CN112266496B - Multilayer composite film based on polyimide modification and preparation process thereof - Google Patents

Multilayer composite film based on polyimide modification and preparation process thereof Download PDF

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CN112266496B
CN112266496B CN202011180844.0A CN202011180844A CN112266496B CN 112266496 B CN112266496 B CN 112266496B CN 202011180844 A CN202011180844 A CN 202011180844A CN 112266496 B CN112266496 B CN 112266496B
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polyimide
multilayer composite
modification
composite film
stirring
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CN112266496A (en
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翁星星
贾培梁
沈亚定
盛夏
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Jiangsu Housheng New Energy Technology Co Ltd
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Jiangsu Housheng New Energy Technology Co Ltd
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
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    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
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    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention discloses a polyimide modification-based multilayer composite film and a preparation process thereof. The multilayer composite membrane comprises a base membrane and a filtering and adsorbing layer, and a filter core layer is arranged between the base membrane and the filtering and adsorbing layer; the base film is a multilayer composite film consisting of one or more of a polyethylene film, a polypropylene film and a polyimide film; the filter element layer is formed by coating porous filler and binder, and the filter absorption layer is formed by coating modified polyimide slurry. According to the method, polycaprolactone, isocyanate and ferroferric oxide particles are modified to form a coordination compound with a cross-linked network structure, the coordination compound modifies polyimide to obtain modified polyimide slurry, and the modified polyimide slurry is coated on a composite membrane, so that the excellent adsorption effect of the ferroferric oxide particles on suspended solid, phosphorus and heavy metal ions in sewage can be exerted, and meanwhile, the mechanical strength and the high-temperature resistance of the multilayer composite membrane can be improved.

Description

Multilayer composite film based on polyimide modification and preparation process thereof
Technical Field
The invention relates to the technical field of water treatment filtering membranes, in particular to a polyimide modification-based multilayer composite membrane and a preparation process thereof.
Background
Currently, the severity and importance of water pollution problems has become increasingly common in all communities. The shortage of fresh water resources in China is extreme, and the water pollution phenomenon is serious, so the research and development of economic, environment-friendly and efficient water treatment technology is one of the most important development directions in the field of water treatment. The membrane separation technology is favored in the field of water treatment by virtue of high efficiency, energy conservation, environmental protection, simple process and easy control. Microfiltration membranes are widely used as important components in the membrane separation industry in the fields of medicine, food, chemical industry, biology and the like. The high molecular micro-filtration membrane is usually prepared by methods such as thermally induced phase separation, stretching pore-forming, non-solvent phase conversion, electrostatic spinning and the like, and the inorganic micro-filtration membrane is mainly prepared by a sintering method, a sol-gel method, anodic oxidation, chemical vapor deposition and the like. Polyolefin materials are the most widely used thermoplastic polymer materials, and have been widely used in water treatment polymer microfiltration membranes. The invention aims to provide the polyolefin composite microfiltration membrane with high mechanical strength, excellent high-temperature resistance and high water pollutant treatment efficiency.
Disclosure of Invention
The invention aims to provide a polyimide modification-based multilayer composite film and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a multilayer composite membrane based on polyimide modification comprises a base membrane, a filtering adsorption layer; and a filter core layer is arranged between the base film and the filtering adsorption layer.
Furthermore, the base film is a multilayer composite film composed of one or more of polyethylene film, polypropylene film and polyimide film, and the aperture of the multilayer composite film is 1-150 nm.
Further, the filter element layer is formed by coating filler and adhesive; the filler is any one or more of activated carbon, multi-level magnesium silicate and molecular sieve; the binder is any one or more of water-based polyacrylate, polyvinyl alcohol and ethylene-vinyl acetate copolymer.
Further, the filtering and adsorbing layer is formed by coating modified polyimide slurry.
Further, the modified polyimide slurry is mainly prepared by reacting polyimide, polycaprolactone, dimethylacetamide, dopamine hydrochloride, ferroferric oxide particles and a catalyst.
Further, the catalyst is any one or more of stannous octoate, dibutyltin dilaurate, dialkyl tin dimaleate and dithiol alkyl tin.
