Polyamine containing triazole ring and preparation method and application thereof

A technology of polyamines and triazole rings, applied in the field of polyamines containing triazole rings and its preparation, can solve the problems of low yield, difficult synthesis, high cost, etc., and achieve excellent heat resistance and wide application prospects

Inactive Publication Date: 2010-07-14

安徽中科达美新材料科技有限公司

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AI-Extracted Technical Summary

Problems solved by technology

The introduction of aromatic, symmetrical, basic and polar pyridine rings into polyimide not only maintains the excellent thermal stability and chemical stability of polyimide, but also greatly improves the processing properties of polymers such as Solubility and film-forming properties (a.Sus...

Abstract

The invention relates to polyamine containing a triazole ring and a preparation method and application thereof. The preparation method of the polyamine comprises the following steps of: preparing an azide by a nucleophilic substitution reaction; synthesizing the polyamine containing the triazole ring by the Huisgen cycloaddition reaction of the azide and a compound with alkynyl amine; and applying the polyamine containing the triazole ring to the preparation of polyimide. The invention has the following advantages that: polytriazole imide has superior processable property and can be dissolved in polar solvents, such as DMAc, DMF, DMSO, NMP and the like; the prepared polytriazole imide has the properties of the polyimide, such as superior heat resistance, low-temperature resistance, chemical resistance, mechanical properties, dielectric and insulation properties, fire retardance, bonding properties and the like; the polytriazole imide can be used as a functional polyimide material and is especially suitable for serving as a metal coating material and a corrosion-resistant material; and the novel polytriazole imide material has extensive application prospect in the fields of aviation, spaceflight, ships, micro-electronics and the like.

Application Domain

Organic chemistry

Technology Topic

SolventCorrosion resistant +13

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Examples

Experimental program(6)

Example Embodiment

[0046] Example 1

[0047] (1) Synthesis of 1,4-diazide methylbenzene

[0048] Add p-dichloromethylbenzene (0.05mol) and NaN in a three-necked flask 3 (0.15mol), toluene (20mL), and N,N-dimethylformamide (20mL), heated to 70~75℃ with stirring, reacted at constant temperature for 3 hours, after the reaction, the reaction product was cooled to room temperature and poured into In 200 mL of deionized water, stand overnight under freezing conditions to precipitate white flake crystals, filtered, and the filter cake was washed with deionized water, and dried to obtain a white powdery solid with a yield of 90%. Melting point: 27~29℃; FT-IR (KBr, v, cm -1 ): 2089(-N 3 Stretching vibration); 1 H-NMR(CDCl 3 , TMS) δ: 7.33 (s, 4H, Ha), 4.35 (s, 4H, Hb), its structural formula is:

[0049]

[0050] (2) Synthesis of 1,4-bis[4-(3-aminophenyl)-1,2,3-triazole-1-methylene]benzene

[0051] Add 1,4-diazide methylbenzene (0.01mol), m-aminophenylacetylene (0.02mol), CuSO to the flask 4 ·5H 2 O (0.005mol), sodium ascorbate (0.01mol), N,N-dimethylformamide (25mL), stir on a magnetic stirrer at room temperature for 48 hours; after the reaction, pour the product into 300mL deionized water and let it stand After 2h, filter, wash with deionized water twice, and finally wash with ethanol several times, filter, and dry to obtain a gray powdery solid with a yield of 92%. Melting point: 151~154℃; FT-IR (KBr, v, cm -1 ): 3420, 3339 (NH 2 Stretching vibration), 3134 (triazole ring-H); 1 H-NMR(CDCl 3 , TMS) δ: 8.45 (s, 2H, Hc), 7.43 (s, 4H, Ha), 7.15 (s, 4H, Hd, f), 6.92 (d, 2H, Hg), 6.53 (d, 2H, He ), 5.62 (s, 4H, Hb), 5.05 (s, 4H, Hh), the structural formula is:

[0052]

Example Embodiment

[0053] Example 2

[0054] (1) Synthesis of 4,4-diazide methyl biphenyl

[0055] Add p-dichloromethyl biphenyl (0.05mol) and NaN in a three-necked flask 3 (0.15mol), toluene (20mL) and DMF (20mL), heated to 70~75℃ under stirring, reacted at constant temperature for 3 hours, after the reaction, the reaction product was cooled to room temperature, poured into 200mL deionized water, and left to stand overnight , A white solid precipitated, filtered, the filter cake was washed with deionized water, and dried to obtain a white powder solid with a yield of 89%. Melting point 68~71℃; FT-IR(KBr, v, cm -1 ): 2089(-N 3 Stretching vibration); 1 H-NMR(CDCl 3 , TMS) δ: 7.33 (s, 4H, Ha), 7.29 (s, 4H, Ha), 4.35 (s, 4H, Hb), its structural formula is:

[0056]

