CN116283829A - Co-crystal with thiadiazole and imidazole structure, and preparation method and application thereof - Google Patents
Co-crystal with thiadiazole and imidazole structure, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high molecular compounds, and discloses a eutectic with a thiadiazole and imidazole structure, and a preparation method and application thereof. The chemical formula of the eutectic is (C 2 H 3 N 3 S 2 )(C 4 H 6 N 2 ): wherein C is 2 H 3 N 3 S 2 Is 2-amino-5-mercapto-1, 2, 3-thiadiazole, C 4 H 6 N 2 Is 2-methylimidazole. The thiadiazole-imidazole co-crystal is formed by N-H. Of methylimidazole and thiadiazole N atomsThe N hydrogen bond and the N-H.S hydrogen bond between the amino group of the thiadiazole and the thioketone group are tightly connected to form a three-dimensional eutectic. The eutectic not only has the property of the thiadiazole structural compound, but also has the catalytic performance of imidazole and effectively improves the solubility of the thiadiazole compound; the co-crystal of the thiadiazole and imidazole structure can be applied to a polymer to remarkably improve the mechanical strength.
Description
Technical Field
The invention belongs to the technical field of high molecular compounds, and particularly relates to a eutectic with a thiadiazole and imidazole structure, and a preparation method and application thereof.
Background
The thiadiazole compound has poor water solubility, has a large limitation on the choice of solvents, and limits its wide application. Patent CN 113999254A proposes that the solubility can be enhanced by introducing an imidazole ring, but the patent is prepared by synthesizing a suitable thiadiazole structure and synthesizing the imidazole ring through a multi-step chemical reaction, the preparation method is complicated, and the tertiary nitrogen electron-deficient structure on the thiadiazole ring can be connected with a secondary amine electron-donating body of imidazole to form a hydrogen bond, so that the solubility of the thiadiazole compound is reduced.
Current methods for preparing compounds having imidazole and thiadiazole structures: (1) Firstly selecting a required imidazole structure, then carrying out substitution reaction on hydrogen on-NH-of imidazole, and then synthesizing a thiadiazole structure by using a thiosemicarbazide as a raw material acid catalysis method, an N, N' -dihydrazide as a raw material method, a Schiff base as a raw material method, a microwave radiation synthesis method and the like; (2) Or by synthesizing imidazole with halogen and then reacting with thiadiazole compound with mercapto; (3) There are also compounds having an imidazole structure and a thiadiazole structure prepared by first selecting a desired thiadiazole compound and then synthesizing an imidazole ring. These all require multi-step reactions, the reaction conditions are strictly controlled, the used raw materials and intermediates are numerous, the reaction process is complicated, and the method is difficult to be suitable for industrial high-efficiency production.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a co-crystal with a thiadiazole and imidazole structure.
Another object of the present invention is to provide a method for preparing the co-crystal having a thiadiazole and imidazole structure. The method utilizes the characteristic that the tertiary nitrogen electron-deficient structure on the thiadiazole ring can be connected with the secondary amine electron-donating body of imidazole to form a hydrogen bond, designs and synthesizes a eutectic with thiadiazole and imidazole heterocycle, not only introduces the property of the imidazole structure, but also increases the selectivity of the compound with the thiadiazole structure to the solvent and improves the solubility.
It is a further object of the present invention to provide the use of the co-crystal having a thiadiazole and imidazole structure described above.
The aim of the invention is achieved by the following technical scheme:
a co-crystal having a thiadiazole and imidazole structure, the co-crystal having the chemical formula (C 2 H 3 N 3 S 2 )(C 4 H 6 N 2 ): wherein C is 2 H 3 N 3 S 2 Is 2-amino-5-mercapto-1, 2, 3-thiadiazole, C 4 H 6 N 2 Is 2-methylimidazole.
Preferably, said C 2 H 3 N 3 S 2 And C 4 H 6 N 2 In a molar ratio of 1:0.5 to 4 to form a eutectic.
