CN102585220B - Hyperbranched polytriazole formate as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses a hyperbranched polytriazole formate and its preparation method and application. The preparation method of hyperbranched polytriazole formate is as follows: first synthesize the dibasic azide compound containing tetraphenylethylene unit; ; Finally, the target polymer is obtained with a high yield by using the azide compound and the alkyne-containing ester compound to carry out metal-free catalyzed "click" polymerization under heating conditions in a polar solvent. The hyperbranched polytriazole carboxylate prepared by the invention has high 1,4-stereoregularity, good processability, high thermal stability, degradability, photopatterning and aggregation-induced luminescence performance, and the invention also discloses the application of the hyperbranched polytriazole formate in the detection of polynitroaromatic explosives.

Description

A kind of hyperbranched polytriazole formate and its preparation method and application

technical field

The invention relates to the fields of polymer chemistry and material science, in particular to a novel hyperbranched polytriazole formate and its preparation method and application.

Background technique

In the 1960s, German chemist Rolf Huisgen first studied the 1,3-dipolar cycloaddition reaction of cyclic triazoles prepared from organic azide and alkyne compounds (Chem. Ber. 1967, 100, 2494). However, due to the slow reaction rate and the lack of stereoselectivity of the product, this reaction has not been widely used. In 2002, the Meldal and Sharpless research groups independently reported the monovalent copper salt catalyzed azide-alkynyl cycloaddition reaction, and found that the reaction rate was greatly accelerated, and the product was stereoselective, only generating 1,4-disubstituted 1,2,3-triazole compounds (J.Org.Chem.2002, 67, 3057, Angew.Chem., Int.Ed.2011, 40, 2004). Immediately, Sharpless et al named the reaction "click chemistry" reaction.

The "click" reaction is characterized by simple reaction conditions, easy access to raw materials, strong stereoselectivity and atom economy. As a typical "click" reaction, the azide-alkynyl cycloaddition reaction catalyzed by monovalent copper salts has been widely used in many fields such as functional polymer synthesis, surface modification, and preparation of biological and chemical sensors.

In terms of polymer synthesis, monovalent copper-catalyzed azide-alkynyl cycloaddition reactions are mostly used for post-functional modification of polymers. There are few studies on this reaction as a polymerization reaction to prepare polymers, especially hyperbranched polymers. In 2004, Voit et al. tried to prepare hyperbranched polymers using AB ₂ type monomers under the catalysis of copper sulfate and sodium ascorbate, but only insoluble polymers were obtained (Macromol. Rapid Commun. 2004, 25, 1175). In 2008, Katritzky's research group prepared hyperbranched polymers by changing the type of monomers and using A ₂ + B ₃ monomers under the conditions of catalytic or thermal polymerization of copper sulfate and sodium ascorbate. The resulting polymers had poor solubility. And the reaction time is longer (J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 238). The research group of the present invention prepared soluble 1,4- and 1,5-stereoregular hyperbranches respectively by using A ₂ +B ₃ type monomers under the catalysis of organic solvent-soluble monovalent copper and divalent ruthenium Polymerization, and tried metal-free catalyzed thermal polymerization, obtained soluble stereotactic hyperbranched polymers (Macromolecules, 2008, 41, 3808). Li Zhen’s research group at Wuhan University prepared soluble hyperbranched polymers using A ₂ +B ₃ type monomers under the catalysis of copper sulfate and sodium ascorbate by changing the reaction solvent, temperature and end-capping reaction (Macromolecules 2009, 42, 1589, J. Polym. Sci., Part A: Polym. Chem. 2011, 49, 1977).

Monovalent copper-catalyzed click polymerization to prepare hyperbranched polymers often leads to poor solubility of the polymer, and it is difficult to remove the residual copper catalyst in the polymer. If such polymers are used in the fields of biomedicine and optoelectronics, they will produce cytotoxicity and destroy the photophysical properties of the polymer, thereby limiting the application of monovalent copper-catalyzed click polymerization, so the development of metal-free catalyzed click polymerization The preparation of hyperbranched polymers has very important academic and application value.

