CN115028834A - Polyaryl triazole and preparation method and application thereof - Google Patents
Polyaryl triazole and preparation method and application thereof Download PDFInfo
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- 150000003852 triazoles Chemical class 0.000 title claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 42
- -1 aryl benzyl azide Chemical compound 0.000 claims description 33
- 150000001540 azides Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- 238000006243 chemical reaction Methods 0.000 description 57
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- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
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- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 7
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- GFBKCJQKMJUEHL-UHFFFAOYSA-N 1-(azidomethyl)-2-[4-[4-[2-(azidomethyl)phenyl]phenyl]phenyl]benzene Chemical compound C1(=CC=C(C=C1)C1=CC=CC=C1CN=[N+]=[N-])C1=CC=C(C=C1)C1=CC=CC=C1CN=[N+]=[N-] GFBKCJQKMJUEHL-UHFFFAOYSA-N 0.000 description 2
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- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to a polyaryl triazole and a preparation method and application thereof. The polyaryl triazole has a structure shown in a formula (I):
wherein R is
n is an integer of 26 to 45. The polyaryl triazole provided by the invention has better high temperature resistance by introducing the skeleton structures of a benzene ring and a triazole ring; and can be dissolved in various organic solvents, and has excellent processability; in addition, the polyaryltriazole can be obtained by CuAACP polymerization, the preparation conditions are mild, and the cost of the required raw materials is low.
Description
Technical Field
The invention belongs to the field of preparation of high molecular polymers, and particularly relates to polyaryltriazoles and a preparation method and application thereof.
Background
Since Michel discovered that 1,2, 3-triazole can be formed by the reaction of azidobenzene and alkyne dimethyldicarboxylate in 1893, the 1, 3-cycloaddition reaction of azide and alkyne becomes one of the most important methods for preparing 1,2, 3-triazole compounds and derivatives thereof. Click chemistry is a new chemical concept proposed by Sharpless equal to 2001, and refers to a nearly perfect organic reaction, which has modularization, high reaction efficiency, mild conditions, good atom economy, wide substrate application range and good selectivity. No toxic by-products, simple purification and the like, and is widely applied to the preparation of drug carrier materials, biological functional materials, photoelectric functional materials, surface modification and the like.
In the development of click chemistry, polymer scientists developed a novel polymer synthesis method by utilizing the advantages of simple and efficient click chemistry reaction conditions, and directly applied to the preparation of novel polymers, namely click polymerization. Now, many click reactions have been developed into click polymerization, one of the most influential is cu (i) catalyzed azide-alkyne click polymerization (CuAACP), which has many advantages of high reaction efficiency, mild conditions, good atom economy, insensitivity to water and oxygen, good product stereoselectivity, and the like, and has wide applications in molecular design and synthesis of polymer materials. The di-azide and di-alkynyl monomers can generate 1,3 dipolar cycloaddition reaction under the condition of heating or Cu (I) catalysis to obtain a plurality of polytriazole high polymer materials with excellent performance, so that the polytriazole high polymer materials are widely researched, the triazole ring produced by using the azide and the alkyne has the characteristics of rigidity and high temperature resistance, can be developed into high-performance resin and is expected to be applied as engineering plasticsIn many fields. Chinese patent 'a trifunctional alkyne-derived polytriazole resin and a preparation method thereof' discloses that an aromatic triphenol compound is used for preparing aromatic propargyl ether through substitution reaction, and then the aromatic triphenol compound and azide are subjected to 1, 3-dipolar cycloaddition reaction to prepare the trifunctional alkyne-derived novel polytriazole resin, so that the obtained trifunctional alkyne-derived novel polytriazole resin has more benzene ring structures and better heat resistance, and T is T g Is 310 ℃; t is d5 Was 361 ℃. The Chinese patent 'polytriazole resin containing polyphenyl and composite material and preparation method thereof' discloses that the resin is prepared through 1, 3-dipolar cycloaddition reaction, the reaction is efficient, the temperature is low, and the conditions are mild; the obtained resin has excellent processing performance, can be crosslinked and cured at 60-80 ℃, the cured product has excellent mechanical property and heat resistance, the bending strength of the T700 unidirectional carbon fiber reinforced composite material reaches 1450-1500 MPa, the bending modulus is 140-145 GPa, the interlaminar shear strength is 50-55 MPa, and the T700 unidirectional carbon fiber reinforced composite material has T g Is 251 ℃; t is d5 The temperature was 360 ℃. Although the performance of the prepared polytriazole resin is excellent, the defects of complex process, high reaction conditions and the like still exist, and meanwhile, the application prospect of the polytriazole resin is limited due to high raw material cost.
