Polyaromatic ether amide containing anthrone and pyridine structures and preparation method of polyaromatic ether amide

Abstract

The invention relates to polyaromatic ether amide containing anthrone and pyridine structures and a preparation method of the polyaromatic ether amide. The preparation method includes: subjecting anthrone, thionyl chloride and phenol to one-pot two-step condensation to obtain 10,10-di(4-hydroxy phenyl)-9(10H)-anthrone, subjecting the 10,10-di(4-hydroxy phenyl)-9(10H)-anthrone and 2-chloro-5-nitropyridine to nucleophilic substitution to obtain dinitro-compound 10,10-di[4-(4-nitro-3-pyridineoxy)phenyl]-9(10H)-anthrone, performing palladium carbon / hydrazine hydrate reduction to obtain aromatic diamine 10,10-di[4-(4-nitro-3-pyridineoxy)phenyl]-9(10H)-anthrone, and subjecting aromatic diacid chloride such as paraphthaloyl chloride to condensation to prepare the polyaromatic ether amide containing anthrone and pyridine structures. The polyaromatic ether amide has the advantages that the polyaromatic ether amide is a novel high-performance high polymer material, excellent in heat resistance and mechanical performance, high in dielectric constant, capable of being dissolved in polar solvents such as DMAc and NMP at normal temperature and good in film forming performance; a polymer film obtained by subjecting the polyaromatic ether amide to solution processing is good in toughness and has potential application prospect in fields such as aerospace and electric products.

Description

technical field

[0001] The invention relates to a polyarylether amide containing anthrone and pyridine structures and a preparation method thereof. The polyarylether amide containing anthrone and pyridine structures is a new type of special polymer material and belongs to the technical field of polymer synthesis . Background technique

[0002] Aromatic Polyamides (Aromatic Polyamides) is an important class of special engineering plastics, with good thermal stability, outstanding mechanical properties and strong chemical corrosion resistance, is widely used in aerospace, transportation, electronic appliances, chemical industry In high-tech fields such as military industry. However, commercialized varieties, such as Kevlar fiber (polyparaphenylene terephthalamide, called aramid fiber 1414 in my country) and Nomex fiber (polyisophthalamide isophthalamide) developed successively by DuPont Company of the United States Amine, which is called aramid fiber 1313 in my country), etc....

Examples

Embodiment 1

[0045] (1) Synthesis of 10,10-bis(4-hydroxyphenyl)anthracene-10(9H)-one(4)

[0046] Add anthrone 3.88g (20mmol) and thionyl chloride (15mL) into a 100mL single-necked bottle, reflux for 2h, evaporate and recover the remaining thionyl chloride, continue to add 15mL of xylene and excess phenol 3.76g (40mmol ), slowly heated to 130 ° C, reacted for 3 hours, stopped the reaction, cooled to room temperature, filtered, and the residual solid was washed with an appropriate amount of dichloromethane to obtain a crude product. The crude product was recrystallized with acetone, and after drying, 6.81 g of a light gray powder solid was obtained. The rate is 90%, and the melting point is 306-307°C. 1 H NMR (400MHz, DMSO-d 6 ): δ=9.44(s, 2H), 8.11(d, J=9.6Hz, 2H), 7.59(t, J=7.0Hz, 2H), 7.47(t, J=7.4Hz, 2H), 7.16(d ,J=7.9Hz,2H),6.72(d,J=8.7Hz,4H),6.65(d,J=8.7Hz,4H)( figure 1 ).

[0047] (2) Synthesis of 10,10-bis[4-(4-nitro-3-pyridyloxy)phenyl]-9(10H)-anthrone (5)

[0048] Add (4) 3.78...

Embodiment 2

[0052] Preparation of polyaryletheramide (PA-1a~PEA-1e):

[0053] Taking polyarylether amide (PA-1b) as an example, there are N 2 10,10-bis[4-(4-amino-3-pyridyloxy)phenyl]-9(10H)-anthrone (2) (5mmol, 2.8131g) and DMAc( 10mL), stirred in an ice-water bath until completely dissolved, then added isophthaloyl dichloride (3b) (5mmol, 1.0151g), and then added DMAc to adjust the solid content of the reaction system to about 20%. The reaction was carried out for 1 h at room temperature, and then at room temperature for 10 h to obtain a yellow transparent viscous solution. After the reaction, the viscous solution was transferred into 100 mL of methanol to obtain a white fibrous solid, which was filtered with suction, ground into solids, put into a Soxhlet extractor and extracted with hot methanol for 48 hours, and then vacuum-dried at 80°C for 12 hours. The remaining polyaryletheramides were synthesized in a similar way.

Embodiment 3

[0055] Preparation of Polyaryletheramide Films

[0056] Take 0.5g polymer sample, add appropriate amount of anhydrous DMAc to make a dilute solution, put the cleaned glass plate on a constant temperature heating plate at 60-70°C, apply the solution evenly on the glass plate, and wait for the solvent to dry , remove the polymer film, put it in a vacuum oven and dry it at 100°C for 12 hours.