In addition, most organic light-emitting materials usually show a phenomenon of reduced luminous efficiency or even no light emission in the aggregated state or solid state, that is, aggregation fluorescence quenching, which greatly limits the application range of organic light-emitting materials.

In 2001, Tang Benzhong's research group discovered that silole does not emit light in solution, but exhibits strong luminescent properties in solid state (Chem.Commun.2001, 1740), and named this phenomenon Aggregation-induced emission (Aggregation-induced emission) , AIE): That is, no fluorescence is emitted in the solution state, but the fluorescence is enhanced in the aggregated state. Since the discovery of the AIE phenomenon, a series of small molecules and linear and branched polymers with AIE properties have been synthesized and widely used as fluorescent probes and electroluminescent materials in analysis and detection, biosensing and electroluminescence. Light-emitting devices and other fields (Chem.Commun.2009, 4332). Compared with other types of polymers, hyperbranched polymers exhibit many excellent properties such as low viscosity, no chain entanglement and good compatibility due to their highly branched three-dimensional spherical structure and many functional end groups. And its synthesis method is simple and the cost is low, so the hyperbranched polymer has important application value in the fields of coatings, processing aids, biomedical carriers, photoelectric functional materials, molecular catalysis and reactors. But so far, there are few reports on the preparation of hyperbranched polymers with AIE activity. Our research group recently used A ₂ + B ₃ monomers to prepare polymers with AIE properties under the catalysis of monovalent copper (Chinese patent, application number: 201010590712.5, J.Mater.Chem.2011, 21, 4056,) but The residual copper catalyst in the polymer is difficult to remove, which often affects the biological and photoelectric properties of the polymer. Therefore, it is of great scientific significance and application value to prepare hyperbranched polymers with aggregation-induced luminescent properties by metal-free click polymerization.

Contents of the invention

The invention provides a hyperbranched polytriazole formate, a preparation method of the hyperbranched polytriazole formate and an application for detecting polynitroaromatic explosives in an aggregated state.

In order to achieve the above object, the technical scheme adopted in the present invention is: a kind of hyperbranched polytriazole formic acid ester has the structure shown in formula (I):

where R is:

The preparation method of the hyperbranched polytriazole formic acid ester of the present invention is: carry out metal-free "click" polymerization reaction under the heating condition of dibasic azide compound and alkyne group-containing tribasic ester compound in polar solvent, Obtain the hyperbranched polytriazole formic acid ester. Its preparation steps are:

(1) Preparation of binary azide compounds

Through the McMurry coupling reaction of 4-methylbenzophenone, bromination with NBS, and finally nucleophilic substitution reaction with sodium azide, the binary azide compound is synthesized. The preparation process is divided into three steps:

In the first step, react 4-methylbenzophenone, zinc powder and titanium tetrachloride under the protection of nitrogen in tetrahydrofuran to obtain the first intermediate.

In the second step, the first intermediate, N-bromosuccinimide (NBS) and dibenzoyl peroxide (BPO) are reacted under the protection of nitrogen in carbon tetrachloride to obtain the second intermediate.

In the third step, the second monomer and sodium azide are reacted in dimethyl sulfoxide (DMSO) to generate a binary azide compound, whose structural formula is:

(2) Preparation of tribasic ester compounds containing alkyne groups

The tribasic alcohol and propiolic acid are used as raw materials to prepare the tribasic ester compound containing alkynyl group through esterification. Toluene; add p-toluenesulfonic acid (TsOH) in a catalytic amount, the reaction temperature is 90-140°C, the reaction time is 24-72h, and its structural formula is:

where R is:

(3) Preparation of hyperbranched polytriazole formate

1,3-dipolar cycloaddition polymerization reaction (that is, metal-free catalyzed "click" Polymerization).