Further, the co-crystal has an X-ray powder diffraction pattern with characteristic absorption peaks at 2θ angles of 12.58 °, 15.56 °, 16.38 °, 17.26 °, 19.18 °, 22.4 °, 23.74 °, 24.24 °, 25.88 °, 26.5 °, 27.96 °, 28.3 °, 30.6 °, 31.34 °, 32.74 °, 33.1 °, 33.56 °, 34.98 °, 35.44 °, 37.5 °, 39.32 °, 44.48 °.
Further, the unit cell parameters of the co-crystal are: a= 7.4731 (3) a, b= 7.6939 (2) a, c= 17.6071 (6) a, α=90.00°, β=90.00 °, γ=90.00 °, v= 1012.36 (6) a 3.
Further, the co-crystal is formed by two hydrogen bonds: the hydrogen bond between methylimidazole and thiadiazole N atoms is N4-H.cndot.N2=2.793A (< N4-H.cndot.N2= 163.01 °) and N1-H.cndot.N5= 2.763A (< N1-H.cndot.cndot.N5= 170.94 °); the hydrogen bond between the amino group and the thioketone group of the thiadiazole is N3-H3 B.S2A= 3.374A (< N3-H3B) s2a= 164.58 °) and n3—h3a·s2b= 3.406 a (+n3—h3a·s2b= 159.28 °).
The preparation method of the co-crystal with the thiadiazole and imidazole structure comprises the following steps:
s1, a molar ratio is 1: reflux the 2-amino-5-mercapto-1, 2, 3-thiadiazole compound and 2-methylimidazole of 0.5-4 in acetone at 20-90 ℃ for 2-10 h to obtain a reaction solution;
s2, carrying out reduced pressure suction filtration on the reaction liquid, and carrying out rotary evaporation on the obtained filtrate to obtain the eutectic with the thiadiazole and imidazole structure.
Preferably, in the step S2, the pressure of the rotary steaming is-0.06 to-0.1 MPa, the temperature of the rotary steaming is 20-40 ℃, and the time of the rotary steaming is 15-60 min.
The eutectic with the thiadiazole and imidazole structure is applied to the field of preparing polymers or adhesives.
Compared with the prior art, the invention has the following beneficial effects:
1. the thiadiazole-imidazole co-crystal has a thiadiazole structure and an imidazole structure, and the two are tightly connected through an N-H.N hydrogen bond and an N-H.S hydrogen bond to form a three-dimensional co-crystal, namely, the methyl imidazole and the thiadiazole N atom hydrogen bond and the hydrogen bond between the amino group of the thiadiazole and the thioketone group, the co-crystal has the property of a compound with the thiadiazole structure, and meanwhile, the catalytic performance of the imidazole effectively improves the solubility of the thiadiazole compound, effectively improves the solubility of the compound with the thiadiazole structure, and increases the application possibility;
2. the thiadiazole-imidazole co-crystal disclosed by the invention not only introduces the property of an imidazole structure, but also increases a compound with a thiadiazole structure, increases the selectivity to a solvent and improves the solubility.
Drawings
FIG. 1 is a crystallographic structural diagram of a starting material 2-amino-5-mercapto-1, 2, 3-thiadiazole.
FIG. 2 is a crystallographic structural diagram of the starting material 2-methylimidazole.
FIG. 3 is a graph of the molecular stacking hydrogen bonding of the thiadiazole-imidazole co-crystal prepared in example 1.
Fig. 4 is a photograph of an industrial camera of the thiadiazole-imidazole co-crystal prepared in example 1.
Fig. 5 is a powder diffraction pattern of the thiadiazole-imidazole co-crystal prepared in example 1.
FIG. 6 is an infrared spectrum of the thiadiazole-imidazole co-crystal prepared in example 1.
FIG. 7 is a melting point diagram of the thiadiazole-imidazole co-crystal prepared in example 1.
FIG. 8 is a thermogram of a thiadiazole-imidazole co-crystal prepared in example 1.
Fig. 9 is a graph of water contact angle for thiadiazole-imidazole co-crystals prepared in example 1.
Fig. 10 is a photograph of an industrial camera of the thiadiazole-imidazole co-crystal prepared in example 3.
