CN114716664B - Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof - Google Patents

Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof Download PDF

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CN114716664B
CN114716664B CN202210425989.5A CN202210425989A CN114716664B CN 114716664 B CN114716664 B CN 114716664B CN 202210425989 A CN202210425989 A CN 202210425989A CN 114716664 B CN114716664 B CN 114716664B
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任浩浩
严永刚
张刚
李鹏程
戢觅之
吴娅男
杨杰
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Sichuan University
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Abstract

The invention relates to a semi-aromatic copolymerized polyarylether amide, a complex thereof and a preparation method thereof, belonging to the field of polymer synthesis and processing. The invention provides a semi-aromatic copolymerized polyarylether amide, which has a structural formula shown in a formula I, wherein m is more than or equal to 0 and less than 100, and n is more than 0 and less than or equal to 100. The polymer prepared by the invention has better toughness, processability and processing window due to the introduction of ether bond in the molecular structure. The obtained semi-aromatic polyaryletheramide complex has the functional characteristics of high temperature resistance, high mechanics, chemical corrosion resistance, antibiosis, fluorescence, magnetism, light filtering or radiation protection and the like; the application of the semi-aromatic polyaryletheramide is expanded.
Figure DDA0003609599300000011

Description

Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof
Technical Field
The invention relates to semi-aromatic copolymerized polyarylether amide (polyether ether amide), a complex thereof and a preparation method thereof, belonging to the field of polymer synthesis and processing.
Background
The semi-aromatic polyamide has good heat resistance, mechanical property and chemical corrosion resistance, so that the semi-aromatic polyamide has a very wide application prospect in the fields of chemical industry, energy, automobiles and the like. State of the art patents are on semi-aromatic nylons such as: the synthesis of PA6T copolymer, PA9T, etc. is reported. Such as: chinese patent CN104497305A uses high temperature nylon salt, aliphatic nylon salt and polyamine as raw materials to prepare semi-aromatic polyamide with high fluidity; chinese patent CN110041520A takes dimer acid, terephthalic acid, isophthalic acid and aliphatic diamine as raw materials, and prepares the semiaromatic polyamide containing dimer acid through salinization, prepolymerization and solid-phase reaction. Although the synthesis of semi-aromatic polyamides is well established, they are also widely used. Regarding their functional modifications, such as: the performances of antibacterial property, fluorescence, magnetism, flame retardance and the like are generally that particles are mixed in a semi-aromatic polymer, but the interface action of the particles and the semi-aromatic polyamide is poor, phase separation occurs for a long time, the particles seep out, and the service life and the performances of the composite material are influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a semi-aromatic copolymerized polyarylether amide with a novel structure, a semi-aromatic copolymerized polyarylether amide complex and a preparation method thereof.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a semi-aromatic copolymerized polyarylether amide, wherein the structural formula of the semi-aromatic copolymerized polyarylether amide is shown as a formula I:
Figure BDA0003609599280000011
wherein m is more than or equal to 0 and less than 100, n is more than 0 and less than or equal to 100;
Figure BDA0003609599280000012
Figure BDA0003609599280000021
Figure BDA0003609599280000022
any one of the above;
Figure BDA0003609599280000023
Figure BDA0003609599280000024
any one of the above;
Figure BDA0003609599280000025
Figure BDA0003609599280000031
Figure BDA0003609599280000032
any of the above.
Further, the starting material of the semi-aromatic copolymerized polyarylether amide shown in the formula I consists of the following components:
Figure BDA0003609599280000033
wherein m is more than or equal to 0 and less than 100, n is more than 0 and less than or equal to 100; x = F or Cl.
The second technical problem to be solved by the present invention is to provide a preparation method of the semi-aromatic copolymerized polyaryletheramide represented by the formula I, wherein the preparation method comprises the following steps: reacting a semi-aromatic dihalodiamide X-Ar 2 -X, aromatic diphenol, semi-aromatic dihalodiamide X-Ar 3 adding-X, a catalyst, an auxiliary agent, a dehydrating agent and a polar solvent into a reaction kettle, performing dehydration reaction for 0.5-3 hours at 150-200 ℃ under the protection of inert gas, and continuing to react for 0.5-12 hours at 150-260 ℃; reaction junctionAfter that, the product is washed by water and dried at 80-200 ℃ to obtain semi-aromatic copolymerized polyaryletheramide;
the mol ratio of the raw materials is as follows:
Figure BDA0003609599280000034
Figure BDA0003609599280000041
m is more than or equal to 0 and less than 100, n is more than 0 and less than or equal to 100; x = F or Cl;
wherein the content of the first and second substances,
Figure BDA0003609599280000042
Figure BDA0003609599280000043
Figure BDA0003609599280000044
any one of the above;
Figure BDA0003609599280000045
Figure BDA0003609599280000051
Figure BDA0003609599280000052
any one of them.
Further, the aromatic diol is any one of hydroquinone, resorcinol, biphenol, 4 '-dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfide, 2, 6-naphthalenediol, 1, 4-naphthalenediol, bisphenol AP, bisphenol Z, 4 '-cyclopentane-1, 1' -bis (4-hydroxyphenyl), bisphenol A, bisphenol AF, 4 '-dihydroxybenzophenone, 4' -dihydroxydiphenyl sulfone, phenolphthalein, or 1, 5-dinaphthol.