The polymerization reaction is as follows: adding the binary azide compound and the tribasic ester compound containing the alkyne group into the polymerization tube at a material ratio of 1 to 1.5:1, adding a polar aprotic solvent, and preparing Alkyne group-containing tribasic ester compound with a concentration of 0.1-0.2 mol/L, preferably 0.12-0.17 mol/L, after fully dissolving, heat up to 50-80°C, preferably 60-70°C , stirred and reacted for 2-12 hours, preferably 4-8 hours, to obtain a polymer solution, which was diluted with a small amount of chloroform, and the polymer solution was added dropwise to an appropriate amount of n-hexane to obtain a white precipitate, which was left to stand, filtered, and dried Obtain hyperbranched polytriazole formic acid ester, its reaction formula is:

Among them: R is:

The polar aprotic solvent can be selected from conventional polar aprotic solvents, preferably: N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methyl pyrrolidone.

The hyperbranched polytriazole carboxylate prepared by the present invention has higher 1,4-stereoregularity, and is soluble in common organic solvents at room temperature, such as dichloromethane, chloroform, tetrahydrofuran, acetone, N,N- Dimethylformamide and dimethyl sulfoxide, etc., have high thermal stability, rapid degradability, cross-linking and patterning under light, and have aggregation-induced luminescent properties.

The hyperbranched polytriazole formic acid ester of the present invention has good processability, high thermal stability, fast degradability, photopatternable and aggregation-induced luminescent properties.

The method for preparing functionalized hyperbranched polytriazole formate by metal-free catalyzed click polymerization of the present invention has easy-to-obtain reaction raw materials, which can be purchased directly or prepared by simple reactions; the polymerization reaction conditions are mild, and it is not harmful to air and water Sensitive, without inert gas protection; the polymerization reaction has a high stereoselective type (1,4-isomer content up to 90%); no by-products are generated during the polymerization process, which is in line with atom economy; the polymerization reaction has good The compatibility of functional groups can easily introduce a variety of functional groups; the polymerization reaction does not use metal catalysts, which can eliminate the cytotoxicity caused by catalyst residues and the impact on the photoelectric performance of materials.

The hyperbranched polytriazole carboxylate of the invention has aggregation-induced luminescent properties, can detect nitroaromatic explosives with high sensitivity, and has important application prospects in preventing explosive attacks.

Description of drawings

)与其相应单体在DMSO-d₆中的核磁共振氢谱对比图(*代表溶剂峰)；Fig. 1 is hyperbranched polytriazole formic acid ester (wherein

) and its corresponding monomer in DMSO-d ₆ in the H NMR comparison chart (* represents the solvent peak);

Figure 2 is a hyperbranched polytriazole formate Three-dimensional fluorescent pattern;

的AIE曲线；Figure 3 is a hyperbranched polytriazole formate

The AIE curve;

在聚集态下检测苦味酸(PA)的荧光淬灭曲线；Figure 4 is a hyperbranched polytriazole formate

Detect the fluorescence quenching curve of picric acid (PA) in the aggregation state;

在聚集态下检测苦味酸(PA)的Stem-Volmer曲线。Figure 5 is a hyperbranched polytriazole formate

The Stem-Volmer curve of picric acid (PA) was detected in aggregated state.

Detailed ways

The present invention will be specifically described below in conjunction with examples, but the protection scope of the present invention is not limited to the following examples.

Example 1

(1) Synthesis of the first monomer containing a binary azide group

Add 9.81g (50mmol) of 4-methylbenzophenone and 6.54g (100mmol) of zinc powder into a 250mL two-necked flask, vacuum three times with nitrogen, add 100mL of tetrahydrofuran, and add 5.56mL of titanium tetrachloride dropwise under ice-cooling (50mmol), after the reaction system was returned to room temperature, heated to reflux for 12h, cooled, filtered, and spin-dried, the resulting crude product was separated and purified by a chromatographic column, and dried in vacuo to obtain 8.59g (95.3% yield) of a white solid, which was first intermediate. ¹ H NMR (400MHz, CDCl ₃ ), δ (TMS, ppm): 7.81(d, 2H), 7.74(d, 2H), 7.54(t, 1H), 7.08(m, 10H), 6.98(m, 8H ), 2.23(d, 6H).