Therefore, obtaining a polytriazole resin with better high temperature resistance and easy synthesis at low cost through structural design has important research value.
Disclosure of Invention
The present invention is directed to overcoming the disadvantages or shortcomings of the prior art and to providing a polyaryltriazole. The polyaryl triazole provided by the invention has better high temperature resistance by introducing the skeleton structures of a benzene ring and a triazole ring; and can be dissolved in various organic solvents, and has excellent processability; in addition, the polyaryltriazole can be obtained by CuAACP polymerization, the preparation condition is mild, and the cost of the required raw materials is low.
Another object of the present invention is to provide a process for the preparation of the above-mentioned polyarylaltriazoles.
The invention also aims to provide application of the polyaryltriazole in preparation of high-temperature-resistant resin.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a polyaryltriazole having the structure shown in formula (I):
wherein R is
n is an integer of 27 to 52.
The polyaryl triazole provided by the invention contains a benzene ring and a skeleton structure of a triazole ring, and is matched with other specific structures and groups to obtain the T of the polyaryl triazole g (glass transition temperature) 196.4 to 230.6 ℃ and T dmax (the maximum thermal cracking temperature in nitrogen) reaches 385.1-395.7 ℃, and the heat resistance is excellent; and has better solubility in various organic solvents and excellent processing performance.
In addition, the polyaryl triazole provided by the invention can be prepared by cycloaddition reaction of azide-alkyne catalyzed by Cu (I), the reaction condition is mild, and the cost of the required raw materials is low.
Preferably, R is
Preferably, n is an integer of 35-45.
Preferably, the average molecular weight of the polyaryltriazole is 11000-17000.
The preparation method of the polyaryltriazole comprises the following steps:
carrying out click polymerization reaction on a two-end-group aryl benzyl azide monomer shown in a formula (II) and a two-end-group aryl alkyne monomer shown in a formula (III) under the action of a click polymerization catalyst to obtain the polyaryl triazole;
the preparation method provided by the invention takes the two-end-group aryl benzyl azide monomer and the two-end-group aryl alkyne monomer as raw materials, and is efficiently prepared by click reaction, the process is simple, no intermediate product is generated, the reaction condition is mild, and the reaction efficiency is high.
Preferably, the two-terminal-group benzyl azide monomer is obtained through the following processes: raw materials: 4,4' -dimethyl biphenyl, p-xylene or m-xylene, reacting with NBS (N-bromosuccinimide) under an initiator (such as dibenzoyl peroxide) to generate benzyl bromide, and carrying out nucleophilic substitution reaction on the benzyl bromide and sodium azide to obtain the di-terminal group aryl benzyl azide monomer.
4,4' -dimethyl biphenyl, p-xylene and m-xylene are cheap and easily available, and the cost is low.
More preferably, the molar ratio of the dibenzoyl peroxide to the raw material to the NBS is 1 (30-60) to (80-120).
More preferably, the reaction temperature of the raw materials and NBS is 70-80 ℃, and the reaction time is 1-5 h.
More preferably, a solvent, such as CCl, is also present in the reaction system of the starting material and NBS 4 And the concentration of the raw materials in the reaction system is 0.4-0.5 g/L.
More preferably, the molar ratio of the benzyl bromide to the sodium azide is 1 (2-3).
More preferably, the reaction of the raw material and NBS further comprises the steps of reduced pressure evaporation and silica gel column chromatography.
Specifically, the reaction process of the raw material and NBS is as follows: mixing the raw material, N-bromosuccinimide and dibenzoyl peroxide, and adding CCl under the condition of nitrogen 4 Stirring, condensing and refluxing the solvent at 70-80 ℃, and reacting overnight. Filtering, evaporating under reduced pressure to remove solvent, and purifying the residue by silica gel column chromatography with petroleum ether/dichloromethane (10:1/v: v) as eluent to obtain the benzyl bromide.
More preferably, the temperature of the nucleophilic substitution reaction is 55-65 ℃ and the time is 1-5 h.