[0057] (1) Structural analysis of polyaryletheramide

[0058] Taking polyarylether amide (PA-1b) as an example, Figure 4 It is the infrared spectrogram of PA-1b. It can be seen from the data in the figure that –NH does not appear 2 The characteristic absorption peak at 1656cm –1 The characteristic absorption peak of C=O in the amide group appeared at , and at 1225cm –1 The characteristic absorption peak of aryl ether (Ar–O–Ar) appeared at , indicating that the polymerization reaction between diamine and diacid chloride monomer occurred to form an amide bond.

[0059] Polyaryletherami...

technical field

[0001] The invention relates to a polyarylether amide containing anthrone and pyridine structures and a preparation method thereof. The polyarylether amide containing anthrone and pyridine structures is a new type of special polymer material and belongs to the technical field of polymer synthesis . Background technique

[0002] Aromatic Polyamides (Aromatic Polyamides) is an important class of special engineering plastics, with good thermal stability, outstanding mechanical properties and strong chemical corrosion resistance, is widely used in aerospace, transportation, electronic appliances, chemical industry In high-tech fields such as military industry. However, commercialized varieties, such as Kevlar fiber (polyparaphenylene terephthalamide, called aramid fiber 1414 in my country) and Nomex fiber (polyisophthalamide isophthalamide) developed successively by DuPont Company of the United States Amine, which is called aramid fiber 1313 in my country), etc....

Examples

Embodiment 1

[0045] (1) Synthesis of 10,10-bis(4-hydroxyphenyl)anthracene-10(9H)-one(4)

[0046] Add anthrone 3.88g (20mmol) and thionyl chloride (15mL) into a 100mL single-necked bottle, reflux for 2h, evaporate and recover the remaining thionyl chloride, continue to add 15mL of xylene and excess phenol 3.76g (40mmol ), slowly heated to 130 ° C, reacted for 3 hours, stopped the reaction, cooled to room temperature, filtered, and the residual solid was washed with an appropriate amount of dichloromethane to obtain a crude product. The crude product was recrystallized with acetone, and after drying, 6.81 g of a light gray powder solid was obtained. The rate is 90%, and the melting point is 306-307°C. 1 H NMR (400MHz, DMSO-d 6 ): δ=9.44(s, 2H), 8.11(d, J=9.6Hz, 2H), 7.59(t, J=7.0Hz, 2H), 7.47(t, J=7.4Hz, 2H), 7.16(d ,J=7.9Hz,2H),6.72(d,J=8.7Hz,4H),6.65(d,J=8.7Hz,4H)( figure 1 ).

[0047] (2) Synthesis of 10,10-bis[4-(4-nitro-3-pyridyloxy)phenyl]-9(10H)-anthrone (5)

[0048] Add (4) 3.78...

Embodiment 2

[0052] Preparation of polyaryletheramide (PA-1a~PEA-1e):

[0053] Taking polyarylether amide (PA-1b) as an example, there are N 2 10,10-bis[4-(4-amino-3-pyridyloxy)phenyl]-9(10H)-anthrone (2) (5mmol, 2.8131g) and DMAc( 10mL), stirred in an ice-water bath until completely dissolved, then added isophthaloyl dichloride (3b) (5mmol, 1.0151g), and then added DMAc to adjust the solid content of the reaction system to about 20%. The reaction was carried out for 1 h at room temperature, and then at room temperature for 10 h to obtain a yellow transparent viscous solution. After the reaction, the viscous solution was transferred into 100 mL of methanol to obtain a white fibrous solid, which was filtered with suction, ground into solids, put into a Soxhlet extractor and extracted with hot methanol for 48 hours, and then vacuum-dried at 80°C for 12 hours. The remaining polyaryletheramides were synthesized in a similar way.

Embodiment 3

[0055] Preparation of Polyaryletheramide Films

[0056] Take 0.5g polymer sample, add appropriate amount of anhydrous DMAc to make a dilute solution, put the cleaned glass plate on a constant temperature heating plate at 60-70°C, apply the solution evenly on the glass plate, and wait for the solvent to dry , remove the polymer film, put it in a vacuum oven and dry it at 100°C for 12 hours.

[0057] (1) Structural analysis of polyaryletheramide

[0058] Taking polyarylether amide (PA-1b) as an example, Figure 4 It is the infrared spectrogram of PA-1b. It can be seen from the data in the figure that –NH does not appear 2 The characteristic absorption peak at 1656cm –1 The characteristic absorption peak of C=O in the amide group appeared at , and at 1225cm –1 The characteristic absorption peak of aryl ether (Ar–O–Ar) appeared at , indicating that the polymerization reaction between diamine and diacid chloride monomer occurred to form an amide bond.

[0059] Polyaryletherami...

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