Further, the catalyst is any one of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, calcium bicarbonate or barium bicarbonate.
Further, the auxiliary agent is any one of sodium formate, sodium acetate, lithium formate, calcium chloride, calcium acetate, lithium acetate, sodium dodecyl benzene sulfonate, sodium phosphate, lithium chloride or sodium benzoate.
Further, the dehydrating agent is any one of toluene, xylene or chlorobenzene.
Further, the polar solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, N-dimethylpropyleneurea, diphenylsulfone, or sulfolane.
Further, the semi-aromatic dihalodiamide X-Ar 2 -X is prepared by the following method: adding aliphatic diamine, alkali and a surfactant into deionized water for dissolving; after dissolving, slowly dripping the dissolved solution into the mixed solution of the organic solvent 1 and the p-chlorobenzoyl chloride or the p-fluorobenzoyl chloride, and reacting for 4 to 10 hours after dripping; then distilling off the organic solvent 1, filtering, and recrystallizing with the organic solvent 2 to obtain the semi-aromatic dihalogenated diamide X-Ar 2 -X, X = Cl or F; wherein the aliphatic diamine is: any of bis (4-halobenzoyl) -1, (2-18) alkanediamine, bis (4-halobenzoyl) -2, 2-dimethylpropanediamine, bis (4-halobenzoyl) -2, 4-trimethylhexanediamine, bis (4-halobenzoyl) -2, 4-trimethylhexanediamine, bis (4-halobenzoyl) -1, 4-cyclohexanediamine, bis (4-halobenzoyl) dicyclohexylmethane or bis (4-halobenzoyl) -3,3' -dimethyldicyclohexylmethane.
Further, the semi-aromatic dihalodiamide X-Ar 3 -X is prepared by the following process: adding aliphatic diamine, alkali and a surfactant into deionized water for dissolving; to be treatedAfter dissolution, slowly dripping the dissolved solution into a mixed solution of the organic solvent 1 and p-chlorobenzoyl chloride or p-fluorobenzoyl chloride, and reacting for 4-10 hours after dripping; then evaporating the organic solvent 1, filtering, and recrystallizing with the organic solvent 2 to obtain the semi-aromatic dihalogenodiamide X-Ar 3 -X, X = Cl or F; wherein the aliphatic diamine is: bis (4-halobenzoyl) -cis-1, 4-cyclohexanediamine, bis (4-halobenzoyl) -trans-1, 4-cyclohexanediamine, bis (4-halobenzoyl) carboxamide, bis (4-halobenzoyl) -2, 4-dithiobiuret, bis (4-halochlorobenzoyl) -2, 5-dithiobiurea.
Further, the alkali is any one of NaOH, KOH or LiOH.
Further, the surfactant is any one of triethylammonium bromide, dodecyltriethylammonium bromide, hexadecyldimethylammonium bromide, sodium sulfanilate, tetrabutylammonium bromide, benzyltriethylammonium chloride, sodium dodecylbenzenesulfonate, sodium benzenesulfonate, sodium alginate, sodium dodecylsulfonate or sodium stearate.
Further, the organic solvent 1 is any one of dichloromethane, 1, 2-dichloroethane, chloroform, cyclohexane, or petroleum ether.
Further, the inert gas is any one of argon, helium, carbon dioxide or nitrogen.
Further, the recrystallization organic solvent 2 is any one of methanol, ethanol, isopropanol, acetone, butanone, tetrahydrofuran, acetamide, N-dimethylformamide, or N, N-dimethylacetamide.
The third technical problem to be solved by the invention is to provide a semi-aromatic copolymerized polyaryletheramide complex, which is prepared by the following method: dissolving semi-aromatic copolymerized polyaryletheramide shown in formula I, soluble salt and a polar solvent at 150-230 ℃ and stirring for 0.5-2 h, then pouring the mixed solution into deionized water, crushing, and repeatedly washing in the deionized water for at least 3 times to obtain the semi-aromatic copolymerized polyaryletheramide complex.
Further, the molar ratio of the semi-aromatic copolymerized polyarylether amide to the soluble salt is 1:1 to 1:9.
further, the soluble salt is at least one of sulfate, nitrate or chloride of Cu, ag, au, fe, co, ni, nd, ca, zn, mn, eu, te, pb, ba, cd and Gd.
Further, the polar organic solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, N-dimethylpropyleneurea, diphenylsulfone, or sulfolane.
In the present invention, the raw materials are not particularly limited, and they are all in terms of mole number.
The invention has the beneficial effects that:
1. the raw materials used in the invention are all commercial chemical products, and are easy to obtain.
2. Compared with semi-aromatic nylon products at the present stage, the polymer prepared by the invention has better toughness, processability and processing window due to the introduction of ether bond in the molecular structure.
3. The semi-aromatic polyarylether amide complex prepared by the invention has the functional characteristics of high temperature resistance, high mechanics, chemical corrosion resistance, antibiosis, fluorescence, magnetism, light filtering or radiation protection and the like; the application of the semi-aromatic polyaryletheramide is expanded.
