CN117510916A - Preparation method of high-temperature-resistant modified polyethylene isolating film - Google Patents

Preparation method of high-temperature-resistant modified polyethylene isolating film Download PDF

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CN117510916A
CN117510916A CN202311462455.0A CN202311462455A CN117510916A CN 117510916 A CN117510916 A CN 117510916A CN 202311462455 A CN202311462455 A CN 202311462455A CN 117510916 A CN117510916 A CN 117510916A
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modified polyethylene
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phenylenediamine
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temperature
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CN117510916B (en
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刘群
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Cangzhou Zhaoyang Paper Plastic Packaging Co ltd
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Abstract

The invention relates to the technical field of polyethylene, and discloses a preparation method of a high-temperature-resistant modified polyethylene isolating film, wherein m-phenylenediamine, isophthaloyl dichloride and phosphorus-containing m-phenylenediamine are subjected to polycondensation reaction to obtain modified polyamide. The carboxyl in the 5-vinyl isophthalic acid and the thiol group of KH590 modified nano-silica are subjected to catalytic esterification under the condition of p-toluenesulfonic acid to obtain vinyl nano-silica, and the vinyl nano-silica, maleic anhydride and polyethylene react under the initiation of dicumyl peroxide to obtain the modified polyethylene. And finally, uniformly mixing the modified polyethylene and the modified polyamide, extruding, granulating and compression molding to obtain the modified polyethylene isolating film. The modified polyethylene isolating film prepared by the invention has excellent mechanical property, flame retardant property and high temperature resistance.

Description

Preparation method of high-temperature-resistant modified polyethylene isolating film
Technical Field
The invention relates to the technical field of polyethylene isolating films, in particular to a preparation method of a high-temperature-resistant modified polyethylene isolating film.
Background
Polyethylene is thermoplastic resin prepared by polymerization reaction of ethylene monomer, has excellent low temperature resistance, chemical stability, electrical insulation and other performances, and is widely applied to the fields of packaging materials, films, wires, cables and the like, but has poor mechanical properties.
Polyamide is commonly called nylon, is a generic name of thermoplastic resin with a molecular main chain containing repeated amide groups, has excellent mechanical property, heat resistance, abrasion resistance and other properties, is widely applied to the fields of engineering plastics, knitwear, medical supplies and the like, is subjected to blending modification with other substances, and can improve the comprehensive performance of the composite material so as to expand the application range of the composite material.
The phosphorus-containing flame retardant is a high-efficiency, smokeless and low-pollution flame retardant. Silica is an inorganic compound, has excellent fire resistance, high temperature resistance, corrosion resistance and other properties, and is widely applied to the fields of glass, electronic industry, optical instruments, refractory materials and the like.
The invention discloses a preparation method of a heat-resistant polyethylene-nylon composite film, which is characterized in that hyperbranched imide polyamide is prepared by blending and modifying the hyperbranched imide polyamide and nylon, and the prepared polyethylene-nylon composite film has high thermal decomposition temperature and strong thermal stability, but does not improve the mechanical property and flame retardant property.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a preparation method of a high-temperature-resistant modified polyethylene isolating film.
(II) technical scheme
A preparation method of a high-temperature-resistant modified polyethylene isolating film comprises the following steps:
(1) Adding m-phenylenediamine, isophthaloyl dichloride and phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of between-10 and-5 ℃ under the nitrogen condition, heating to 20-35 ℃, reacting for 20-60min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(2) Adding vinyl nano silicon dioxide, maleic anhydride and dicumyl peroxide into an acetone solvent, adding polyethylene into the acetone solvent, uniformly stirring, heating to 180-240 ℃, reacting for 5-20min, and drying after the reaction is finished to obtain the modified polyethylene.
(3) Mixing the dried modified polyethylene and modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 40-70r/min, granulating, and compression molding to obtain the modified polyethylene isolating film.
Preferably, in the step (1), the mass ratio of the m-phenylenediamine to the m-phthaloyl chloride to the phosphorus-containing m-phenylenediamine is 100:180-240:5-20.
Preferably, in the step (2), the mass ratio of the vinyl nano silicon dioxide to the maleic anhydride to the dicumyl peroxide to the polyethylene is 1-3:2-4:0.5-1.5:100.
Preferably, in the step (3), the mass ratio of the modified polyethylene to the modified polyamide is 100:80-120.