More preferably, a solvent such as DMF is also present in the reaction system of the nucleophilic substitution reaction, and the concentration of benzyl bromide in the reaction system is 0.4-0.5 g/L.
More preferably, the nucleophilic substitution reaction further comprises the steps of extraction, washing, drying, reduced pressure evaporation and silica gel column chromatography.
Specifically, the nucleophilic substitution reaction process is as follows: adding benzyl bromide and sodium azide into a reactor, adding a DMF (dimethyl formamide) solvent in the nitrogen atmosphere, stirring at 55-65 ℃ for reacting overnight, cooling the reaction liquid to room temperature, pouring deionized water, extracting with diethyl ether, collecting an organic layer, washing with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, performing reduced pressure evaporation to remove the diethyl ether solvent, and performing silica gel column chromatography on the product by using petroleum ether/dichloromethane (10:1/v: v) as an eluent to obtain the di-terminal-group arylbenzyl azide monomer.
Preferably, the click polymerization catalyst is a cuprous salt catalyst.
Preferably, the mole ratio of the click polymerization catalyst to the double-end aromatic benzyl azide monomer is (1-3): 50.
Preferably, the temperature of the click polymerization reaction is 30-80 ℃.
Preferably, the molar ratio of the two terminal group aryl benzyl azide monomers to the two terminal group aryl alkyne monomers is 1: 1.
Specifically, the click polymerization reaction process is as follows: sequentially adding a two-terminal-group aryl alkyne monomer and a two-terminal-group aryl benzyl azide monomer into a reactor, adding a DMSO solvent to dissolve the monomers, and stirring for a period of time at 30-80 ℃ in a nitrogen atmosphere. Dissolving copper sulfate pentahydrate and sodium ascorbate in deionized water, dropwise adding into the reaction solution by using a constant pressure dropping hole, and reacting overnight. After the reaction is finished, pouring the reaction solution into a saturated aqueous solution of EDTA disodium, generating precipitates, filtering, washing with deionized water for three times, filtering, dissolving a filter cake in a DMSO solvent, pouring a methanol/water mixed solution, separating out the precipitates, washing with methanol for 2-3 times, drying and weighing to obtain the polyaryltriazole.
The application of the polyaryltriazoles in the preparation of high temperature resistant resin is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
the polyaryl triazole provided by the invention has better high temperature resistance by introducing the skeleton structures of a benzene ring and a triazole ring; and can be dissolved in various organic solvents, and has excellent processability; in addition, the polyaryltriazole can be obtained by CuAACP polymerization, the preparation conditions are mild, and the cost of the required raw materials is low.
Drawings
FIG. 1 shows two terminal aromatic benzyl azide monomers II-1 and their starting materials, intermediates in CDCl 3 Is/are as follows 1 H NMR comparison chart.
FIG. 2 shows two terminal aromatic benzyl azide monomers II-2 and their starting materials, intermediates in CDCl 3 Is/are as follows 1 H NMR comparison chart.
FIG. 3 shows the presence of two terminal group benzyl azide monomers II-3 and their starting materials, intermediates in CDCl 3 Is/are as follows 1 H NMR comparison chart.
FIG. 4 shows the preparation of a bis-terminated phenylsulfone ether alkyne monomer III in CDCl 3 Is 1 H NMR comparison chart.
Fig. 5 is DSC curves for PTA1, PTA2, PTA3 and PTA1 ', PTA2 ', PTA3 '.
FIG. 6 is a diagram of TG (a) and DTG (b) of PTA1, PTA2, PTA3, PTA1 ', PTA2 ', PTA3 '.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the examples below, generally according to conditions conventional in the art or as recommended by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The reagents selected in the various embodiments of the invention are all commercially available.
Example 1
This example provides two terminal group benzyl azide monomers II-1 to two terminal group benzyl azide monomers II-3 and a poly (aryl triazole) (designated as PTA1), which are prepared by the following steps:
(1) 9.1130g (50mmol) of 4,4' -dimethylbiphenyl, 17.7984g (100mmol) of N-bromosuccinimide and 0.2422g (1mmol) of dibenzoyl peroxide are placed in a three-necked flask equipped with a reflux condenser, and 200ml of CCl is added under nitrogen 4 The solvent is stirred, condensed and refluxed at 78 ℃ and reacted overnight. After filtration, the solvent was removed by evaporation under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/methylene chloride (10:1/v: v) as an eluent to give 12.6100g of a white solid powder, i.e., 4' -dibromomethylbiphenyl, in a yield of 74.2%.