Take 7.21g (20mmol) of the first intermediate, 7.48g (40mmol) of NBS, and 0.05g (0.2mmol) of BPO into a 250mL double-necked flask, vacuum three times with nitrogen, add 125mL of carbon tetrachloride to dissolve, heat and reflux overnight , after the reaction, suction filtration, spin-drying, dissolving with dichloromethane, washing with water three times, spin-drying the organic phase, and drying in vacuo to obtain a yellow solid (11.13g), which is the second intermediate, without further purification, directly proceeds to the next step reaction . Dissolve the yellow solid in 100mL DMSO, add NaN ₃ (3.10g), stir at room temperature, react overnight, add water to terminate the reaction, extract with ether, dry the organic phase, and spin dry, the obtained crude product is separated and purified by chromatography to obtain 4.70 g of white solid (total yield of two-step reaction 53.1%), which is the first monomer.

IR (KBr), v (cm ^-1 ): 2094, 1597, 1508, 1248, 1491, 1443, 1246, 752, 699. ¹ H NMR (400MHz, DMSO-d ₆ ), δ (TMS, ppm): 7.12 (m, 10H), 6.98(m, 8H), 4.36(s, 4H). ¹³ C NMR (100MHz, DMSO-d ₆ ), δ(ppm): 143.6, 143.5, 141.2, 134.5, 131.6, 131.3, 128.6 , 128.5, 127.3, 53.8.

(2) Tribasic esters containing alkynyl groups Synthesis of the second monomer

Add 2.47g (20mmol) of pentaerythriol, 1.16g (6mmol) of p-toluenesulfonic acid, 5.69g (80mmol) of propiolic acid and 100mL of toluene into a 250mL two-necked flask equipped with a water separator and a spherical condenser, and heat After reflux for 36 hours, toluene was evaporated, dissolved in dichloromethane, washed three times with water, the organic phase was dried, spin-dried, separated and purified by chromatography, and dried in vacuo to obtain 4.14 g of white solid (75.0% yield), which was the first Two monomers.

IR (KBr), v (cm ^-1 ): 3274, 2936, 2122, 1748, 1594, 1472, 1382, 1228, 995, 752, 698. ¹ H NMR (400MHz, DMSO-d ₆ ), δ (TMS, ppm): 4.59 (s, 3H), 4.12 (s, 6H), 0.98 (s, 3H). ¹³ C NMR (100MHz, DMSO-d ₆ ), δ (ppm): 152.3, 80.0, 74.7, 67.2, 38.4 , 16.6.

(3) Preparation of hyperbranched polytriazole formate by metal-free "click" polymerization

Add 66.3mg (0.15mmol) of the first monomer, 27.6mg (0.10mmol) of the second monomer and 0.6mL N,N-dimethylformamide into a 10mL polymerization tube. After the monomers are completely dissolved, heat up to 60 °C for 5 hours. After the reaction solution was diluted with 5 mL of chloroform, it was added dropwise into 200 mL of rapidly stirring n-hexane to obtain a white flocculent precipitate. Stand overnight, filter and dry to obtain 82.8 mg of polymer (yield 88.2%).

The results of gel permeation chromatography (GPC) showed that the weight average molecular weight (M _w ) was 7200, and the molecular weight distribution (PDI) was 2.65. IR(KBr), v(cm ^-1 ): 3275, 2970, 2867, 2113, 1725, 1545, 1460, 1391, 1357, 1219, 1039, 768, 698. H NMR spectrum of the polymer and its corresponding monomer The comparison diagram is shown in accompanying drawing 1, and it can be determined from the figure that the polymer is a hyperbranched polytriazole formate, and the chemical shifts of 8.92ppm and 8.65ppm respectively correspond to 1,4- and 1,5-isomerism in the polymer According to the characteristic peak of the hydrogen atom on the triazole ring, the integrated area was calculated, and the 1,4-isomer content was 89.2%, which indicated that the polymer had high stereoregularity.

(4) Performance characterization of hyperbranched polytriazole formate

The hyperbranched polytriazole formate is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, acetone, N,N-dimethylformamide and dimethyl sulfoxide at room temperature, indicating that it has good solubility Processability; the 5% thermal weight loss temperature of the polymer is 375°C, indicating that it has high thermal stability; the polymer can be completely degraded within half an hour under the action of a catalytic amount of potassium hydroxide, indicating that it has rapid degradability; The polymer is cross-linked and patterned under ultraviolet light irradiation, as shown in Figure 2; the tetrahydrofuran solution of the polymer does not emit light, but it emits strongly after adding a poor solvent, indicating that it has aggregation-induced luminescent properties, as shown in Figure 3.