Preferably, in the step (1), the preparation method of phosphorus-containing m-phenylenediamine comprises the following steps:
s1, adding 3, 5-dinitrobenzaldehyde and 5-aminoresorcinol into an ethanol solvent, adding a glacial acetic acid catalyst into the ethanol solvent, heating to 60-80 ℃, carrying out reflux reaction for 5-12h, cooling to room temperature after the reaction is finished, filtering, washing with deionized water, and recrystallizing with ethanol to obtain an intermediate 1.
S2, adding the intermediate 1 and triethylamine into a toluene solvent under the condition of nitrogen, adding diphenyl phosphorus chloride into the toluene solvent at the temperature of between minus 5 and 0 ℃, stirring and dispersing, heating to the temperature of between 60 and 80 ℃, reacting for 2 to 5 hours, cooling to room temperature after the reaction is finished, filtering, distilling filtrate under reduced pressure, and recrystallizing acetonitrile to obtain the intermediate 2.
S3, adding the intermediate 2 and Pd/C into an ethanol solvent under the condition of nitrogen, heating to 40-50 ℃, adding 70-80% hydrazine hydrate into the mixture, carrying out reflux reaction for 2-5h, filtering, washing with deionized water, and recrystallizing with ethanol to obtain phosphorus-containing m-phenylenediamine.
Preferably, in the step S1, the mass ratio of the 3, 5-dinitrobenzaldehyde to the 5-aminoresorcinol is 100:60-80.
Preferably, in the step S2, the molar ratio of the intermediate 1 to the triethylamine to the diphenyl phosphorus chloride is 100:5-15:140-180.
Preferably, in the step S3, the mass ratio of the intermediate 2 to Pd/C is 100:3-5.
Preferably, in the step (2), the preparation method of the vinyl nano silica comprises the following steps: adding 5-vinyl isophthalic acid, KH590 modified nano-silica and p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 100-120 ℃, reacting for 10-20h, decompressing and distilling after the reaction is finished, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
Preferably, in the step, the molar ratio of the 5-vinyl isophthalic acid, the KH590 modified nano-silica and the p-toluenesulfonic acid is 100:200-250:18-24.
(III) beneficial technical effects
3, 5-dinitrobenzaldehyde and 5-aminoresorcinol are subjected to Schiff base preparation reaction to obtain an intermediate 1, the intermediate 1 is reacted with diphenyl phosphorus chloride under the catalysis of triethylamine to obtain an intermediate 2, and nitro is reduced to amino under the reduction catalysis of Pd/C to obtain phosphorus-containing m-phenylenediamine. And (3) performing polycondensation reaction on the m-phenylenediamine, the m-phthaloyl chloride and the phosphorus-containing m-phenylenediamine to obtain the modified polyamide. The carboxyl in the 5-vinyl isophthalic acid and the thiol group of KH590 modified nano-silica are subjected to catalytic esterification under the condition of p-toluenesulfonic acid to obtain vinyl nano-silica, and the vinyl nano-silica, maleic anhydride and polyethylene react under the initiation of dicumyl peroxide to obtain the modified polyethylene. And finally, uniformly mixing the modified polyethylene and the modified polyamide, extruding, granulating and compression molding to obtain the modified polyethylene isolating film.
The modified polyethylene isolating film prepared by the invention contains modified polyethylene and modified polyamide, and because the compatibility of the polyethylene and the polyamide is poor, the polyethylene prepared by the invention contains maleic anhydride groups, and side chain groups of the modified polyethylene and the modified polyamide are mutually crosslinked and wound to form more crosslinking sites, and when the modified polyethylene isolating film is impacted, impact energy is mutually transmitted along the crosslinking sites, so that the mechanical property of the material is improved.
The nano silicon dioxide used in the invention is easy to agglomerate, has better dispersibility after organic modification, reduces agglomeration, has better compatibility with organic matters after organic modification, and can be better dispersed in organic media. In addition, the modified polyethylene isolating film contains more silica bonds, the bond energy of the silica bonds is larger than that of carbon-carbon bonds, when the modified polyethylene isolating film is impacted, the silica bonds can absorb more impact energy so as to enhance the mechanical property of the modified polyethylene isolating film, and as the nano silica can be uniformly dispersed in organisms after being organically modified, the crosslinking degree of the nano silica and organism molecules is increased, the binding force at an interface is increased, and when the material is impacted, the nano silica can play a role of stress concentration points and triggering generation of silver pattern shearing bands, so that the mechanical property of the modified polyethylene isolating film is further improved.