Fig. 11 is an infrared spectrum of the thiadiazole-imidazole co-crystal prepared in examples 1 to 3, the thiadiazole-imidazole powder prepared in comparative example 1.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
Weighing 13.32 g of 2-amino-5 mercapto-1, 2, 3-thiadiazole (CAS number: 2349-67-9, simply referred to as NS) and 8.211 g of 2-methylimidazole (CAS number: 693-98-1, simply referred to as MI) into a flask with a rotor, adding 140 mL of acetone, stirring at room temperature at 500 rpm for 5min to form a colorless transparent solution, placing into an oil bath pot, condensing and refluxing at 70 ℃ for 6h to form a pale yellow transparent solution, and after the reaction is finished, performing suction filtration to obtain a filtrate. The filtrate is placed in a rotary steaming device at 35 ℃ to recycle the acetone solvent, so as to obtain pale yellow thiadiazole-imidazole eutectic, which is abbreviated as NSMI-70, and the yield is more than 95 percent.
The structure of a pale yellow transparent single crystal of thiadiazole-imidazole co-crystal was characterized, and the X-ray diffraction data of this single crystal was obtained by collection and Lp factor correction in a w-scan manner using MoKa radiation (λ= 0.71073 a) on a Bruker Smart Apex CCO plane-probe diffractometer, with absorption correction using the SADABS procedure. The crystal parameters of the co-crystal are shown in table 1, and the 2-amino-5-mercapto-1, 2, 3-thiadiazole and 2-methylimidazole are reacted under the condition of a solvent reflux method to obtain a thiadiazole-imidazole co-crystal, and the analysis of an X-ray diffraction single crystal structure shows that the parameters of a unit cell are a= 7.4731 (3) a, b= 7.6939 (2) a, c= 17.6071 (6) a, a=90.00 degrees, beta=90.00 degrees, gamma=90.00 degrees, and v= 1012.36 (6) a 3.
FIG. 1 is a crystallographic structural diagram of a starting material 2-amino-5-mercapto-1, 2, 3-thiadiazole. As can be seen from FIG. 1, the sulfur atom on the thiadiazole ring is S1, the sulfur atom on the mercapto group is S2, the carbon atom attached to the mercapto group is CI, the carbon atom attached to the amino group is C2, the nitrogen atom on the mercapto side is N1, the nitrogen atom on the amino side is N2, and the nitrogen atom on the amino group is N3. FIG. 2 is a crystallographic structural diagram of the starting material 2-methylimidazole. As can be seen from FIG. 2, the secondary amine on the imidazole ring is N4, the tertiary nitrogen is N5, the carbon atom to which the methyl group is attached is C3, the carbon atom on the secondary amine side is C4, the carbon atom on the tertiary nitrogen side is C5, and the carbon atom of the methyl group is C6.
FIG. 3 is a graph of molecular stacking hydrogen bonding of thiadiazole-imidazole co-crystals. As can be seen from fig. 3, the thiadiazole-imidazole co-crystal is three-dimensional, formed by two hydrogen bonding interactions, the hydrogen bond between methylimidazole and thiadiazole N atom is N4-H.cndot.N2=2.793A (< N4-H.cndot.N2= 163.01) o ) And N1-H n5= 2.763 a (< N1-H. Cndot. N5= 170.94) o ) The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen bond between the amino group and the thioketone group of the thiadiazole is N3-H3B··S2A= 3.374 a (+N3-H3 B·S2A= 164.58) o ) And N3-H3A s2b= 3.406 a (< N3-H3A. S2 B= 159.28) o ). Fig. 4 is a photograph of an industrial camera of the thiadiazole-imidazole co-crystal prepared in example 1. As can be seen from FIG. 4, NSMI-70 samples had a relatively large number of single crystals, and exhibited a regular light-transmitting rectangular parallelepiped shape.
Fig. 5 is an X-ray powder diffraction pattern of the thiadiazole-imidazole co-crystal prepared in example 1, and as can be seen from fig. 5, there are characteristic absorption peaks at 2θ=12.58 °, 15.56 °, 16.38 °, 17.26 °, 19.18 °, 22.4 °, 23.74 °, 24.24 °, 25.88 °, 26.5 °, 27.96 °, 28.3 °, 30.6 °, 31.34 °, 32.74 °, 33.1 °, 33.56 °, 34.98 °, 35.44 °, 37.5 °, 39.32 ° and 44.48 °, and the tested curves and the theoretically predicted curves coincide well, which indicates that the prepared thiadiazole-imidazole co-crystal has no impurity and has high purity.