[0057] (2) Synthesis of 4,4-bis[4-(3-aminophenyl)-1,2,3-triazole-1-methylene]biphenyl

[0058] Add 1,4-diazide methylbenzene (0.01mol), m-aminophenylacetylene (0.02mol), CuSO to the flask 4 ·5H 2 O (0.005 mol), sodium ascorbate (0.01 mol), triethylamine (0.02 mol), N,N-dimethylacetamide (25 mL), and stirring on a magnetic stirrer at room temperature for 40 hours. After the reaction, the product was poured into 300mL deionized water, after standing for 2 hours, filtered, then washed with deionized water twice, and finally washed with ethanol several times, filtered, and dried to obtain a pale yellow powdery solid with a yield of 90% . Melting point: 163~166℃; FT-IR (KBr, v, cm -1 ): 3410, 3319 (NH 2 Stretching vibration), 3130 (triazole ring-H); 1 H-NMR(CDCl 3 , TMS) δ: 8.42 (s, 2H, Hc), 7.30 (s, 8H, Ha), 7.22 (s, 4H, Hd, f), 6.95 (d, 2H, Hg), 6.53 (d, 2H, He ), 5.22(s, 4H, Hb), 5.01(s, 4H, Hh), the structural formula is:

[0059]

Example Embodiment

[0060] Example 3

[0061] (1) Synthesis of diethylene glycol diazide

[0062] The synthesis reaction is carried out in two steps, firstly the chlorination of polyethylene glycol, and then azide, the reaction equation is:

[0063]

[0064] Add 0.08mol of polyethylene glycol, SOCl into a 500mL flask equipped with stirring 2 200mL, equipped with spherical condenser and gas absorption tube, heated to 65℃ with oil bath, and stirred for 72h. After the reaction, the excess SOCl was removed by vacuum distillation on the rotary evaporator 2 , Join NaHCO 3 The aqueous solution is filtered to pH>7. 50mL CHCl for filtrate 3 Extract three times, then add anhydrous magnesium sulfate to dry, filter with suction, and distill off the solvent to obtain polyethylene glycol chlorinated product.

[0065] Add 0.08mol of the chlorinated product of the above-synthesized polyethylene glycol into a 250mL single-necked round bottom flask equipped with stirring, NaN 3 0.4mol, 150mL deionized water, install a spherical condenser, heat to 100°C with an oil bath, and react for 100h under stirring. After the reaction, cool down and use 100mL CHCl 3 After three extractions, the chloroform layer was washed three times with water, then collected in a 250 mL single-neck round bottom flask, added with anhydrous magnesium sulfate to dry, filtered with suction, and evaporated to remove the solvent to obtain a colorless transparent liquid with a yield of 90%. FT-IR (KBr, v, cm -1 ): 2800~2900 (C-H stretching vibration), 2089 (-N 3 Stretching vibration), 1110 (-O- stretching vibration); 1 H-NMR(CDCl 3 , TMS)δ: 3.68 (tr, 8H, Hb), 3.38 (tr, 4H, Ha), the structural formula is:

[0066]

[0067] (2) Synthesis of bis[4-(3-aminophenyl)1,2,3-triazole-1-methylene]diethylene glycol

[0068] Add diethylene glycol azide (0.01mol), m-aminophenylacetylene (0.02mol), and CuSO to the flask 4 ·5H 2 O (0.01mol), sodium ascorbate (0.01mol), N,N-dimethylformamide (25mL), stirred for 48 hours at room temperature under a magnetic stirrer. After the reaction, the product was poured into 300 mL of deionized water. After standing for 2 hours, it was filtered, washed with deionized water twice, and finally washed with ethanol several times, filtered, and dried to obtain a pale yellow powdery solid with a yield of 90%. . Melting point: 116-118°C; FT-IR (KBr, v, cm-1): 3345, 3219 (NH 2 Stretching vibration), 3126 (triazole ring-H); 1 H-NMR (CDCl3, TMS) δ: 8.42 (s, 2H, Hc), 7.22 (s, 4H, Hf, g), 6.95 (s, 2H, Hd), 6.53 (s, 2H, He), 5.12 ( s, 4H, Hh), 4.53 (tr, 4H, Ha), 3.82 (tr, 4H, Ha), 3.53 (s, 4H, Hb), the structural formula is:

[0069]

PUM

Property	Measurement	Unit
Thermal decomposition temperature	360.0	°C

Description & Claims & Application Information

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Classification and recommendation of technical efficacy words

Broad application prospects
Good heat resistance

Polyamine containing triazole ring and preparation method and application thereof

A technology of polyamines and triazole rings, applied in the field of polyamines containing triazole rings and its preparation, can solve the problems of low yield, difficult synthesis, high cost, etc., and achieve excellent heat resistance and wide application prospects

AI-Extracted Technical Summary

Problems solved by technology

Abstract

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Examples

Example Embodiment

Example Embodiment

Example Embodiment

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Description & Claims & Application Information

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