A preparation process of a multilayer composite film based on polyimide modification comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating and melting polycaprolactone, dissolving the polycaprolactone in a dimethylacetamide solvent, adding diisocyanate and a catalyst, stirring, heating to 90-105 ℃, and reacting to obtain a reaction solution A; dissolving dopamine hydrochloride in a dimethylacetamide solvent, adding triethylamine, mixing and stirring, adding the mixture into a reaction solution A, keeping the temperature at 47-53 ℃, reacting, precipitating and drying to obtain modified polycaprolactone, melting, adding ferroferric oxide particles, uniformly stirring, and naturally drying to obtain a modifier;
the ferroferric oxide particles can also be ferroferric oxide nanoparticles modified by oleic acid groups.
S2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 80-90 ℃, reacting, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modified multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring and adsorbing; evaporating the solvent, roasting and drying to obtain the pretreated filler; mixing the pretreated filler with the binder, uniformly coating the mixture on the surface of a base film, and carrying out ventilation drying to form a filter core layer; uniformly coating modified polyimide slurry on the surface of the filter element layer, and heating and curing to form a filtering adsorption layer; and preparing the multilayer composite film based on polyimide modification.
Furthermore, the preparation process of the multilayer composite film based on polyimide modification also comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating polycaprolactone to 60-70 ℃, melting for 15-20min, dissolving in a dimethylacetamide solvent, adding diisocyanate and a catalyst, stirring, heating to 90-105 ℃, and reacting for 2-3h to obtain a reaction solution A; dissolving dopamine hydrochloride in a dimethylacetamide solvent, adding triethylamine, mixing and stirring, adding the mixture into the reaction solution A, keeping the temperature at 47-53 ℃, reacting for 5-7 hours, precipitating, drying to obtain modified polycaprolactone, melting, adding ferroferric oxide particles, uniformly stirring, and naturally drying to obtain a modifier;
s2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 80-90 ℃, reacting for 30-40min, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modified multilayer composite film:
taking a base film, wiping the surface of the base film, and carrying out high-voltage corona with the current value of 1-3A; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring, and adsorbing for 2-3h; evaporating the solvent and roasting to obtain the pretreated filler; mixing the pretreated filler and the binder in a mass ratio of 20;
the polarity of the surface of the base film can be enhanced and the adhesion force of the base film and the porous filler can be enhanced through high-voltage corona treatment of the base film; the porous filler is treated by a small amount of aluminum sulfate in advance, so that the pores of the porous filler contain a small amount of aluminum sulfate, and phosphorus left by filtration of the filtration adsorption layer can be further removed while the adsorption effect of the porous filler is not influenced.
Uniformly coating modified polyimide slurry on the surface of the filter element layer, and heating and curing to form a filtering adsorption layer; the multilayer composite membrane based on polyimide modification is prepared.
Further, the temperature rise and solidification process in the step (2) comprises the steps of preserving heat for 2-3h at the temperature of 80-100 ℃ and preserving heat for 1-2h at the temperature of 120-160 ℃; keeping the temperature at 200-220 ℃ for 0.5-2h; keeping the temperature at 270-300 ℃ for 0.5-1.5h.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a multilayer composite membrane for water treatment, which consists of a multilayer polyolefin composite membrane and a filtering and adsorbing layer, wherein a filter core layer is arranged between the multilayer polyolefin composite membrane and the filtering and adsorbing layer. Wherein the filtering and adsorbing layer is formed by coating modified polyimide slurry, and the slurry mainly comprises polyimide, ferroferric oxide particles and polycaprolactone; because the ferroferric oxide particles have a porous network structure, the solid suspended substances, phosphorus and Cu in the sewage can be effectively adsorbed 2+ 、Cd 2 + 、Pb 2+ The heavy metal ions are the same, but the ferroferric oxide particles are easy to agglomerate and are easy to be oxidized into ferric oxide when being placed in the air, so the adsorption effect is greatly reduced. In order to solve the problem, the scheme adopts dopamine hydrochloride, isocyanate and the like to modify polycaprolactone, the modified polycaprolactone can form stable coordination with ferroferric oxide, and the modified polycaprolactone has a stable cross-linked network structure, can protect the ferroferric oxide from being oxidized, and can keep the ferroferric oxide to adsorb suspended solid, phosphorus and heavy metal ions in sewage for a long time. In addition, the hydroxyl group on the surface of the compound molecule is bonded with the carboxyl group on the surface of the polyimide molecule, so that the molecular chain structure of the polyimide is increased, and the high-temperature resistance of the polyimide is further improved; the added ferroferric oxide particles can be used as inorganic filler to improve the mechanical strength and the high-temperature resistance of the polyimide; coating the modified polyimide slurry on the surface of the composite membrane to obtain a multilayer composite membrane with higher mechanical strength and high temperature resistance; the filtering and adsorbing layer and the lower filter element layer have the same effect, and can efficiently and continuously adsorb suspended solid and heavy metal ions in sewageThe effect of the method can be widely applied to sewage upgrading treatment.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing raw materials: the filler is the combination of active carbon and multilevel magnesium silicate; the binder is water-based polyacrylate; the catalyst is stannous octoate.