Description of the drawings:
FIG. 1 is a FT-IR transmission spectrum of bis (4-fluorobenzoyl) -trans-1, 2-cyclohexanediamine obtained in example 4; as can be seen from fig. 1: 3332cm -1 The peak at 2925cm is the infrared absorption peak of-NH in bis (4-fluorobenzoyl) -trans-1, 2-cyclohexanediamine -1 ，2854cm -1 Peak at is-CH 2 Infrared absorption peak of 1639cm -1 Infrared absorption peak of-C = O.
FIG. 2 is an H-NMR spectrum of bis (4-fluorobenzoyl) -trans-1, 2-cyclohexanediamine obtained in example 4; as can be seen from fig. 2: the peak between 6.5 and 8.5ppm is the proton peak on the benzene ring of the bis (4-fluorobenzoyl) -trans-1, 2-cyclohexanediamine, the single peak between 3.5 and 4.0ppm is the proton peak of the amine in the amide, and the four peaks between 1.0 and 2.0ppm are the corresponding proton peaks on the cyclohexane.
FIG. 3 is an FT-IR spectrum of a semi-aromatic polyether ether amide obtained in example 4; as can be seen from fig. 3: 3438cm -1 The peak at (A) is an infrared absorption peak of-NH in the semi-aromatic polyether ether amide, and the peak is 2921cm -1 ，2852cm -1 The peak at (A) is the infrared absorption peak of methylene, 1641cm -1 The peak at (A) is an infrared absorption peak of-C = O, 1168cm -1 The peak at (A) is the infrared absorption peak of C-O-C.
FIG. 4 is a graph of the H-NMR spectrum of the semi-aromatic polyether ether amide obtained in example 4, as can be seen from FIG. 4: the peak between 6.5 and 8.5ppm is the proton peak of the benzene ring on the semi-aromatic polyether ether amide, the single peak between 3.5 and 4.0ppm is the proton peak of the amino group in the amide bond, and the peak between 1.0 and 2.0ppm corresponds to the proton peak on the cyclohexane.
FIG. 5 is a DSC of the crystalline semi-aromatic polyether ether amide obtained in example 4, as can be seen from FIG. 5: the semi-aromatic polyether ether amide obtained has a glass transition temperature of 256 ℃.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustrating the present invention, and are not to be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations to the invention described above based on the disclosure of the present invention.
Example 1
(1) Preparation of bis (4-fluorobenzoyl) ethylenediamine
1mol of ethylenediamine, 2mol of sodium hydroxide and 5g of triethylammonium bromide were added to 300ml of deionized water and dissolved. After dissolving, slowly dripping the dissolved solution into a mixed solution of 500 parts of dichloromethane and 2mol of p-fluorobenzoyl chloride, reacting for 4 hours after dripping, distilling off the dichloromethane, filtering, and recrystallizing a methanol solvent to obtain the bis (4-fluorobenzoyl) ethylenediamine.
(2) Preparation of bis (4-fluorobenzoyl) -cis-1, 2-cyclohexanediamine
1mol of cis-1, 2-cyclohexanediamine, 2mol of sodium hydroxide and 5g of triethylammonium bromide were dissolved in 300ml of deionized water. After dissolving, slowly dripping the dissolved solution into a mixed solution of 500 parts of dichloromethane and 2mol of p-fluorobenzoyl chloride, reacting for 4 hours after dripping, distilling off the dichloromethane, filtering, and recrystallizing a methanol solvent to obtain the bis (4-fluorobenzoyl) -cis-1, 2-cyclohexanediamine.
(3) Preparation of semi-aromatic polyether ether amides
1mol of bisphenol AP, 0.95mol of bis (4-fluorobenzoyl) ethylenediamine, 0.05mol of bis (4-fluorobenzoyl) -cis-1, 2-cyclohexanediamine, 3mol of catalyst sodium hydroxide, 1mol of auxiliary agent sodium formate, 10ml of dehydrating agent xylene and 200ml of N, N-dimethylformamide are added into a reaction kettle, and dehydration reaction is carried out for 0.5 hour at 150 ℃ under the protection of helium gas, and the reaction is continued for 0.5 hour at 150 ℃. After the reaction is finished, pouring out the product, washing the product with water, and drying the product for 10 hours at the temperature of 80 ℃ to obtain the semi-aromatic polyether ether amide (semi-aromatic copolymerized polyarylether amide).
(4) Preparation of semi-aromatic polyether ether amide complexes
And (2) adding 0.5mol of the prepared polyether ether amide, 0.5mol of europium nitrate hexahydrate and 100ml of DMF (dimethyl formamide) into a three-necked bottle, dissolving and stirring at 150 ℃ for 0.5h, pouring the mixed solution into deionized water, crushing, and repeatedly washing in the deionized water for 6 times to obtain the semi-aromatic polyether ether amide europium-containing complex with the fluorescence property. The semi-aromatic polyether ether amide europium-containing complex shows green light after being irradiated by an ultraviolet lamp.