Adding 1.70g (5mmol) of 4,4 '-dibromomethylbiphenyl and 0.780g (12mmol) of sodium azide into a three-necked flask with a rotor, adding 20ml of DMF solvent under the atmosphere of nitrogen, stirring at 60 ℃ for reaction overnight, pouring deionized water (30ml) after the reaction liquid is cooled to room temperature, extracting with diethyl ether (3X 20ml), collecting an organic layer, washing with saturated saline solution (3X 20ml), drying with anhydrous magnesium sulfate, filtering, removing the diethyl ether solvent by reduced pressure evaporation, and performing silica gel column chromatography on a product by using petroleum ether/dichloromethane (20:1/v: v) as an eluent to obtain 1.230g of white solid 4,4' -biphenyl dibenzylazide (marked as a di-terminal aromatic benzyl azide monomer II-1) with the yield of 93.1%.
FIG. 1 shows two terminal aromatic benzyl azide monomers II-1 and their raw materials and intermediates in CDCl 3 Is/are as follows 1 H NMR chart. From nuclear magnetic hydrogen spectra, nuclear magnetic comparison of 4,4' -dimethylbiphenyl raw material to bromine intermediate can find that the peak of methyl hydrogen of raw material at 2.48ppm disappears, and chemical shift of methylene hydrogen appears at 4.57ppm, which indicates that hydrogen on alpha position of raw material generates NBS reaction and generates benzyl bromine intermediate. From nuclear magnetic comparison of bromine intermediate and azide product, it can be found that the chemical shift of hydrogen on methylene is obviously shifted to high field to 4.42ppm, mainly because the polarity of azide is smaller than that of bromine, so that the chemical shift is changed, and further, the azide is explainedSodium and benzyl bromide have nucleophilic substitution reaction, an azide product is synthesized, and the successful preparation of the double-end aromatic benzyl azide monomer II-1 is verified.
(2) 17.80g N-bromosuccinimide (NBS,100mmol), 5.3082g of p-xylene (50mmol), 0.2422g of dibenzoyl peroxide (BPO,1mmol) and 60mL of carbon tetrachloride were charged in a 250mL three-necked flask equipped with a rotor, and after condensing reflux at 78 ℃ for 12 hours under a nitrogen atmosphere, the suspension was filtered, the filtrate was concentrated, and recrystallized with methanol to obtain white crystals (8.2312 g of 1, 4-bis- (bromomethylbenzene) in 62.4% yield.
2.6395g (10mmol) of 1, 4-bis- (bromomethylbenzene) and 1.430g (22mmol) of sodium azide are added into a 100mL three-neck flask provided with a rotor, 20mL of DMF is added under the nitrogen atmosphere, the reaction solution is poured into 100mL of deionized water and is extracted three times by 30mL of anhydrous ether, an organic phase is collected and is washed by 100mL of saturated saline, the anhydrous magnesium sulfate is dried, the solvent is evaporated after filtration to obtain 1.7216g of oily liquid p-benzyl diazide (marked as a two-terminal arylbenzyl azide monomer II-2), and the yield is 91.5%.
FIG. 2 shows two terminal aromatic benzyl azide monomers II-2 and their starting materials and intermediates in CDCl 3 Is/are as follows 1 H NMR comparison chart. As can be seen from the figure, the peak of methyl hydrogen at 2.48ppm of the starting material disappeared, and the chemical shift of methylene hydrogen appeared at 4.50ppm, indicating that hydrogen at the α -position of the starting material underwent NBS reaction to produce a benzyl bromide intermediate. Similar to the synthetic monomer 1, nuclear magnetic comparison of a bromine intermediate and an azide product can find that the chemical shift of hydrogen on a methylene group obviously shifts to 4.36ppm towards a high field, mainly because the polarity of azide is relatively small compared with bromine, so that the chemical shift changes, further, the nucleophilic substitution reaction of sodium azide and benzyl bromide is illustrated, and the bi-terminal arylbenzyl azide monomer II-2 is successfully prepared.