FIG. 6 is an infrared spectrum of the thiadiazole-imidazole co-crystal prepared in example 1. At 4000-400 cm -1 The raw materials (2-amino-5-mercapto-1, 2, 3-thiadiazole and 2-methylimidazole) and the products (NSMI-70) were subjected to infrared spectral scanning in the wavelength range. As can be seen from fig. 6, the infrared spectrum of 2-methylimidazole: at 1850 cm -1 And 1300 cm -1 Five peaks were present in the vicinity, and analysis was considered to be caused by stretching vibration of c=c double bond and c=n double bond in the heterocyclic compound, at 3137 cm -1 ，3110 cm -1 And 3019 cm -1 Weak absorption peaks at the positions are respectively caused by stretching vibration of N-H bonds and unsaturated C-H bonds, and are 1155 cm to 910 cm -1 Four peaks between the two peaks are caused by the stretching vibration of C-N bonds, and the peak is 900 cm to 600cm -1 Is caused by bending vibrations of the C-H bonds and the N-H bonds. Infrared spectrum of 2-amino-5-mercapto-1, 2, 3-thiadiazole: 1610 cm -1 And 1326 cm -1 Five peaks in the vicinity are caused by stretching vibration of the c=n double bond in the heterocyclic compound, at 3342 cm -1 And 3257 cm -1 The symmetrical absorption peak is-NH 2 Peak of stretching vibration at 3133cm -1 The absorption peak at the position is caused by the stretching vibration of the N-H bond of primary amine, at 2655 cm -1 The weak absorption peak is caused by S-H stretching vibration of sulfhydryl group, and is 1176-1029 cm -1 The three peaks are caused by the expansion and contraction vibration of C-N bond, 900-600 cm -1 Is caused by bending vibrations of the C-H bonds and the N-H bonds. Infrared spectrum of NSMI-70: the characteristic peak of NH bond in imidazole ring is 3137 cm -1 Migration to 3290 cm -1 The characteristic peak of C=N double bond of 2-amino-5-mercapto-1, 2, 3-thiadiazole is also from original 1704 cm -1 ，1627 cm -1 ，1515 cm -1 ，1471 cm -1 ，1332 cm -1 Migrate to 1718 cm -1 ，1614 cm -1 ，1556 cm -1 ，1482 cm -1 ，1336 cm -1 The result is that the N atom in the c=n bond forms a hydrogen bond with the H atom in the imidazole as a hydrogen bond acceptor. -NH in 2-amino-5-mercapto-1, 2, 3-thiadiazole 2 Is characterized by the symmetrical characteristic peak of 3342 cm -1 And 3257 cm -1 Migrate to 3313 cm -1 And 3252 cm -1 Due to-NH 2 And self-SH produce weak hydrogen bonding forces.
FIG. 7 is a melting point diagram of the thiadiazole-imidazole co-crystal prepared in example 1. As can be seen from FIG. 7, the co-crystal had only one relatively sharp endothermic peak at about 163℃and both the endothermic peak of 2-methylimidazole which appeared around 147℃and the endothermic peak of 2-amino-5-mercapto-1, 2, 3-thiadiazole which appeared around 243 ℃. It is clear from this that 2-methylimidazole and 2-amino-5-mercapto-1, 2, 3-thiadiazole have disappeared, but a new thiadiazole-imidazole co-crystal is formed, which means that the co-crystal changes the intermolecular forces and thus the melting point.
FIG. 8 is a thermogram of the thiadiazole-imidazole co-crystal prepared in example 1, as can be seen from FIG. 8, the co-crystal has a thermal stability between the starting materials 2-amino-5-mercapto-1, 2, 3-thiadiazole and 2-methylimidazole. Fig. 9 is a graph of water contact angle for thiadiazole-imidazole co-crystals prepared in example 1. As can be seen from fig. 9, the water contact angle of the thiadiazole-imidazole co-crystal is more hydrophilic than the two starting materials 2-amino-5-mercapto-1, 2, 3-thiadiazole and 2-methylimidazole.
