N-bis (2-hydroxyethyl) piperazine (0.174 g,1 equiv) and 1, 6-hexanediol dipropionate (0.222 g,1 equiv) were added to a 10mL single port polymerization flask, a water/dimethyl sulfoxide mixed solvent (0.5 mL volume ratio 1:4) was added, and the mixture was stirred in air at 60℃for 24 hours. After the reaction was completed, the polymer was precipitated by n-hexane to obtain a linear polymer in 82% yield and 97% E configuration. The polymer was characterized by volume exclusion chromatography with a weight average molecular weight of 11585g/mol and a molecular weight distribution of 1.50. The fluorescence properties of the polymers were characterized using a fluorescence spectrometer and exhibited concentration-dependent enhancement and excitation wavelength-dependent fluorescence properties (fig. 7). The method can realize spontaneous polymerization to prepare linear polymers with higher molecular weight and regular structure.
Example 9:
triethanolamine (0.1492 g,1 equiv), ethylene glycol dipropionate (0.1660 g,1 equiv) and N, N-dimethylformamide (0.3 mL) were each added to a 10mL single-port polymerization bottle, and the reaction was stirred under an air atmosphere at 25℃for 24 hours. After the reaction is finished, the polymer is settled by diethyl ether to obtain a branched polymer with 84 percent yield and 98 percent E configuration, the nuclear magnetic resonance hydrogen spectrum is adopted to confirm the structure of the target polymer, and the branching degree of the polymer is calculated to be 0.72. The polymer was characterized by volume exclusion chromatography with a weight average molecular weight of 48000g/mol and a molecular weight distribution of 2.68. The fluorescence properties of the polymers were characterized using a fluorescence spectrometer and exhibited concentration-dependent enhancement and excitation wavelength-dependent fluorescence properties (fig. 8). The method is shown to be capable of realizing the spontaneous polymerization to prepare the branched fluorescent polymer with higher molecular weight and regular structure.
Example 10:
triethanolamine (0.1492 g,1 equiv), ethylene glycol dipropionate (0.249 g,1.5 equiv) and methylene chloride (0.3 mL) were added to a 10mL single port polymerization flask, and reacted under stirring at 25℃for 12 hours in an air atmosphere. After the reaction is finished, the polymer is settled by diethyl ether to obtain a branched polymer with 88 percent of yield and 99 percent of E configuration, the branching degree of the polymer is calculated to be 0.69 by adopting nuclear magnetic resonance hydrogen spectrum, the weight average molecular weight of the polymer is 69200g/mol by adopting volume exclusion chromatography, and the molecular weight distribution is 3.04, so that the branched polymer with higher molecular weight and regular structure can be prepared by the method.
Example 11:
triethanolamine (0.1492 g,1 equiv), 1, 6-hexanediol dipropionate (0.222 g,1 equiv) and dimethylformamide (0.5 mL) were each added to a 10mL single port polymerization flask and reacted under stirring at 25℃for 12 hours in an air atmosphere. After the reaction was completed, the polymer was settled with diethyl ether to obtain a branched polymer having a yield of 90% and an E configuration of 99%, the branching degree of the polymer was calculated to be 0.70 by using nuclear magnetic resonance hydrogen spectrum, the weight average molecular weight of the polymer was 62500g/mol by using volume exclusion chromatography, the molecular weight distribution was 2.95, the fluorescence property of the polymer was characterized by using a fluorescence spectrometer, and the polymer exhibited concentration-dependent enhancement and excitation wavelength-dependent fluorescence characteristics (FIG. 9). The method is shown to be capable of realizing the spontaneous polymerization to prepare the branched fluorescent polymer with higher molecular weight and regular structure.
Example 12:
triisopropanolamine (0.1912 g,1 equiv), ethylene glycol dipropionate (0.1660 g,1 equiv) and methylene chloride (0.3 mL) were added separately to a 10mL single port polymerization bottle and reacted under stirring at 25℃for 12h in an air atmosphere. After the reaction is finished, the polymer is settled by diethyl ether to obtain a nitrogen-containing branched polymer with 81 percent of yield, and the volume exclusion chromatography is adopted to characterize the weight average molecular weight of the polymer to be 20200g/mol, and the molecular weight distribution to be 2.94, which indicates that the method can prepare the nitrogen-containing branched polymer with higher molecular weight.
Claims (5)
1. A method for preparing a nitrogen-containing polymer by click polymerization without a catalyst, which is characterized by comprising the following steps: the method comprises the steps of (1) carrying out spontaneous click polymerization reaction on an alcohol hydroxyl monomer containing tertiary amine and an activated terminal alkyne monomer under the condition of no catalyst, so as to prepare a linear or branched nitrogen-containing polymer with a regular structure;
the tertiary amine-containing alcohol hydroxyl monomer is aliphatic and containsA diol or triol monomer of tertiary amine structure or a cycloaliphatic tertiary amine-containing diol monomer; the structure of the cycloaliphatic tertiary amine-containing dihydric alcohol monomer is as follows:；
the activated terminal alkyne monomer is a difunctional activated terminal alkyne monomer or a polyfunctional activated terminal alkyne monomer;
the difunctional activated terminal alkyne monomer has the structural formula:
or->n is 1 to 4, m is 1 to 3;
the polyfunctional activated terminal alkyne monomer has the structural formula:
。
2. the method for preparing a nitrogen-containing polymer by click polymerization without catalyst according to claim 1, wherein the aliphatic diol structure containing tertiary amine structure is:n is 1-5; r is methyl, butyl or alicyclic group; the aliphatic tertiary amine structure-containing triol structure is +.>；R 1 Is hydrogen or methyl.
3. The method for preparing a nitrogen-containing polymer by click polymerization without catalyst according to claim 1, wherein the reaction temperature in the polymerization reaction condition is in the range of-25 to 60 ℃ and the reaction time is within 24 hours.
4. The method for preparing a nitrogen-containing polymer by click polymerization without catalyst according to claim 1, wherein the polymerization reaction conditions are under nitrogen or air; with or without solvent.
5. Use of a nitrogen-containing polymer prepared according to the method of any one of claims 1-4 as a fluorescent material.
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| WO2019157857A1 (en) * | 2018-02-13 | 2019-08-22 | 江南大学 | Method for realizing mercapto-alkyne deep layer photopolymerization and composition thereof |
| CN110498917A (en) * | 2019-09-29 | 2019-11-26 | 常州大学 | A kind of preparation method of high molecular weight branched polymer |
| CN110845714A (en) * | 2019-11-19 | 2020-02-28 | 常州大学 | Water-soluble aggregation-induced emission polymer and preparation method and application thereof |
| CN110845725A (en) * | 2019-11-19 | 2020-02-28 | 常州大学 | Preparation method of pH and concentration dependent tertiary amine chromophore polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019157857A1 (en) * | 2018-02-13 | 2019-08-22 | 江南大学 | Method for realizing mercapto-alkyne deep layer photopolymerization and composition thereof |
| CN110498917A (en) * | 2019-09-29 | 2019-11-26 | 常州大学 | A kind of preparation method of high molecular weight branched polymer |
| CN110845714A (en) * | 2019-11-19 | 2020-02-28 | 常州大学 | Water-soluble aggregation-induced emission polymer and preparation method and application thereof |
| CN110845725A (en) * | 2019-11-19 | 2020-02-28 | 常州大学 | Preparation method of pH and concentration dependent tertiary amine chromophore polymer |
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