Example 2
(1) Preparation of bis (4-chlorobenzoyl) hexanediamine
1mol of hexamethylenediamine, 2mol of sodium hydroxide and 30g of dodecyltriethylammonium bromide are dissolved in 1000ml of deionized water. After dissolving, slowly dripping the dissolved solution into 3000 parts of mixed solution of 1, 2-dichloroethane and 2mol of p-chlorobenzoyl chloride, reacting for 10 hours after dripping, distilling out the 1, 2-dichloroethane, filtering, and recrystallizing the ethanol solvent to obtain the bis (4-fluorobenzoyl) hexanediamine.
(2) Preparation of bis (4-chlorobenzoyl) -trans-1, 2-cyclohexanediamine
1mol of trans-1, 2-cyclohexanediamine, 2mol of sodium hydroxide and 25g of sodium stearate are dissolved in 500ml of deionized water. After dissolving, slowly dripping the dissolved solution into a mixed solution of 3000ml of petroleum ether and 2mol of p-chlorobenzoyl chloride, reacting for 4 hours after dripping, evaporating the petroleum ether, filtering, and recrystallizing by a methanol solvent to obtain the bis (4-chlorobenzoyl) -trans-1, 2-cyclohexanediamine.
(3) Preparation of semi-aromatic polyether ether amides
0.5mol of hydroquinone, 0.4mol of bis (4-chlorobenzoyl) hexamethylenediamine, 0.1mol of bis (4-chlorobenzoyl) -trans-1, 2-cyclohexanediamine, 1.5mol of potassium hydroxide, 1.5mol of auxiliary agent sodium acetate, 100ml of toluene and 1000ml of N, N-dimethylacetamide are added into a reaction kettle, dehydration reaction is carried out for 3 hours at 150 ℃ under the protection of argon, and the reaction is continued for 12 hours at 150 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 200 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
(4) Preparation of semi-aromatic polyether ether amide complexes
And (2) adding the prepared polyether ether amide with 0.5mol,3mol terbium chloride hexahydrate and 500ml N-methyl pyrrolidone into a three-necked bottle, dissolving and stirring at 190 ℃ for 2h, pouring the mixed solution into deionized water, crushing, and repeatedly washing in the deionized water for 6 times to obtain the semi-aromatic polyether ether amide terbium-containing complex with the fluorescence property. The semiaromatic polyether ether amide terbium-containing complex can show green light by ultraviolet irradiation.
Example 3
(1) Preparation of bis (4-fluorobenzoyl) -trimethylhexanediamine
2, 4-trimethyldiamine (1 mol), sodium hydroxide (2 mol), and cetyldimethylammonium bromide (20 g) were dissolved in 800ml of deionized water. After dissolving, slowly dripping the dissolved solution into 2000ml of mixed solution of chloroform and 2mol of p-fluorobenzoyl chloride, reacting for 6 hours after dripping, distilling off the chloroform, filtering, and recrystallizing an isopropanol solvent to obtain the bis (4-fluorobenzoyl) -trimethylhexanediamine.
(2) Preparation of bis (4-chlorobenzoyl) -carboxamide
1mol of urea, 2mol of sodium hydroxide and 15g of sodium dodecyl benzene sulfonate are added into 500ml of deionized water for dissolution. After dissolving, slowly dripping the dissolved solution into a mixed solution of 3000ml of petroleum ether and 2mol of p-chlorobenzoyl chloride, reacting for 4 hours after dripping, evaporating the petroleum ether, filtering, and recrystallizing an isopropanol solvent to obtain the bis (4-chlorobenzoyl) -carbamide.
(3) Preparation of semi-aromatic polyether ether amides
1mol of diphenol, 0.95mol of bis (4-fluorobenzoyl) -trimethylhexanediamine, 0.05mol of bis (4-chlorobenzoyl) -carbamide, 3mol of lithium hydroxide, 3mol of auxiliary agent lithium formate, 80ml of chlorobenzene and 500ml of dimethyl sulfoxide are added into a reaction kettle, dehydration reaction is carried out for 3 hours at 180 ℃ under the protection of carbon dioxide gas, and reaction is carried out for 8 hours at 190 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 100 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
(4) Preparation of semi-aromatic polyether ether amide complexes
And (2) adding 0.5mol of the prepared polyether ether amide, 0.5mol of zinc nitrate hexahydrate and 200ml of 1, 3-dimethyl-2-imidazolidinone into a three-neck bottle, dissolving and stirring at 230 ℃ for 2h, pouring the mixed solution into deionized water, crushing, and repeatedly washing in the deionized water for 6 times to obtain the semi-aromatic polyether ether amide zinc-containing complex with antibacterial property.
Example 4
(1) Preparation of bis (4-fluorobenzoyl) -trans-1, 2-cyclohexanediamine
1mol of trans-1, 2-cyclohexanediamine, 2mol of sodium hydroxide and 20g of sodium sulfanilate are added into 500ml of deionized water for dissolution. After dissolving, slowly dripping the dissolved solution into a mixed solution of 3000ml of cyclohexane and 2mol of p-fluorobenzoyl chloride, reacting for 4 hours after dripping, distilling off the cyclohexane, filtering, and recrystallizing by using an acetone solvent to obtain the bis (4-fluorobenzoyl) -trans-1, 2-cyclohexanediamine.