A preparation process of a multilayer composite film based on polyimide modification comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating polycaprolactone to 60 ℃, melting for 15min, dissolving in a dimethylacetamide solvent, adding diisocyanate and stannous octoate, stirring, heating to 90 ℃, and reacting for 2h to obtain a reaction solution A; dissolving dopamine hydrochloride in a dimethylacetamide solvent, adding triethylamine, mixing and stirring, adding the mixture into the reaction solution A, keeping the temperature at 47 ℃, reacting for 5 hours, precipitating, drying to obtain modified polycaprolactone, melting, adding ferroferric oxide particles, stirring uniformly, and naturally drying to obtain a modifier;
s2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 80 ℃, reacting for 30min, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modification-based multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona with the current value of 1A; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring, and adsorbing for 2 hours; evaporating the solvent, roasting and drying to obtain the pretreated filler; mixing the pretreated filler and the binder according to a mass ratio of 20;
uniformly coating modified polyimide slurry on the surface of the filter element layer, heating and curing, wherein the curing process is heat preservation at 80 ℃ for 2h and heat preservation at 120 ℃ for 1h; keeping the temperature at 200 ℃ for 0.5h; keeping the temperature at 270 ℃ for 0.5h; forming a filtering and adsorbing layer with the thickness of 1 mu m; and preparing the multilayer composite film based on polyimide modification.
Example 2
Preparing raw materials: the filler is activated carbon; the binder is polyvinyl alcohol; the catalyst was dibutyltin dilaurate.
A preparation process of a multilayer composite film based on polyimide modification comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating polycaprolactone to 67 ℃, melting for 17min, dissolving in a dimethylacetamide solvent, adding ferroferric oxide particles, uniformly stirring, evaporating the solvent, and naturally drying to obtain a modifier;
s2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 85 ℃, reacting for 35min, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modification-based multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona with the current value of 1A; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring, and adsorbing for 2.5 hours; evaporating the solvent, roasting and drying to obtain the pretreated filler; mixing the pretreated filler and the binder in a mass ratio of 20;
uniformly coating the modified polyimide slurry on the surface of the filter element layer, heating and curing, wherein the curing process comprises the steps of keeping the temperature at 90 ℃ for 2.5h and keeping the temperature at 155 ℃ for 1.5h; keeping the temperature at 210 ℃ for 0.9h; keeping the temperature at 275 ℃ for 1h; forming a filtering and adsorbing layer with the thickness of 2 mu m; and preparing the multilayer composite film based on polyimide modification.
Example 3
Preparing raw materials: the filler is a molecular sieve; the binder is polyvinyl alcohol; the catalyst was dibutyltin dilaurate.
A preparation process of a multilayer composite film based on polyimide modification comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating polycaprolactone to 70 ℃, melting for 17min, dissolving in a dimethylacetamide solvent, adding diisocyanate and dibutyltin dilaurate, stirring, heating to 105 ℃, and reacting for 3h to obtain a reaction solution A; dissolving dopamine hydrochloride in a dimethylacetamide solvent, adding triethylamine, mixing and stirring, adding the mixture into a reaction solution A, keeping the temperature at 53 ℃, reacting for 7 hours, precipitating, drying to obtain modified polycaprolactone, melting, adding ferroferric oxide particles, uniformly stirring, and naturally drying to obtain a modifier;
s2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 90 ℃, reacting for 40min, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modification-based multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona with the current value of 3A; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring, and adsorbing for 3 hours; evaporating the solvent, roasting and drying to obtain the pretreated filler; mixing the pretreated filler and the binder according to a mass ratio of 20;
uniformly coating modified polyimide slurry on the surface of the filter element layer, heating and curing, wherein the curing process is heat preservation at 100 ℃ for 3h and at 160 ℃ for 2h; preserving heat for 2 hours at 220 ℃; keeping the temperature at 300 ℃ for 1.5h; forming a filtering adsorption layer with the thickness of 3 mu m; the multilayer composite membrane based on polyimide modification is prepared.