Example 2
Weighing 13.32 g of 2-amino-5 mercapto-1, 2, 3-thiadiazole (CAS number: 2349-67-9, simply referred to as NS) and 8.211 g of 2-methylimidazole (CAS number: 693-98-1, simply referred to as MI) into a flask with a rotor, adding 140 mL of acetone, stirring at room temperature at 500 rpm for 5min to form a colorless transparent solution, placing into an oil bath pot, condensing and refluxing at 50 ℃ for 6h to form a pale yellow transparent solution, and after the reaction is finished, performing suction filtration to obtain a filtrate. The filtrate is placed in a rotary steaming device with the temperature of 35 ℃ to recycle the acetone solvent, and light yellow thiadiazole-imidazole eutectic, abbreviated as NSMI-50, is obtained. NSMI-50 samples have yields greater than 95%, with fewer single crystals and many of the stacked crystal forms.
Example 3
Weighing 13.32 g of 2-amino-5 mercapto-1, 2, 3-thiadiazole (CAS number: 2349-67-9, simply referred to as NS) and 8.211 g of 2-methylimidazole (CAS number: 693-98-1, simply referred to as MI) into a flask with a rotor, adding 140 mL of acetone, stirring at room temperature at 500 rpm for 5min to form a colorless transparent solution, placing into an oil bath pot, condensing and refluxing at 30 ℃ for 6h to form a pale yellow transparent precipitate-free solution, and after the reaction is finished, performing suction filtration to obtain a filtrate. And (3) placing the filtrate in a rotary steaming device at the temperature of 35 ℃, and recovering the acetone solvent to obtain a yellow thiadiazole-imidazole eutectic, which is abbreviated as NSMI-30. The NSMI-30 sample yield is more than 95 percent. Fig. 10 is a photograph of an industrial camera of the thiadiazole-imidazole co-crystal prepared in example 3. As can be seen from fig. 10, the thiadiazole-imidazole co-crystals all present a stacked crystalline form without the presence of a single crystal.
Comparative example 1
13.32 g of 2-amino-5 mercapto-1, 2, 3-thiadiazole (CAS number: 2349-67-9, abbreviated as NS) and 8.211 g of 2-methylimidazole (CAS number: 693-98-1, abbreviated as MI) were weighed into a pan, milled in a shaking stirrer, and stirred at 30℃for 20 days at a stirring speed of 1000 rpm to obtain pale yellow thiadiazole-imidazole powder, the appearance of which abbreviated as F-NSMI was consistent with that of the milled thiadiazole-imidazole co-crystal, which was subjected to infrared test.
Fig. 11 is an infrared spectrum of the thiadiazole-imidazole co-crystal of examples 1 to 3, the thiadiazole-imidazole powder prepared in comparative example 1. As can be seen from FIG. 11, the flow rate is 4000 to 400 cm -1 Is carried out by carrying out infrared spectrum scanning on thiadiazole-imidazole co-crystal NSMI-70, NSMI-50, NSMI-30 and F-NSMI prepared by adopting a mixing method in comparative example 1, and characteristic peak of NH bond in imidazole ring in the infrared spectrum of NSMI-50 is 3137 cm -1 Migration to 3290 cm -1 The characteristic peak of C=N double bond of 2-amino-5-mercapto-1, 2, 3-thiadiazole is also from original 1704 cm -1 ，1627 cm -1 ，1515 cm -1 ，1471 cm -1 ，1332 cm -1 Migration to1718 and 1718 cm -1 ，1614 cm -1 ，1556 cm -1 ，1482 cm -1 ，1336 cm -1 The result is that the N atom in the c=n bond forms a hydrogen bond with the H atom in the imidazole as a hydrogen bond acceptor. -NH in 2-amino-5-mercapto-1, 2, 3-thiadiazole 2 Is characterized by the symmetrical characteristic peak of 3342 cm -1 And 3257 cm -1 Migrate to 3313 cm -1 And 3252 cm -1 Due to-NH 2 And self-SH produce weak interaction forces. Infrared spectrum of NSMI-30: the characteristic peak of NH bond in imidazole ring is 3137 cm -1 Migration to 3290 cm -1 The characteristic peak of