(2) Preparation of semi-aromatic polyether ether amides
0.5mol of diphenol, 0.5mol of bis (4-fluorobenzoyl) -trans-1, 2-cyclohexanediamine, 1.5mol of calcium hydroxide, 1mol of auxiliary agent calcium chloride, 80ml of chlorobenzene and 1000ml of N-methylpyrrolidone are added into a reaction kettle, and the mixture is dehydrated and reacted for 3 hours at 200 ℃ under the protection of nitrogen and is continuously reacted for 6 hours at 200 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 100 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
(3) Preparation of semi-aromatic polyether ether amide complexes
And (2) adding 0.4mol,0.4mol and 200ml of N-methylpyrrolidone hexahydrate europium nitrate of the polyether ether amide into a three-necked bottle, dissolving and stirring for 2h at 190 ℃, then pouring the mixed solution into deionized water, crushing, and repeatedly washing for 6 times in the deionized water to obtain the semi-aromatic polyether ether amide europium-containing complex with the green fluorescence property. The semi-aromatic polyether ether amide europium-containing complex shows green light after being irradiated by an ultraviolet lamp.
Example 5
(1) Preparation of bis (4-chlorobenzoyl) decamethylenediamine
Decamethylenediamine (1 mol), sodium hydroxide (2 mol) and tetrabutylammonium bromide (15 g) were added to 1000ml of deionized water and dissolved. After dissolving, slowly dripping the dissolved solution into a mixed solution of 3000ml1, 2-dichloroethane and 2mol p-chlorobenzoyl chloride, reacting for 10 hours after dripping, distilling out the 1, 2-dichloroethane, filtering, and recrystallizing by butanone solvent to obtain the bis (4-fluorobenzoyl) decamethylenediamine.
(2) Preparation of bis (4-chlorobenzoyl) -2, 4-dithiobiuret
2, 4-dithiobiuret 1mol, sodium hydroxide 2mol and tetrabutylammonium bromide 15g are added into 500ml deionized water for dissolution. After the solution is dissolved, slowly dripping the dissolved solution into a mixed solution of 3000ml1, 2-dichloroethane and 2mol of p-chlorobenzoyl chloride, reacting for 4 hours after dripping, evaporating petroleum ether, filtering, and recrystallizing butanone to obtain the bis (4-chlorobenzoyl) -2, 4-dithiobiuret.
(3) Preparation of semi-aromatic polyether ether amides
Adding 0.5mol of phenolphthalein, 0.25mol of bis (4-fluorobenzoyl) decamethylene diamine, 0.25mol of bis (4-chlorobenzoyl) -2, 4-dithiobiuret, 1.5mol of barium hydroxide, 1.5mol of auxiliary agent calcium acetate, 80ml of chlorobenzene and 1000ml of N-cyclohexyl pyrrolidone into a reaction kettle, dehydrating for 3 hours at 150 ℃ under the protection of nitrogen, and continuously reacting for 6 hours at 150 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 100 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
(4) Preparation of semi-aromatic polyether ether amide complex
Adding 0.4mol and 3.6mol of neodymium chloride hexahydrate and 2000ml of 1, 3-dimethyl-2-imidazolidinone into a three-necked bottle, dissolving and stirring at 230 ℃ for 2 hours, then pouring the mixed solution into deionized water, crushing, and repeatedly washing in the deionized water for 6 times to obtain the semi-aromatic polyether ether amide neodymium-containing complex with the light absorption performance at 580 nm.
Example 6
(1) Preparation of bis (4-fluorobenzoyl) -1, 4-cyclohexanediamine
1, 4-cyclohexanediamine (1 mol), sodium hydroxide (2 mol) and benzyltriethylammonium bromide (25 g) were dissolved in 600ml of deionized water. After dissolving, slowly dripping the dissolved solution into a mixed solution of 1000 parts of cyclohexane and 317 parts of p-fluorobenzoyl chloride, reacting for 6 hours after dripping, distilling off cyclohexane, filtering, and recrystallizing tetrahydrofuran solvent to obtain the bis (4-fluorobenzoyl) -1, 4-cyclohexanediamine.
(2) Preparation of bis (4-chlorobenzoyl) -2, 5-dithiobiurea
1mol of 2, 5-dithiobiurea, 2mol of sodium hydroxide and 25g of benzyltriethylammonium bromide were added to 600ml of deionized water and dissolved. After the solution is dissolved, slowly dropping the dissolved solution into a mixed solution of 1000 parts of cyclohexane and 317 parts of p-fluorobenzoyl chloride, reacting for 6 hours after the dropping is finished, distilling off the cyclohexane, filtering, and recrystallizing by using a tetrahydrofuran solvent to obtain the bis (4-chlorobenzoyl) -2, 5-dithiobiurea.
(3) Preparation of semi-aromatic polyether ether amides
0.4mol of bisphenol A, 0.35mol of bis (4-fluorobenzoyl) -1, 4-cyclohexanediamine, 0.05mol of bis (4-chlorobenzoyl) -2, 5-dithiobiurea, 1.5mol of lithium carbonate, 1.5mol of auxiliary agent lithium acetate, 80ml of chlorobenzene and 1000ml of N-cyclohexyl pyrrolidone are added into a reaction kettle, and dehydration reaction is carried out for 3 hours at 200 ℃ under the protection of nitrogen and the reaction is continued for 8 hours at 220 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 100 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
(4) Preparation of semi-aromatic polyether ether amide complexes
Adding 0.4mol and 0.4mol of ferrous sulfate of the polyether ether amide prepared above and 2000ml of hexamethyl phosphoramide into a three-necked bottle, dissolving and stirring for 2h at 230 ℃, then pouring the mixed solution into deionized water, crushing, and repeatedly washing for 6 times in the deionized water to obtain the semi-aromatic polyether ether amide iron-containing complex with paramagnetic performance.