(3) A250 mL three-necked flask equipped with a rotor was charged with 17.80g N-bromosuccinimide (NBS,100mmol), 5.3083g of m-xylene (50mmol), 0.2422g of dibenzoyl peroxide (BPO,1mmol) and 60mL of carbon tetrachloride, and condensed at 78 ℃ under nitrogen and refluxed for 12 hours. The suspension was filtered, the filtrate was concentrated, and recrystallized from methanol to give 6.8342g of white crystals (1, 3-bis- (bromomethylbenzene) in 51.8% yield.
2.6395g (10mmol) of 1, 3-bis- (bromomethylbenzene) and 1.430g (22mmol) of sodium azide are added into a 100mL three-neck flask provided with a rotor, 20mL of DMF is added under the nitrogen atmosphere, the mixture is reacted for 10 hours at 60 ℃, reaction liquid is poured into 100mL of deionized water, extracted for three times by 30mL of anhydrous ether, an organic phase is collected, washed by 100mL of saturated saline, dried by anhydrous magnesium sulfate, filtered, and the solvent is evaporated to obtain 1.7126g of oily liquid m-diazide benzyl (marked as a two-end arylbenzyl azide monomer II-3), and the yield is 91.0%.
FIG. 3 shows two-terminal benzyl azide monomers II-3 and their starting materials and intermediates in CDCl 3 Is/are as follows 1 H NMR comparison chart. As is clear from the figure, the peak of methyl hydrogen at 2.43ppm of the starting material disappeared, and the chemical shift of methylene hydrogen appeared at 4.51ppm, indicating that hydrogen at the α -position of the starting material underwent NBS reaction to produce a benzyl bromide intermediate. The nuclear magnetic comparison of the bromine intermediate and the azide product can find that the chemical shift of hydrogen on a methylene group is obviously shifted to 4.38ppm towards a high field, which indicates that sodium azide and benzyl bromide have nucleophilic substitution reaction, and the double-end-group arylbenzyl azide monomer II-3 is successfully prepared.
(4) 0.1261g (1mmol) of p-diynylbenzene and 0.2643g (1mmol) of 4,4' -biphenyldibenzylazide were charged into a three-necked flask equipped with a rotor, and dissolved by adding 20ml of DMSO solvent, and stirred at 45 ℃ for 30min under a nitrogen atmosphere. 0.0125g (5% mmol) of copper sulfate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10ml of deionized water, and added dropwise to the reaction solution with a constant pressure dropping hole for overnight reaction. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated disodium EDTA to generate precipitates, washing the precipitates for three times by using 20ml of deionized water after filtration, filtering the precipitates, dissolving filter cakes in DMSO solvent, pouring 50ml of mixed solution of methanol/water (3:2/v: v), separating out the precipitates, washing the precipitates for 2 to 3 times by using methanol, drying and weighing the precipitates to obtain light yellow solid powder 0.2891g, namely PTA1, and the yield is 74.1%.
Meanwhile, this example also provides a polyphenylsulfone ether triazole (PTA 1') as a comparison, which has the structural formula,
wherein R is
The preparation process comprises the following steps:
(1) 2.5027g (10mmol) of p-methylbenzene, 3.5688g (30mmol) of 3-bromopropyne, 5.5284g (40mmol) of anhydrous potassium carbonate and 50mL of anhydrous acetone solvent are added into a 100mL three-neck flask, nitrogen is introduced, the mixture is stirred at the temperature of 60 ℃ overnight for reaction, thin-plate chromatography TLC is used for tracking the reaction, the reaction is stopped after the reaction is completed, potassium carbonate is removed by filtration, the reaction solution is poured into 100mL of deionized water, extracted for 3 times by 50mL of ethyl acetate, an organic layer is collected, washed twice by saturated saline, anhydrous magnesium sulfate is added for drying, and the solvent is removed under reduced pressure to obtain 2.7838g of a white solid product of propargyl-4, 4' -sulfonyl diphenol ether (marked as a di-terminal phenylsulfone ether alkyne monomer III), wherein the yield is 85.3%.
FIG. 4 shows a diagram of a terminal phenylsulfone ether alkyne monomer III, starting material and intermediate thereof in CDCl 3 Is/are as follows 1 H NMR comparison chart. As can be seen from the figure, the hydrogen of the raw material-OH disappears at 10.54ppm, the characteristic absorption peaks of hydrogen in-CH 2 and C.ident.CH appear in the product at 4.90ppm and 3.64ppm respectively, the integrated ratio of the peak areas of 1,2,3 and 4 in the product is 2:2:2:1, and the theoretical value is consistent, thus the successful preparation of the di-terminal phenylsulfone ether alkyne monomer III is demonstrated.