C=N double bond of 2-amino-5-mercapto-1, 2, 3-thiadiazole is also from original 1704 cm -1 ，1627 cm -1 ，1515 cm -1 ，1471 cm -1 ，1332 cm -1 Migrate to 1718 cm -1 ，1614 cm -1 ，1556 cm -1 ，1482 cm -1 ，1336 cm -1 The result is that the N atom in the c=n bond forms a hydrogen bond with the H atom in the imidazole as a hydrogen bond acceptor. -NH in 2-amino-5-mercapto-1, 2, 3-thiadiazole 2 Is characterized by the symmetrical characteristic peak of 3342 cm -1 And 3257 cm -1 Migrate to 3313 cm -1 And 3252 cm -1 Due to-NH 2 And self-SH produce weak interaction forces. Infrared spectrum of F-NSMI: the characteristic peak of NH bond in imidazole ring is 3137 cm -1 Migration to 3290 cm -1 The characteristic peak of C=N double bond of 2-amino-5-mercapto-1, 2, 3-thiadiazole is also from original 1704 cm -1 ，1627 cm -1 ，1515 cm -1 ，1471 cm -1 ，1332 cm -1 Migrate to 1718 cm -1 ，1614 cm -1 ，1556 cm -1 ，1482 cm -1 ，1336 cm -1 The result is that the N atom in the c=n bond forms a hydrogen bond with the H atom in the imidazole as a hydrogen bond acceptor. -NH in 2-amino-5-mercapto-1, 2, 3-thiadiazole 2 Is characterized by the symmetrical characteristic peak of 3342 cm -1 And 3257 cm -1 Migrate to 3313 cm -1 And 3252 cm -1 This is due to-NH 2 And self-SH produce weak interaction forces. Such asThe infrared curve of F-NSMI in comparative example 1 in FIG. 11 shows that the infrared peak is coincident with that of the co-crystal, but the intensity of the peak is significantly weaker.
Example 4
The 2-amino-5-mercapto-1, 2, 3-thiadiazole of 0.2. 0.2 g and the thiadiazole-imidazole eutectic prepared in example 1 are respectively weighed into acetonitrile, acetone, absolute ethyl alcohol and deionized water of 10 mL, stirred for 30 min by ultrasonic waves, and whether the solution is dissolved or not is observed. The results are shown in Table 2:
table 2 shows the solvent selectivity comparisons of 2-amino-5-mercapto-1, 2, 3-thiadiazole and thiadiazole-imidazole co-crystals. As can be seen from Table 2, the 2-amino-5 mercapto-1, 2, 3-thiadiazole is insoluble in acetonitrile, absolute ethyl alcohol and deionized water, and insoluble in acetone, and the prepared thiadiazole-imidazole eutectic is good in acetonitrile, absolute ethyl alcohol, deionized water and acetone, which means that the thiadiazole-imidazole eutectic has increased diversity in solvent selectivity and increased solubility compared with 2-amino-5-mercapto-1, 2, 3-thiadiazole.
Example 5
Respectively weighing NSMI-70 powder prepared in example 1 of 0.292 and g, 2-amino-5-mercapto-1, 2, 3-thiadiazole and 2-methylimidazole in 3 beakers, respectively adding 1 mL of N, N-dimethylacetamide, stirring to dissolve completely to form orange transparent solution, colorless transparent solution and colorless transparent solution respectively, respectively adding 2 g of bisphenol A epoxy resin, stirring to form uniform solution, respectively pouring into 3 polytetrafluoroethylene moulds with diameter of 7cm, and heating at 90 ℃ for 8 hours to form orange polymer film, yellow transparent polymer film and brown opaque polymer film respectively. And then transferring the mixture to a vacuum drying oven at 90 ℃ for drying for 2 hours to obtain thiadiazole-imidazole eutectic polymers, thiadiazole polymers and imidazole polymers which are respectively abbreviated as PNSMI, PNS and PMI. The samples were cut into standard tensile bars according to the standard of GB/T1040.3-2006, and tensile experiments were performed at a rate of 5mm/min using an electronic universal tester at a temperature of 25℃and the mechanical properties of the samples were determined as shown in Table 3:
table 3 shows the comparison of properties of polymer films prepared from 2-amino-5-mercapto-1, 2, 3-thiadiazole, 2-methylimidazole and thiadiazole-imidazole cocrystals. As is clear from Table 3, the yield stress of the PNSMI polymer film was 680 MPa and the elongation at break was 15%. The yield stress of the PNS polymer film was 90 MPa and the elongation at break was 4%. The PMI polymer film had a yield stress of 52 MPa and an elongation at break of 6%. Therefore, the mechanical property of the polymer film prepared from the thiadiazole-imidazole eutectic is far stronger than that of the polymer film prepared from the raw materials of 2-amino-5-mercapto-1, 2, 3-thiadiazole and 2-methylimidazole, and the mechanical property of the polymer film is remarkably improved due to the fact that the hydrogen bond formed between the 2-amino-5-mercapto-1, 2, 3-thiadiazole and 2-methylimidazole enhances the network structure of the polymer, and the mechanical strength of the PNSMI polymer film is remarkably improved.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. A co-crystal having a thiadiazole and imidazole structure, characterized in that the co-crystal has the chemical formula (C 2 H 3 N 3 S 2 )(C 4 H 6 N 2 ): wherein C is 2 H 3 N 3 S 2 Is 2-amino-5-mercapto-1, 2, 3-thiadiazole, C 4 H 6 N 2 Is 2-methylimidazole.
2. The co-crystal having a thiadiazole and imidazole structure according to claim 1, wherein said C 2 H 3 N 3 S 2 And C 4 H 6 N 2 In a molar ratio of 1:0.5 to 4 to form a eutectic.
3. The co-crystal having a thiadiazole and imidazole structure according to claim 1, wherein said co-crystal has an X-ray powder diffraction pattern having characteristic absorption peaks at 12.58 °, 15.56 °, 16.38 °, 17.26 °, 19.18 °, 22.4 °, 23.74 °, 24.24 °, 25.88 °, 26.5 °, 27.96 °, 28.3 °, 30.6 °, 31.34 °, 32.74 °, 33.1 °, 33.56 °, 34.98 °, 35.44 °, 37.5 °, 39.32 °, 44.48 ° 2Θ angles.
4. The co-crystal having a thiadiazole and imidazole structure according to claim 1, wherein the unit cell parameters of said co-crystal are: a= 7.4731 (3) a, b= 7.6939 (2) a, c= 17.6071 (6) a, α=90.00°, β=90.00 °, γ=90.00 °, v= 1012.36 (6) a 3.
5. The co-crystal having a thiadiazole and imidazole structure according to claim 1, wherein said co-crystal is formed by two hydrogen bonding:
the hydrogen bond between methylimidazole and thiadiazole N atom is N4-H.cndot.N2=2.793A, < N4-H.cndot.N2= 163.01 °, and N1-H.cndot.N5= 2.763A, < N1-H.cndot.N5= 170.94 °; the hydrogen bond between the amino group and the thiodiazole is N3-H3 B.cndot.S2A= 3.374A, < N3-H3 B.cndot.S2A= 164.58 DEG, N3-H3 A.cndot.S2B= 3.406A, < N3-H3 A.cndot.S2B= 159.28 deg.
6. The method for producing a co-crystal having a thiadiazole and imidazole structure according to any one of claims 1-5, comprising the steps of:
s1, a molar ratio is 1: reflux the 2-amino-5-mercapto-1, 2, 3-thiadiazole compound and 2-methylimidazole of 0.5-4 in acetone at 20-90 ℃ for 2-10 h to obtain a reaction solution;
s2, carrying out reduced pressure suction filtration on the reaction liquid, and carrying out rotary evaporation on the obtained filtrate to obtain the eutectic with the thiadiazole and imidazole structure.
7. The method for preparing a co-crystal with a thiadiazole and imidazole structure according to claim 6, wherein the pressure of the rotary evaporation in the step S2 is-0.06 to-0.1 MPa, the temperature of the rotary evaporation is 20-40 ℃, and the time of the rotary evaporation is 15-60 min.
8. Use of a co-crystal having a thiadiazole and imidazole structure according to any one of claims 1-5 in the field of the preparation of polymers.
9. Use of a co-crystal having a thiadiazole and imidazole structure according to any one of claims 1-5 in the field of adhesive preparation.
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