Example 7
(1) Preparation of bis (4-chlorobenzoyl) decamethylenediamine
Decamethylenediamine (1 mol), sodium hydroxide (2 mol) and tetrabutylammonium bromide (15 g) were added to 1000ml of deionized water and dissolved. After dissolving, slowly dripping the dissolved solution into a mixed solution of 3000ml1, 2-dichloroethane and 2mol p-chlorobenzoyl chloride, reacting for 10 hours after dripping, distilling out the 1, 2-dichloroethane, filtering, and recrystallizing by butanone solvent to obtain the bis (4-fluorobenzoyl) decamethylenediamine.
(2) Preparation of bis (4-chlorobenzoyl) -2, 4-dithiobiuret
2, 4-dithiobiuret 1mol, sodium hydroxide 2mol, tetrabutylammonium bromide 15g were added to 500ml of deionized water and dissolved. After the solution is dissolved, slowly dripping the dissolved solution into a mixed solution of 3000ml1, 2-dichloroethane and 2mol of p-chlorobenzoyl chloride, reacting for 4 hours after dripping, evaporating petroleum ether, filtering, and recrystallizing butanone to obtain the bis (4-chlorobenzoyl) -2, 4-dithiobiuret.
(3) Preparation of semi-aromatic polyether ether amides
0.5mol of phenolphthalein, 0.25mol of bis (4-fluorobenzoyl) decamethylenediamine, 0.25mol of bis (4-chlorobenzoyl) -2, 4-dithiobiuret, 1.5mol of barium hydroxide, 1.5mol of auxiliary agent calcium acetate, 80ml of chlorobenzene and 1000ml of N-cyclohexyl pyrrolidone are added into a reaction kettle, and dehydration reaction is carried out for 3 hours at 150 ℃ under the protection of nitrogen and the reaction is continued for 6 hours at 150 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 100 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
(4) Preparation of semi-aromatic polyether ether amide complexes
And adding 0.4mol,0.4mol and 2000ml of cadmium chloride and N-cyclohexyl pyrrolidone into a three-necked bottle, dissolving and stirring at 230 ℃ for 2h, pouring the mixed solution into deionized water, crushing, and repeatedly washing in the deionized water for 6 times to obtain the semi-aromatic polyether ether amide cadmium-containing complex with the X-ray shielding property.
Example 8
(1) Preparation of bis (4-chlorobenzoyl) decamethylenediamine
Decamethylenediamine (1 mol), sodium hydroxide (2 mol) and tetrabutylammonium bromide (15 g) were added to 1000ml of deionized water and dissolved. After dissolving, slowly dripping the dissolved solution into a mixed solution of 3000ml1, 2-dichloroethane and 2mol p-chlorobenzoyl chloride, reacting for 10 hours after dripping, distilling out the 1, 2-dichloroethane, filtering, and recrystallizing by butanone solvent to obtain the bis (4-fluorobenzoyl) decamethylenediamine.
(2) Preparation of bis (4-chlorobenzoyl) -2, 4-dithiobiuret
2, 4-dithiobiuret 1mol, sodium hydroxide 2mol and tetrabutylammonium bromide 15g are added into 500ml deionized water for dissolution. After dissolving, slowly dripping the dissolved solution into a mixed solution of 3000ml1, 2-dichloroethane and 2mol of p-chlorobenzoyl chloride, reacting for 4 hours after dripping, evaporating petroleum ether, filtering, and recrystallizing butanone to obtain the bis (4-chlorobenzoyl) -2, 4-dithiobiuret.
(3) Preparation of semi-aromatic polyether ether amides
0.5mol of phenolphthalein, 0.25mol of bis (4-fluorobenzoyl) decamethylenediamine, 0.25mol of bis (4-chlorobenzoyl) -2, 4-dithiobiuret, 1.5mol of barium hydroxide, 1.5mol of auxiliary agent calcium acetate, 80ml of chlorobenzene and 1000ml of N-cyclohexyl pyrrolidone are added into a reaction kettle, and dehydration reaction is carried out for 3 hours at 150 ℃ under the protection of nitrogen and the reaction is continued for 6 hours at 150 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 100 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
(4) Preparation of semi-aromatic polyether ether amide complexes
Adding 0.4mol and 0.4mol of zinc nitrate and 2000ml of N, N-dimethyl propylene urea into a three-necked bottle, dissolving and stirring at 220 ℃ for 2 hours, then pouring the mixed solution into deionized water, crushing, and repeatedly washing in the deionized water for 6 times to obtain the semi-aromatic polyether ether amide zinc-containing complex with antibacterial property.