The modified polyethylene isolating film prepared by the invention contains silicon element, phosphorus element and nitrogen element. When heated, the phosphorus element contained in the material is heated to generate acidic substances such as phosphoric acid, metaphosphoric acid and the like, so that the material can be promoted to be dehydrated to form carbon, a compact carbon layer is formed, and along with the rise of the temperature, the phosphoric acid and metaphosphoric acid further form polymetaphosphoric acid, and the polymetaphosphoric acid covers the surface of the material; the silicon element contained in the carbon layer has larger silicon-oxygen bond energy, can absorb more heat, and can form a continuous and oxidation-resistant silicate protective layer due to the rise of temperature, so that the silicon-oxygen bond in the carbon layer covers the surface of the material to block the material from transporting and transferring the external substances; the nitrogen element contained in the flame-retardant material can generate flame-retardant gas and dilute the concentration of flammable gas in the air, and the flame-retardant property of the flame-retardant material is improved by the cooperation of the nitrogen element, the flame-retardant material and the air.
The modified polyethylene isolating film prepared by the invention contains modified polyamide, the polyamide macromolecule chain is broken and decomposed into small units when heated at high temperature, and then the small units are subjected to polycondensation to form aromatic compounds with larger structures, so that the high temperature resistance of the material is improved, and in addition, the strong interface effect between the inorganic nano silicon dioxide and the material matrix can limit the thermal movement of the molecular chain segments of the material matrix, and the high temperature resistance of the material can also be improved. The modified polyethylene isolating film prepared by the invention has excellent mechanical property, flame retardant property and high temperature resistance.
Drawings
FIG. 1 shows a preparation route of phosphorus-containing metaphenylene diamine.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation of KH590 modified nano-silica: adding 10g of nano silicon dioxide into 30% ethanol solution, stirring and dispersing, adjusting the pH to 4 by using hydrochloric acid, adding 0.15g of KH590 into the solution, heating to 80 ℃, reacting for 10 hours, cooling to room temperature, filtering, washing and drying to obtain the KH590 modified nano silicon dioxide.
Example 1
(1) 5g of 3, 5-dinitrobenzaldehyde and 3.8g of 5-aminoresorcinol are added into ethanol solvent, 6mL of glacial acetic acid catalyst is added into the mixture, the temperature is raised to 75 ℃, the reflux reaction is carried out for 12 hours, the mixture is cooled to room temperature after the reaction is finished, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 3g of triethylamine are added into toluene solvent, 35g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of minus 5 ℃, the mixture is stirred and dispersed, the temperature is raised to 80 ℃ for 2 hours of reaction, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, thus obtaining intermediate 2.
(3) 15g of intermediate 2 and 0.6g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 50 ℃, 80% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 4 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 1.5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 45min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 4.2g of KH590 modified nano-silica and 0.45g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 110 ℃, reacting for 18h, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 0.5g of vinyl nano silicon dioxide, 1.8g of maleic anhydride and 0.6g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 200 ℃, reacting the mixture for 15min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 160g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 60r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Example 2
(1) 5g of 3, 5-dinitrobenzaldehyde and 3.2g of 5-aminoresorcinol are added into an ethanol solvent, 4.5mL of glacial acetic acid catalyst is added into the ethanol solvent, the temperature is raised to 60 ℃, the reflux reaction is carried out for 10 hours, the reaction is finished, the reaction is cooled to room temperature, the filtration and the washing with deionized water are carried out, and the ethanol is recrystallized, thus obtaining an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 2.5g of triethylamine are added into toluene solvent, 30g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of minus 5 ℃, stirred and dispersed, the temperature is raised to 75 ℃ for reaction for 5 hours, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, so that intermediate 2 is obtained.
(3) 15g of intermediate 2 and 0.7g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 50 ℃, 70% hydrazine hydrate is added into the mixture, the mixture is subjected to reflux reaction for 2 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 54g of m-phthaloyl chloride and 3g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to the temperature of 30 ℃, reacting for 60min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 4.5g of KH590 modified nano-silica and 0.48g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 110 ℃, reacting for 15h, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 0.75g of vinyl nano silicon dioxide, 1.8g of maleic anhydride and 0.3g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, stirring the mixture uniformly, heating the mixture to 240 ℃, reacting the mixture for 10min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 180g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 60r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Example 3
(1) 5g of 3, 5-dinitrobenzaldehyde and 3.6g of 5-aminoresorcinol are added into ethanol solvent, 5mL of glacial acetic acid catalyst is added into the mixture, the temperature is raised to 70 ℃, the reflux reaction is carried out for 10 hours, the mixture is cooled to room temperature after the reaction is finished, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 3g of triethylamine are added into a toluene solvent, 28g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of 0 ℃, the mixture is stirred and dispersed, the temperature is raised to 80 ℃, the reaction is carried out for 3 hours, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, thus obtaining intermediate 2.