(2) 0.3264g (1mmol) of propargyl-4, 4 '-sulfonyldiphenol ether and 0.2643g (1mmol) of 4,4' -biphenyldibenzylazide were charged into a three-necked flask equipped with a rotor, dissolved by adding 20mL of DMSO solvent, and stirred at 45 ℃ for 30min under a nitrogen atmosphere. 0.0125g (5% mmol) of copper sulfate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate are dissolved in 10mL of deionized water, and added dropwise to the reaction solution by using a constant pressure dropping hole for reaction overnight. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated disodium EDTA to generate precipitates, washing the precipitates with 20mL of deionized water for three times after filtration, filtering, dissolving the filter cake in DMSO solvent, pouring 50mL of mixed solution of methanol/water (3:2/v: v), separating out the precipitates, washing the precipitates for 2 to 3 times with methanol, drying and weighing to obtain 0.4378g of light yellow solid powder, namely PTA 1', wherein the yield is 74.1%.
Example 2
This example provides a polyaryltriazole (designated PTA2) prepared by the following procedure:
0.1261g (1mmol) of p-diynylbenzene and 0.1882g (1mmol) of p-diazidobenzyl were charged into a three-necked flask equipped with a rotor, dissolved by adding 20ml of DMSO solvent, and stirred at 45 ℃ for 30min under a nitrogen atmosphere. 0.0125g (5% mmol) of copper sulfate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate are dissolved in 10ml of deionized water, and are added into the reaction solution dropwise through a constant pressure dropping hole for reaction overnight. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated disodium EDTA to generate precipitate, washing the precipitate with 20ml of deionized water for three times after filtering, dissolving the filter cake in DMSO solvent, pouring 50ml of mixed solution of methanol/water (3:2/v: v) into the DMSO solvent to separate out the precipitate, washing the precipitate with methanol for 2-3 times, drying and weighing to obtain 0.2363g of light yellow solid powder, namely PTA2, and the yield is 75.2%.
Meanwhile, this example also provides a polyphenylsulfone ether triazole (designated as PTA 2') for comparison. The structural formula of the compound is shown as follows,
wherein R is
The preparation process comprises the following steps:
0.3264g (1mmol) of propargyl-4, 4' -sulfonyldiphenol ether and 0.1882g (1mmol) of p-diazeniumyl were charged into a three-necked flask equipped with a rotor, dissolved by adding 20mL of DMSO solvent, and stirred at 45 ℃ for 30min under a nitrogen atmosphere. 0.0125g (5% mmol) of copper sulfate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate are dissolved in 10mL of deionized water, and added dropwise to the reaction solution by using a constant pressure dropping hole for reaction overnight. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated disodium EDTA to generate precipitates, washing the precipitates with 20mL of deionized water for three times after filtration, filtering, dissolving the filter cake in a DMSO solvent, pouring 50mL of mixed solution of methanol/water (3:2/v: v), separating out the precipitates, washing the precipitates for 2 to 3 times with methanol, drying and weighing to obtain 0.3870g of light yellow solid powder, namely PTA 2', with the yield of 75.2%.
Example 3
This example provides a polyaryltriazole (designated PTA3) prepared by the following procedure:
0.1261g (1mmol) of p-diynylbenzene and 0.1882g (1mmol) of m-diazabenzyl were charged into a three-necked flask equipped with a rotor, dissolved by adding 20ml of DMSO solvent, and stirred at 45 ℃ for 30min under a nitrogen atmosphere. 0.0125g (5% mmol) of copper sulfate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10ml of deionized water, and added dropwise to the reaction solution with a constant pressure dropping hole for overnight reaction. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated disodium EDTA to generate precipitates, washing the precipitates for three times by using 20ml of deionized water after filtration, filtering the precipitates, dissolving filter cakes in DMSO solvent, pouring 50ml of mixed solution of methanol/water (3:2/v: v), separating out the precipitates, washing the precipitates for 2 to 3 times by using methanol, drying and weighing the precipitates to obtain light yellow solid powder 0.2401g, namely PTA3, and the yield is 76.4%.