Comparative example 1
1mol of bis (4-fluorobenzoyl) hexamethylene diamine, 1mol of hydroquinone, 1.5mol of lithium hydroxide, 1.5mol of auxiliary agent lithium formate, 80ml of chlorobenzene and 1000ml of N-methyl pyrrolidone are added into a reaction kettle, dehydration reaction is carried out for 3 hours at 180 ℃ under the protection of carbon dioxide gas, and the reaction is carried out for 8 hours at 190 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 100 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
The polyether ether amide prepared above, 0.4mol terbium chloride hexahydrate and 2000ml N-cyclohexyl pyrrolidone were added into a three-necked flask, dissolved and stirred at 230 ℃ for 2 hours, and then the mixed solution was poured into deionized water, pulverized, and repeatedly washed in deionized water for 6 times. The obtained material is irradiated by an ultraviolet lamp and has no fluorescent reaction.
Comparative example 2
1mol of diphenol, 1mol of bis (4-fluorobenzoyl) -trimethylhexanediamine, 2mol of potassium carbonate, 1.5mol of auxiliary calcium chloride, 80ml of chlorobenzene and 1000ml of N-methylpyrrolidone are added into a reaction kettle, and the mixture is dehydrated and reacted for 3 hours at 200 ℃ under the protection of nitrogen and is continuously reacted for 6 hours at 200 ℃. After the reaction is finished, pouring out the product, washing with water, and drying at 100 ℃ for 10 hours to obtain the semi-aromatic polyether ether amide.
The polyether ether amide prepared above, 0.4mol zinc chloride and 2000ml N-cyclohexyl pyrrolidone were added to a three-necked flask, dissolved and stirred at 230 ℃ for 2 hours, and then the mixed solution was poured into deionized water, pulverized, and repeatedly washed in deionized water for 6 times. The obtained material does not contain zinc element through EDX detection.

Claims (12)

1. A semi-aromatic copolymerized polyarylether amide, wherein the structural formula of the semi-aromatic copolymerized polyarylether amide is shown as formula I:
Figure FDA0003964347390000011
wherein m is more than or equal to 0 and less than 100, n is more than 0 and less than or equal to 100;
Ar 1 ＝
Figure FDA0003964347390000012
Figure FDA0003964347390000013
any one of the above;
Ar 2 ＝
Figure FDA0003964347390000014
Figure FDA0003964347390000021
Figure FDA0003964347390000022
any one of (1) and (b);
Ar 3 ＝
Figure FDA0003964347390000023
Figure FDA0003964347390000024
any of the above.
2. The semi-aromatic copolymerized polyaryletheramide of claim 1, wherein the starting material of the semi-aromatic copolymerized polyaryletheramide represented by formula I is composed of the following components:
Figure FDA0003964347390000025
Figure FDA0003964347390000031
wherein m is more than or equal to 0 and less than 100, n is more than 0 and less than or equal to 100; x = F or Cl.
3. The method of claim 1 or 2, wherein the method comprises: reacting a semi-aromatic dihalodiamide X-Ar 2 -X, aromatic diphenol, semi-aromatic dihalodiamide X-Ar 3 adding-X, a catalyst, an auxiliary agent, a dehydrating agent and a polar solvent into a reaction kettle, performing dehydration reaction for 0.5-3 hours at 150-200 ℃ under the protection of inert gas, and continuing to react for 0.5-12 hours at 150-260 ℃; after the reaction is finished, washing the product with water, and drying at 80-200 ℃ to obtain semi-aromatic copolymerized polyaryletheramide;
the mol ratio of the raw materials is as follows:
Figure FDA0003964347390000032
m is more than or equal to 0 and less than 100, n is more than 0 and less than or equal to 100; x = F or Cl;
wherein Ar is 2 ＝
Figure FDA0003964347390000033
Figure FDA0003964347390000041
Any one of (1) and (b);
Ar 3 ＝
Figure FDA0003964347390000042
Figure FDA0003964347390000043
any one of them.
4. The method of claim 3, wherein the aromatic diol is any one of hydroquinone, resorcinol, biphenol, 4 '-dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfide, 2, 6-naphthalenediol, 1, 4-naphthalenediol, bisphenol AP, bisphenol Z, 4 '-cyclopentane-1, 1' -bis (4-hydroxyphenyl), bisphenol A, bisphenol AF, 4 '-dihydroxybenzophenone, 4' -dihydroxydiphenyl sulfone, phenolphthalein, or 1, 5-dinaphthol.
5. The method of claim 3, wherein the catalyst is any one of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, calcium bicarbonate, or barium bicarbonate;
the auxiliary agent is any one of sodium formate, sodium acetate, lithium formate, calcium chloride, calcium acetate, lithium acetate, sodium dodecyl benzene sulfonate, sodium phosphate, lithium chloride or sodium benzoate;
the dehydrating agent is any one of toluene, xylene or chlorobenzene;
the polar solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, N-dimethylpropyleneurea, diphenyl sulfone or sulfolane.