(5) Detection of hyperbranched polytriazole carboxylate on nitroaromatic explosives

The process of detecting picric acid (PA): first prepare a tetrahydrofuran solution (water content volume fraction 90%) of hyperbranched polytriazole formate with a content of 10 ^-5 M as the test substance, and then add different contents of the test substance PA in turn , respectively rapid test fluorescence spectra. The results showed that: when no PA was added, the fluorescence of the test object was very strong; when PA was added, the fluorescence was weakened, and with the increase of the added PA content, the fluorescence was gradually weakened, see Figure 4. The fluorescence attenuation multiple of the detected substance is plotted against the amount of PA added, i.e. the Stem-Volmer curve (accompanying drawing 5), and it is found that when the PA content of the detected substance is low, the curve is a straight line; when the PA content is high, the curve Deviation from a straight line bends upward, that is, the fluorescence change of the detected substance increases, indicating that the hyperbranched polytriazole carboxylate can detect nitroaromatic explosives with high sensitivity.

Example 2

(1) The synthesis of the first monomer is the same as in Example 1.

的合成同实施例1。(2) The second monomer

The synthesis is the same as in Example 1.

(3) Preparation of hyperbranched polytriazole formate

Add 66.3mg (0.15mmol) of the first monomer, 27.6mg (0.10mmol) of the second monomer and 1mL of N,N-dimethylformamide into a 10mL polymerization tube. After the monomer is completely dissolved, raise the temperature to 60°C React for 5 hours. After the reaction solution was diluted with 5 mL of chloroform, it was added dropwise into 200 mL of rapidly stirring n-hexane to obtain a white flocculent precipitate. Stand overnight, filter and dry to obtain 73.0 mg of polymer (yield 77.7%). GPC results showed: _Mw = 5100, PDI = 2.63. Other characterization results are the same as in Example 1.

Example 3

(1) The synthesis of the first monomer is the same as in Example 1.

(2) The second monomer The synthesis is the same as in Example 1

(3) Preparation of hyperbranched polytriazole formate

Add 66.3mg (0.15mmol) of the first monomer, 33.2mg (0.12mmol) of the second monomer and 0.5mL N,N-dimethylformamide into a 10mL polymerization tube, and after the monomer is completely dissolved, heat up to 60 °C for 12 hours. After the reaction solution was diluted with 5 mL of chloroform, it was added dropwise into 200 mL of rapidly stirring n-hexane to obtain a white flocculent precipitate. Stand overnight, filter and dry to obtain 82.4 mg of polymer (yield 84.7%). GPC results showed: _Mw = 13000, PDI = 5.27. Other characterization results are the same as in Example 1.

Example 4

(1) The synthesis of the first monomer is the same as in Example 1.

(2) The second monomer The synthesis is the same as in Example 1.

(3) Preparation of hyperbranched polytriazole formate

Add 66.3mg (0.15mmol) of the first monomer, 27.6mg (0.10mmol) of the second monomer and 0.6mL N,N-dimethylformamide into a 10mL polymerization tube, and after the monomer is completely dissolved, heat up to 60 °C for 5 hours. After the reaction solution was diluted with 5 mL of chloroform, it was added dropwise into 200 mL of rapidly stirring n-hexane to obtain a white flocculent precipitate. Stand overnight, filter and dry to obtain 78.3 mg of polymer (yield 83.4%). GPC results showed: _Mw = 6800, PDI = 2.90. Other characterization results are the same as in Example 1.

Example 5

(1) The synthesis of the first monomer is the same as in Example 1.

的合成同实施例1。(2) The second monomer

The synthesis is the same as in Example 1.