Meanwhile, this example also provides a polyphenylsulfone ether triazole (designated as PTA 3') for comparison. The structural formula of the compound is shown as follows,
wherein R is
The preparation process comprises the following steps:
0.3264g (1mmol) of propargyl-4, 4' -sulfonyldiphenol ether and 0.1882g (1mmol) of m-diazabenzyl are charged into a three-necked flask with a rotor, dissolved by addition of 20mL of DMSO solvent and stirred at 45 ℃ for 30min under a nitrogen atmosphere. 0.0125g (5% mmol) of copper sulfate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate are dissolved in 10mL of deionized water, and added dropwise to the reaction solution by using a constant pressure dropping hole for reaction overnight. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of saturated disodium EDTA to generate precipitate, washing the precipitate with 20mL of deionized water for three times after filtering, dissolving a filter cake in a DMSO solvent, pouring 50mL of mixed solution of methanol/water (3:2/v: v) into the DMSO solvent to separate out the precipitate, washing the precipitate with methanol for 2-3 times, drying and weighing to obtain 0.3967g of light yellow solid powder, namely PTA 3', and the yield is 76.4%.
And (3) performance testing:
(1) determination of molecular weight and distribution coefficient
The molecular weights and distribution coefficients of PTA1, PTA2 and PTA3 provided in examples 1 to 3 were measured, and the results are shown in Table 1 below.
TABLE 1 molecular weights and distribution coefficients of PTA1, PTA2, PTA3 provided in examples 1-3
(2) Thermal performance testing
The thermal properties of PTA1, PTA2, PTA3 and PTA1 ', PTA2 ' and PTA3 ' provided in examples 1 to 3 were tested. The Tg test process and conditions are that the temperature is raised from 40 ℃ to 300 ℃ at the heating rate of 10 ℃/min, then is raised to 40 ℃ at the cooling rate of 30 ℃/min, and finally is raised to 250 ℃ at the heating rate of 10 ℃/min.
The thermal weight loss test is carried out under the nitrogen atmosphere, the protective gas flow is 30ml/min, the purging gas flow is 30ml/min, and the temperature is increased from 40 ℃ to 600 ℃ at the temperature increasing rate of 10 ℃/min, so as to obtain a thermal weight loss chart of the sample.
Fig. 5 is DSC curves for PTA1, PTA2, PTA3, and PTA1 ', PTA2 ', PTA3 '.
FIG. 6 is a diagram of TG (a) and DTG (b) of PTA1, PTA2, PTA3 and PTA1 ', PTA2 ', PTA3 '.
Table 2 shows the thermal performance test results for PTA1, PTA2, PTA3 and PTA1 ', PTA2 ', PTA3 '.
Table 2 thermal Performance test results of PTA1, PTA2, PTA3 and PTA1 ', PTA 2', PTA3
As can be seen from fig. 5, fig. 6 and table 2, PTA1, PTA2 and PTA3 have better high temperature resistance, and the high temperature resistance of PTA1, PTA2 and PTA3 is better than that of PTA1 ', PTA2 ' and PTA3 '.
The measured glass transition temperature of polytriazole PTA1-PTA3 is PTA1> PTA2> PTA3, and can be explained from the molecular structures of three polymers, the main chain of PTA1 contains a biphenyl structure with higher rigidity, the movement of a chain segment is limited to a great extent, the measured Tg is the largest, and PTA3 has larger intermolecular spacing due to a spiral-like structure, the stacking of the chain is not regular enough, the chain has larger free volume, and the glass transition temperature is greatly reduced relative to PTA1 and PTA 2. Compared with PTA1-PTA3, the glass transition temperature of PTA1 '-PTA 3' is greatly reduced, and the biggest reason is that-O-groups in the alkyne monomer lead the flexibility of the polymer to be improved after the main chain of the polytriazole is introduced, the rotation of the molecular chain is less blocked, and the glass transition temperature is reduced.