(3) 15g of intermediate 2 and 0.6g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 45 ℃, 75% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 5 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 72g of m-phthaloyl chloride and 4.5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 20min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 4.6g of KH590 modified nano-silica and 0.4g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 120 ℃, reacting for 10 hours, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 1g of vinyl nano silicon dioxide, 1.6g of maleic anhydride and 0.5g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 200 ℃, reacting the mixture for 20min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 200g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 70r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Example 4
(1) 5g of 3, 5-dinitrobenzaldehyde and 4g of 5-aminoresorcinol are added into ethanol solvent, 6mL of glacial acetic acid catalyst is added into the ethanol solvent, the temperature is raised to 80 ℃, the reflux reaction is carried out for 6 hours, the reaction is cooled to room temperature after the reaction is finished, the mixture is filtered, washed by deionized water, and ethanol is recrystallized to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 1.9g of triethylamine are added into toluene solvent, 35g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of minus 5 ℃, the mixture is stirred and dispersed, the temperature is raised to 80 ℃ for 2 hours of reaction, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, so that intermediate 2 is obtained.
(3) 15g of intermediate 2 and 0.75g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 40 ℃, 78% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 5 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 50min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 4g of KH590 modified nano-silica and 0.48g of p-toluenesulfonic acid into a toluene solvent, stirring and dispersing, heating to 100 ℃, reacting for 20 hours, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 1.25g of vinyl nano silicon dioxide, 2g of maleic anhydride and 0.25g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 240 ℃, reacting the mixture for 20min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 220g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 50r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Example 5
(1) 5g of 3, 5-dinitrobenzaldehyde and 3g of 5-aminoresorcinol are added into ethanol solvent, 6mL of glacial acetic acid catalyst is added into the ethanol solvent, the temperature is raised to 80 ℃, the reflux reaction is carried out for 10 hours, the reaction is cooled to room temperature after the reaction is finished, the mixture is filtered, washed by deionized water, and ethanol is recrystallized to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 2.5g of triethylamine are added into a toluene solvent, 36g of diphenyl phosphorus chloride is added into the toluene solvent at 0 ℃, the mixture is stirred and dispersed, the temperature is raised to 70 ℃ for 5 hours of reaction, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, so that intermediate 2 is obtained.
(3) 15g of intermediate 2 and 0.6g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 50 ℃, 80% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 5 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 6g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 10 ℃ under the nitrogen condition, heating to 30 ℃, reacting for 60min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Adding 2g of 5-vinyl isophthalic acid, 5g of KH590 modified nano-silica and 0.4g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 120 ℃, reacting for 12 hours, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(6) Adding 1.5g of vinyl nano silicon dioxide, 1.8g of maleic anhydride and 0.6g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, stirring the mixture uniformly, heating the mixture to 220 ℃, reacting the mixture for 20min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(7) Mixing 200g of dried modified polyethylene and 240g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 50r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Comparative example 1
(1) Adding 2g of 5-vinyl isophthalic acid, 4.2g of KH590 modified nano-silica and 0.45g of p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 110 ℃, reacting for 18h, decompressing and distilling, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
(2) Adding 0.5g of vinyl nano silicon dioxide, 1.8g of maleic anhydride and 0.6g of dicumyl peroxide into an acetone solvent, adding 50g of polyethylene into the mixture, uniformly stirring the mixture, heating the mixture to 200 ℃, reacting the mixture for 15min, and drying the mixture after the reaction is finished to obtain the modified polyethylene.
(3) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 1.5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 45min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(4) Mixing 200g of dried modified polyethylene and 160g of modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 60r/min, granulating, and performing compression molding to obtain the modified polyethylene isolating film.
Comparative example 2
(1) 5g of 3, 5-dinitrobenzaldehyde and 3.8g of 5-aminoresorcinol are added into ethanol solvent, 6mL of glacial acetic acid catalyst is added into the mixture, the temperature is raised to 75 ℃, the reflux reaction is carried out for 12 hours, the mixture is cooled to room temperature after the reaction is finished, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain an intermediate 1.