(3) Preparation of hyperbranched polytriazole formate

Add 66.3mg (0.15mmol) of the first monomer and 27.6mg (0.10mmol) of the second monomer into a 10mL polymerization tube, vacuumize and blow nitrogen three times, add 0.6mL N, N-dimethylformamide, and wait until the monomer After complete dissolution, the temperature was raised to 60° C. to react for 5 hours. After the reaction solution was diluted with 5 mL of chloroform, it was added dropwise into 200 mL of rapidly stirring n-hexane to obtain a white flocculent precipitate. Stand overnight, filter and dry to obtain 80.6 mg of polymer (yield 85.8%). GPC results showed: _Mw = 6100, PDI = 2.44. In this polymkeric substance proton nuclear magnetic resonance spectrum, in chemical shift 8.90ppm and 8.62ppm place corresponding respectively in polymkeric substance 1,4- and 1, the characteristic peak of hydrogen atom on the 5-isomer triazole ring, calculate integral area, obtain The 1,4-isomer content was 90.1%. Other characterization results are the same as in Example 1.

Example 6

(1) The synthesis of the first monomer is the same as in Example 1.

的合成同实施例1。(2) The second monomer

The synthesis is the same as in Example 1.

(3) Preparation of hyperbranched polytriazole formate

Add 66.3mg (0.15mmol) of the first monomer, 27.6mg (0.1mmol) of the second monomer and 0.6mL N,N-dimethylformamide into a 10mL polymerization tube. After the monomer is completely dissolved, heat up to 70 °C for 4 hours. After the reaction solution was diluted with 5 mL of chloroform, it was added dropwise into 200 mL of rapidly stirring n-hexane to obtain a white flocculent precipitate. Stand overnight, filter and dry to obtain 76.8 mg of polymer (yield 81.8%). GPC results showed: _Mw = 20600, PDI = 6.06. Other characterization results are the same as in Example 1.

Example 7

(1) The synthesis of the first monomer is the same as in Example 1.

的合成同实施例1。(2) The second monomer

The synthesis is the same as in Example 1.

(3) Preparation of hyperbranched polytriazole formate

Add 66.3mg (0.15mmol) of the first monomer, 27.6mg (0.10mmol) of the second monomer and 0.6mL N,N-dimethylformamide into a 10mL polymerization tube, and after the monomers are completely dissolved, heat up to 80 °C for 4 hours. After the reaction solution was diluted with 5 mL of chloroform, it was added dropwise into 200 mL of rapidly stirring n-hexane to obtain a white flocculent precipitate. Stand overnight, filter and dry to obtain 80.7 mg of polymer (yield 85.9%). GPC results showed: _Mw = 52700, PDI = 7.08. Other characterization results are the same as in Example 1.

Example 8

(1) The synthesis of the first monomer containing a binary azide group is the same as in Example 1.

(2) Synthesis of the second monomer (R=CH ₂ -CH-CH ₂ ) of the alkynyl-containing tribasic ester

Add 1.84g (20mmol) of glycerol, 1.16g (6mmol) of p-toluenesulfonic acid, 5.60g (80mmol) of propiolic acid and 100mL of toluene into a 250mL two-necked flask equipped with a water separator and a spherical condenser, and heat to reflux After reacting for 48h, toluene was evaporated, dissolved in dichloromethane, washed three times with water, the organic phase was dried, spin-dried, separated and purified by chromatographic column, and vacuum-dried to obtain 1.51 g of light yellow oily liquid (28.8% yield), which was The second monomer of R= _CH2 -CH- _CH2 . ¹ H NMR (400MHz, DMSO-d ₆ ), δ (TMS, ppm): 5.40 (m, 1H), 4.66 (d, 3H), 4.44 (m, 4H). ¹³ C NMR (100MHz, DMSO-d ₆ ), δ(ppm): 152.0, 151.7, 80.9, 80.4, 74.5, 74.4, 70.6, 63.8. HRMS (MALDI-TOF), m/z calculated for C ₁₂ H ₈ O ₆ Na[M+Na] ⁺ =271.0219, found=271.0223.