The results of the thermal stability of the PTA1-PTA3 polymer show that the thermal stability of PTA1 is the best, and the residual mass at 600 ℃ is the highest, mainly because the rigidity of PTA1 is the highest, the packing of molecular chains is tighter, the acting force between molecular chains is larger, the polymer can be decomposed by heating to a higher temperature, although the molecular weight of PTA3 is higher, the packing between molecular chains is looser, and from the DTG curve, when the temperature is raised to a certain stage, the decomposition rate is increased, the mass is rapidly reduced, and the residual rate at 600 ℃ is the lowest. Compared with the thermal stability of PTA1-PTA3, the difference between PTA1 '-PTA 3' is small, the trend of TG and DTG curves is very close, and the analysis of the reason can have two aspects: on one hand, the flexibility of PTA1 '-PTA 3' is relatively large, the stacking among molecular chains is loose, and the difference between the molecular chains is not as large as that between PTA3 and PTA1 and PTA 2. On the other hand, the molecular weight of PTA3 ' is larger than that of PTA1 ' and PTA2 ', the difference of thermal stability is reduced to a certain extent, and therefore, the three polytriazole resins macroscopically show smaller difference of thermal stability.
(3) Dissolution Performance test
The solubility of diyne benzene (marked as a diaryl acetylene monomer III, abbreviated as III) and PTA1, PTA2 and PTA3 prepared in examples 1-3 is tested, in the testing process, 0.05g of a substance to be tested is accurately weighed by an electronic balance and added into 5mL of a solvent, the solution is continuously stirred at normal temperature, the solution is kept stand after a certain time, after the solid phase is completely precipitated, the upper layer of the solution is taken for analysis at intervals of a certain time, after the concentrations of the two are basically consistent, the test is finished, the solubility is compared, and if no substance to be tested remains, the substance is defined as complete dissolution; if the residual amount of the object to be detected is 1-90%, defining the object to be detected as partial dissolution; if the residual amount of the analyte is greater than 90%, it is defined as insoluble.
The test results are shown in table 3, where, +: dissolving: partial dissolution; -: not dissolved. As can be seen from Table 2, it can be seen that monomer III is well soluble in a slightly more polar aprotic solvent. PTA1 and PTA2 have relatively poor solubility, can only partially dissolve in strongly polar solvents, such as DMF, DMSO, HFIP and the like, and are almost insoluble in weakly polar aprotic solvents such as chloroform, tetrahydrofuran and the like, while PTA3 has better solubility than PTA1 and PTA2 and can better dissolve in aprotic strongly polar solvents. The main reason for this is probably that the meta-position structure of the M3 monomer makes the molecular chain conformation obtained by polymerization present a helical structure, and compared with the relatively regular linear structure of PTA1 and PTA2, the PTA3 has a larger intermolecular spacing, and the solvent is more easily permeated into the polymer chain, and its solubility is relatively better.
Table 3 dissolution test results of PTA1, PTA2 and PTA3
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. A polyaryltriazole characterized by having the structure shown in formula (i):
wherein R is
n is an integer of 27 to 52.
2. The polyaryltriazole of claim 1 wherein R is
3. The polyaryltriazole according to claim 1 wherein n is an integer from 35 to 45.
4. The polyaryltriazole of claim 1 wherein said polyaryltriazole has an average molecular weight of 11000 to 17000.
5. A process for preparing a polyaryltriazole according to any of claims 1 to 4 comprising the steps of: carrying out click polymerization reaction on a two-end-group aryl benzyl azide monomer shown in a formula (II) and a two-end-group aryl alkyne monomer shown in a formula (III) under the action of a click polymerization catalyst to obtain the polyaryl triazole;
6. the method for preparing polyarylazole of claim 5, wherein said click polymerization catalyst is a cuprous salt catalyst.
7. The preparation method of the polyaryltriazole of claim 5, wherein the molar ratio of the click polymerization catalyst to the di-terminal aryl benzyl azide monomer is (1-3): 50.
8. The method for preparing polyarylamidotriazole as claimed in claim 5, wherein the temperature of the click polymerization reaction is 30 to 80 ℃.
9. The method for preparing the polyaryltriazole of claim 5, wherein the molar ratio of the two terminal group arylbenzyl azide monomer to the two terminal group arylalkyne monomer is 1: 1.
10. Use of a polyaryltriazole according to any of claims 1 to 4 in the preparation of a high temperature resistant resin.
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| CN106519226A (en) * | 2015-09-11 | 2017-03-22 | 华东理工大学 | Three-functional-group alkyne derived polytriazole resin and preparation method thereof |
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| MUSTAFA ARSLAN等: ""Dibenzoyldiethylgermane as a visible light photo-reducing agent for CuAAC click reactions"" * |
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