(2) Under the condition of nitrogen, 20g of intermediate 1 and 3g of triethylamine are added into toluene solvent, 35g of diphenyl phosphorus chloride is added into the toluene solvent at the temperature of minus 5 ℃, the mixture is stirred and dispersed, the temperature is raised to 80 ℃ for 2 hours of reaction, after the reaction is finished, the mixture is cooled to room temperature, filtered, the filtrate is distilled under reduced pressure, and acetonitrile is recrystallized, thus obtaining intermediate 2.
(3) 15g of intermediate 2 and 0.6g of Pd/C are added into ethanol solvent under the condition of nitrogen, the temperature is raised to 50 ℃, 80% hydrazine hydrate is added into the solvent, the mixture is subjected to reflux reaction for 4 hours, and the mixture is filtered, washed by deionized water and recrystallized by ethanol to obtain phosphorus-containing m-phenylenediamine.
(4) Adding 30g of m-phenylenediamine, 60g of m-phthaloyl chloride and 1.5g of phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of minus 5 ℃ under the nitrogen condition, heating to 35 ℃, reacting for 45min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain the modified polyamide.
(5) Mixing dry polyethylene 200g and modified polyamide 160g uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 60r/min, granulating, and compression molding to obtain the modified polyethylene isolating film.
And testing the mechanical properties of the material by using an electronic universal tester.
Tensile Strength (MPa) Tensile modulus (GPa)
Example 1 16.92 0.34
Example 2 18.49 0.39
Example 3 20.64 0.46
Example 4 24.71 0.51
Example 5 22.30 0.49
Comparative example 1 15.64 0.26
Comparative example 2 14.93 0.21
As can be seen from the table, the mechanical properties of examples 1 to 5 are better than those of comparative examples 1 and 2, because the polyamide has fewer side chain groups and less entanglement with polyethylene in comparative example 1, and thus has poorer mechanical properties than examples 1 to 5, and the nanosilica is not contained in comparative example 2, and thus has poorer mechanical properties than examples 1 to 5.
The high temperature resistance of the material was tested using a heat distortion Vicat softening point tester, wherein the rate of temperature rise was 100 ℃/h.
Heat distortion temperature (DEG C)
Example 1 60
Example 2 64
Example 3 76
Example 4 85
Example 5 82
Comparative example 1 58
Comparative example 2 45
The heat resistance of examples 1-5 and comparative example 1 is better than that of comparative example 2 because the absence of nanosilica in comparative example 2, the strong interface between nanosilica and the material matrix can limit thermal movement of the molecular segments of the material matrix.
The limiting oxygen index of the material was measured using an oxygen index meter.
The horizontal vertical burn rating of the material was tested using a horizontal vertical burner.
As can be seen from the table, the flame retardant properties of examples 1 to 5 are better than those of comparative examples 1 and 2.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (10)

1. The preparation method of the high-temperature-resistant modified polyethylene isolating film is characterized by comprising the following steps of:
(1) Adding m-phenylenediamine, isophthaloyl dichloride and phosphorus-containing m-phenylenediamine into a dimethylacetamide solvent at the temperature of between-10 and-5 ℃ under the nitrogen condition, heating to 20-35 ℃, reacting for 20-60min, adding calcium hydroxide to neutralize after the reaction, washing with deionized water, and drying to obtain modified polyamide;
(2) Adding vinyl nano silicon dioxide, maleic anhydride and dicumyl peroxide into an acetone solvent, adding polyethylene into the acetone solvent, uniformly stirring, heating to 180-240 ℃, reacting for 5-20min, and drying after the reaction is finished to obtain modified polyethylene;
(3) Mixing the dried modified polyethylene and modified polyamide uniformly, adding into an extruder for extrusion, wherein the temperature of five areas is 160 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃ and the screw speed is 40-70r/min, granulating, and compression molding to obtain the modified polyethylene isolating film.
2. The method for preparing the high-temperature-resistant modified polyethylene isolating membrane according to claim 1, wherein in the step (1), the mass ratio of m-phenylenediamine to m-phthaloyl chloride to phosphorus-containing m-phenylenediamine is 100:180-240:5-20.
3. The method for preparing a high temperature resistant modified polyethylene isolating membrane according to claim 1, wherein in the step (2), the mass ratio of the vinyl nano silicon dioxide to the maleic anhydride to the dicumyl peroxide to the polyethylene is 1-3:2-4:0.5-1.5:100.
4. The method for producing a high temperature resistant modified polyethylene separator according to claim 1, wherein in the step (3), the mass ratio of the modified polyethylene to the modified polyamide is 100:80-120.