6. The method of claim 3, wherein the semi-aromatic dihalodiamide is X-Ar 2 -X is prepared by the following process: adding aliphatic diamine, alkali and a surfactant into deionized water for dissolving; after dissolving, slowly dripping the dissolved solution into the mixed solution of the organic solvent 1 and the p-chlorobenzoyl chloride or the p-fluorobenzoyl chloride, and reacting for 4 to 10 hours after dripping; then evaporating the organic solvent 1, filtering, and recrystallizing with the organic solvent 2 to obtain the semi-aromaticDihalodiamide X-Ar 2 -X；
Wherein the aliphatic diamine is: any of bis (4-halobenzoyl) -1, (2-18) alkanediamine, bis (4-halobenzoyl) -2, 2-dimethylpropanediamine, bis (4-halobenzoyl) -2, 4-trimethylhexanediamine, bis (4-halobenzoyl) -2, 4-trimethylhexanediamine, bis (4-halobenzoyl) -1, 4-cyclohexanediamine, bis (4-halobenzoyl) dicyclohexylmethane or bis (4-halobenzoyl) -3,3' -dimethyldicyclohexylmethane.
7. The method of claim 3, wherein the semi-aromatic dihalodiamide is X-Ar 3 -X is prepared by the following method: adding aliphatic diamine, alkali and a surfactant into deionized water for dissolving; after dissolving, slowly dripping the dissolved solution into the mixed solution of the organic solvent 1 and the p-chlorobenzoyl chloride or the p-fluorobenzoyl chloride, and reacting for 4 to 10 hours after dripping; then distilling off the organic solvent 1, filtering, and recrystallizing with the organic solvent 2 to obtain the semi-aromatic dihalogenated diamide X-Ar 3 -X；
Wherein the aliphatic diamine is: bis (4-halobenzoyl) -cis-1, 4-cyclohexanediamine, bis (4-halobenzoyl) -trans-1, 4-cyclohexanediamine, bis (4-halobenzoyl) carboxamide, bis (4-halobenzoyl) -2, 4-dithiobiuret, bis (4-halochlorobenzoyl) -2, 5-dithiobiurea.
8. The method of claim 6 or 7, wherein the base is NaOH, KOH or LiOH;
the surfactant is any one of triethyl ammonium bromide, dodecyl triethyl ammonium bromide, hexadecyl dimethyl ammonium bromide, sodium sulfanilate, tetrabutyl ammonium bromide, benzyl triethyl ammonium chloride, dodecyl benzene sulfonate, sodium alginate, sodium dodecyl sulfonate or sodium stearate;
the organic solvent 1 is any one of dichloromethane, 1, 2-dichloroethane, chloroform, cyclohexane or petroleum ether;
the inert gas is any one of argon, helium, carbon dioxide or nitrogen;
the recrystallization organic solvent 2 is any one of methanol, ethanol, isopropanol, acetone, butanone, tetrahydrofuran, acetamide, N-dimethylformamide or N, N-dimethylacetamide.
9. A semi-aromatic copolymerized polyarylether amide complex, wherein said complex is prepared by the following process: dissolving the semi-aromatic copolymerized PAE amide, soluble salt and polar solvent of claim 1 or 2 at 150-230 ℃ and stirring for 0.5-2 h, then pouring the mixed solution into deionized water, crushing, and repeatedly washing in deionized water for at least 3 times to obtain the semi-aromatic copolymerized PAE amide complex.
10. The semi-aromatic copolymerized polyarylether amide complex of claim 9, wherein the molar ratio of semi-aromatic copolymerized polyarylether amide to soluble salt is 1:1 to 1:9.
11. the semi-aromatic copolymerized polyaryletheramide complex of claim 9, wherein the soluble salt is at least one of a sulfate, nitrate or chloride of Cu, ag, au, fe, co, ni, nd, ca, zn, mn, eu, te, pb, ba, cd, gd.
12. The semi-aromatic copolymerized polyaryletheramide complex of claim 9, wherein the polar solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, N-dimethylpropyleneurea, diphenylsulfone, or sulfolane.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0055480A1 (en) * 1980-12-24 1982-07-07 MITSUI TOATSU CHEMICALS, Inc. Process for producing aromatic polyester amide
CN101921396A (en) * 2010-07-29 2010-12-22 四川大学 Semi-aryl poly (phenylene sulfide amide) and preparation method thereof
CN103739839A (en) * 2013-12-31 2014-04-23 四川大学 Semi-aromatic polyarylether amide and preparation method thereof
CN104109236A (en) * 2014-07-21 2014-10-22 四川大学 Fatty cyclosemi aromatic polyarylether amide and preparation method thereof
CN108341947A (en) * 2018-02-09 2018-07-31 四川大学 The intrinsic fire-retardant semi-aromatic of one kind being total to polyarylether amide and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0055480A1 (en) * 1980-12-24 1982-07-07 MITSUI TOATSU CHEMICALS, Inc. Process for producing aromatic polyester amide
CN101921396A (en) * 2010-07-29 2010-12-22 四川大学 Semi-aryl poly (phenylene sulfide amide) and preparation method thereof
CN103739839A (en) * 2013-12-31 2014-04-23 四川大学 Semi-aromatic polyarylether amide and preparation method thereof
CN104109236A (en) * 2014-07-21 2014-10-22 四川大学 Fatty cyclosemi aromatic polyarylether amide and preparation method thereof
CN108341947A (en) * 2018-02-09 2018-07-31 四川大学 The intrinsic fire-retardant semi-aromatic of one kind being total to polyarylether amide and preparation method thereof

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