(3) Preparation of hyperbranched polytriazole formate by metal-free "click" polymerization

Add 132.8mg (0.30mmol) of the first monomer, 49.6mg (0.20mmol) of the second monomer and 1.2mL N,N-dimethylformamide into a 10mL polymerization tube, and after the monomers are completely dissolved, heat up to 60 °C for 5 hours. After the reaction solution was diluted with 10 mL of chloroform, it was added dropwise into 300 mL of rapidly stirring n-hexane to obtain a white flocculent precipitate. Stand overnight, filter and dry to obtain 167.1 mg of polymer (yield 91.6%).

Gel permeation chromatography (GPC) results showed: GPC results showed: M _w =4400, PDI=2.21. In the hydrogen nuclear magnetic resonance spectrogram of this hyperbranched polytriazole formic acid ester, in the chemical shift 8.82ppm and 8.68ppm respectively correspond to the hydrogen atom on the 1,4- and 1,5-isomer triazole ring in the polymer According to the characteristic peaks and the calculation of the integral area, the content of 1,4-isomer is 82.6%, indicating that the polymer has high stereoregularity.

(4) Performance characterization of hyperbranched polytriazole formate

The hyperbranched polytriazole formate is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, acetone, N,N-dimethylformamide and dimethyl sulfoxide at room temperature, indicating that it has good solubility Processability; the 5% thermal weight loss temperature of the polymer is 333 ° C, indicating that it has high thermal stability; the polymer can be rapidly degraded within half an hour under the action of a catalytic amount of potassium hydroxide; the polymer is irradiated with ultraviolet light Cross-linking and patterning can occur under the conditions; the polymer does not emit light in the solution state, but emits strongly after the aggregated or solid state, indicating that it has aggregation-induced luminescent properties.

(5) Detection of hyperbranched polytriazole carboxylate on nitroaromatic explosives

The process of detecting picric acid (PA): first prepare a tetrahydrofuran solution (water content volume fraction 90%) of hyperbranched polytriazole formate with a content of 10 ^-5 M as the test substance, and then add different contents of the test substance PA in turn , respectively rapid test fluorescence spectra. The results showed that: when no PA was added, the fluorescence of the test object was very strong; when PA was added, the fluorescence was weakened, and with the increase of the added PA content, the fluorescence was gradually weakened, see Figure 4. By plotting the fluorescence weakening factor of the detected substance and the amount of PA added, it is found that when the PA content of the detected substance is low, the curve is a straight line; when the PA content is high, the curve deviates from the straight line and bends upward, that is, the fluorescence of the detected substance The change increases, indicating that the hyperbranched polytriazole carboxylate can detect nitroaromatic explosives with high sensitivity.

Claims (7)

1. hyperbranched poly triazole manthanoate is characterized in that: have suc as formula the structure shown in (I):

Wherein: R is:

Or CH ₂--CH--CH ₂

2. the preparation method of a hyperbranched poly triazole manthanoate according to claim 1, it is characterized in that: structural formula is carried out polyreaction suc as formula first monomer shown in (II) and structural formula suc as formula second monomer shown in (III) under the heating condition in polar aprotic solvent, obtain described hyperbranched poly triazole manthanoate;

In the formula (III): R is:

Or CH ₂-CH---CH ₂

The ratio of described first monomer and the second monomeric amount of substance is 1～1.5 ︰ 1, and the second monomeric amount of substance concentration is 0.1～0.2mol/L.

3. the preparation method of hyperbranched poly triazole manthanoate according to claim 2 is characterized in that: the temperature of reaction of described polyreaction is 50～80 ℃.

4. the preparation method of hyperbranched poly triazole manthanoate according to claim 2 is characterized in that: the reaction times of described polyreaction is 2～12 hours.

5. the preparation method of hyperbranched poly triazole manthanoate according to claim 2 is characterized in that: described polar aprotic solvent is: N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or N-Methyl pyrrolidone.

6. the purposes of hyperbranched poly triazole manthanoate according to claim 1 is characterized in that: described hyperbranched poly triazole manthanoate is used for the detection of many nitro arene explosive substances under state of aggregation.

7. the purposes of hyperbranched poly triazole manthanoate according to claim 6 is characterized in that: described state of aggregation is meant that described hyperbranched poly triazole manthanoate is dispersed in the mixed solvent of tetrahydrofuran (THF) that volume ratio is 1 ︰ 1～9 and water.

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