5. The method for preparing a high temperature resistant modified polyethylene insulation film according to claim 1, wherein in the step (1), the method for preparing phosphorus-containing m-phenylenediamine comprises the following steps:
s1, adding 3, 5-dinitrobenzaldehyde and 5-aminoresorcinol into an ethanol solvent, adding a glacial acetic acid catalyst into the ethanol solvent, heating to 60-80 ℃, carrying out reflux reaction for 5-12h, cooling to room temperature after the reaction is finished, filtering, washing with deionized water, and recrystallizing with ethanol to obtain an intermediate 1;
s2, adding the intermediate 1 and triethylamine into a toluene solvent under the condition of nitrogen, adding diphenyl phosphorus chloride into the toluene solvent at the temperature of between minus 5 and 0 ℃, stirring and dispersing, heating to the temperature of between 60 and 80 ℃, reacting for 2 to 5 hours, cooling to room temperature after the reaction is finished, filtering, distilling filtrate under reduced pressure, and recrystallizing acetonitrile to obtain an intermediate 2;
s3, adding the intermediate 2 and Pd/C into an ethanol solvent under the condition of nitrogen, heating to 40-50 ℃, adding 70-80% hydrazine hydrate into the mixture, carrying out reflux reaction for 2-5h, filtering, washing with deionized water, and recrystallizing with ethanol to obtain phosphorus-containing m-phenylenediamine.
6. The method for producing a high temperature resistant modified polyethylene insulation film according to claim 5, wherein in the step S1, the mass ratio of 3, 5-dinitrobenzaldehyde to 5-aminoresorcinol is 100:60-80.
7. The method for preparing a high temperature resistant modified polyethylene isolating film according to claim 5, wherein in the step S2, the molar ratio of the intermediate 1 to triethylamine to diphenyl phosphorus chloride is 100:5-15:140-180.
8. The method for preparing a high temperature resistant modified polyethylene insulation film according to claim 5, wherein in the step S3, the mass ratio of the intermediate 2 to Pd/C is 100:3-5.
9. The method for preparing a high temperature resistant modified polyethylene insulation film according to claim 1, wherein in the step (2), the method for preparing vinyl nano silica comprises the following steps: adding 5-vinyl isophthalic acid, KH590 modified nano-silica and p-toluenesulfonic acid into toluene solvent, stirring and dispersing, heating to 100-120 ℃, reacting for 10-20h, decompressing and distilling after the reaction is finished, washing with deionized water, and recrystallizing with methanol to obtain the vinyl nano-silica.
10. The method for producing a high temperature resistant modified polyethylene insulation film according to claim 9, wherein in the step, the molar ratio of 5-vinylisophthalic acid, KH590 modified nanosilica, p-toluenesulfonic acid is 100:200-250:18-24.
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* Cited by examiner, † Cited by third party
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JPH05339407A (en) * 1992-06-11 1993-12-21 Tonen Chem Corp Production of fuel tank
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US6025423A (en) * 1994-09-28 2000-02-15 Elf Atochem S.A. Flame-retardant thermoplastic compositions for electrical cable coatings
US20020182390A1 (en) * 2001-04-04 2002-12-05 Robert Migliorini Multilayer films including anti-block
CN108017852A (en) * 2017-12-22 2018-05-11 安徽华塑股份有限公司 A kind of high-strength polyvinyl chloride resin and preparation method thereof
CN108314818A (en) * 2018-01-19 2018-07-24 四川厚诚新材料有限公司 A kind of delustring curtain coating PE films and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339407A (en) * 1992-06-11 1993-12-21 Tonen Chem Corp Production of fuel tank
EP0583595A1 (en) * 1992-07-20 1994-02-23 Bayer Ag Impact resistant, optionally filled polyamide mixtures with polyamide-polyethylene laminated film wastes
US6025423A (en) * 1994-09-28 2000-02-15 Elf Atochem S.A. Flame-retardant thermoplastic compositions for electrical cable coatings
US20020182390A1 (en) * 2001-04-04 2002-12-05 Robert Migliorini Multilayer films including anti-block
CN108017852A (en) * 2017-12-22 2018-05-11 安徽华塑股份有限公司 A kind of high-strength polyvinyl chloride resin and preparation method thereof
CN108314818A (en) * 2018-01-19 2018-07-24 四川厚诚新材料有限公司 A kind of delustring curtain coating PE films and preparation method thereof

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