Comparative example 1
Preparing raw materials: the filler is a molecular sieve; the binder is polyvinyl alcohol; the catalyst was dibutyltin dilaurate.
A preparation process of a multilayer composite film based on polyimide modification comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating polycaprolactone to 70 ℃, melting for 17min, dissolving in a dimethylacetamide solvent, adding diisocyanate and dibutyltin dilaurate, stirring, heating to 105 ℃, and reacting for 3h to obtain a reaction solution A; dissolving dopamine hydrochloride in a dimethylacetamide solvent, adding triethylamine, mixing and stirring, adding the mixture into a reaction solution A, keeping the temperature at 53 ℃, reacting for 7 hours, precipitating, drying to obtain modified polycaprolactone, melting, adding ferroferric oxide particles, uniformly stirring, and naturally drying to obtain a modifier;
s2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 90 ℃, reacting for 40min, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modification-based multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona with the current value of 3A; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring, and adsorbing for 3 hours; evaporating the solvent, roasting and drying to obtain the pretreated filler; mixing the pretreated filler and the binder in a mass ratio of 20;
uniformly coating modified polyimide slurry on the surface of the filter element layer, heating and curing, wherein the curing process is heat preservation at 100 ℃ for 3h and at 160 ℃ for 2h; preserving heat for 2 hours at 220 ℃; keeping the temperature at 300 ℃ for 1.5h; forming a filtering and adsorbing layer with the thickness of 3 mu m; the multilayer composite membrane based on polyimide modification is prepared.
Comparative example 2
Preparing raw materials: the filler is a molecular sieve; the binder is polyvinyl alcohol; the catalyst was dibutyltin dilaurate.
A preparation process of a multilayer composite film based on polyimide modification comprises the following steps;
(1) Preparing modified polyimide slurry:
performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding ferroferric oxide particles, stirring, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modification-based multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona with the current value of 3A; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring, and adsorbing for 3 hours; evaporating the solvent, roasting and drying to obtain the pretreated filler; mixing the pretreated filler and the binder in a mass ratio of 20;
uniformly coating modified polyimide slurry on the surface of the filter element layer, heating and curing, wherein the curing process is heat preservation at 100 ℃ for 3h and at 160 ℃ for 2h; preserving heat for 2 hours at 220 ℃; keeping the temperature at 300 ℃ for 1.5h; forming a filtering adsorption layer with the thickness of 3 mu m; and preparing the multilayer composite film based on polyimide modification.
Comparative example 3
Preparing raw materials: the filler is a molecular sieve; the binder is polyvinyl alcohol; the catalyst is dibutyltin dilaurate.
A preparation process of a multilayer composite film based on polyimide modification comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating polycaprolactone to 70 ℃, melting for 17min, dissolving in a dimethylacetamide solvent, adding diisocyanate and dibutyltin dilaurate, stirring, heating to 105 ℃, and reacting for 3h to obtain a reaction solution A; dissolving dopamine hydrochloride in a dimethylacetamide solvent, adding triethylamine, mixing and stirring, adding the mixture into the reaction solution A, keeping the temperature at 53 ℃, reacting for 7 hours, precipitating, drying to obtain modified polycaprolactone, melting, adding ferroferric oxide particles, stirring uniformly, and naturally drying to obtain a modifier;
s2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 90 ℃, reacting for 40min, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modification-based multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona with the current value of 3A; mixing the filler and the binder according to a mass ratio of 20;
uniformly coating modified polyimide slurry on the surface of the filter element layer, heating and curing, wherein the curing process is heat preservation at 100 ℃ for 3h and at 160 ℃ for 2h; preserving heat for 2 hours at 220 ℃; keeping the temperature at 300 ℃ for 1.5h; forming a filtering and adsorbing layer with the thickness of 3 mu m; and preparing the multilayer composite film based on polyimide modification.
Testing and data analysis
The multilayer composite films prepared in examples 1-3 and comparative examples 1-3 are subjected to strength and high temperature resistance detection, and the detection results are shown in the following table 1;
tensile strength, MPa 200 ℃ heat shrinkage,%
Example 1 56 0.2
Example 2 56 0.2
Example 3 57 0.2
Comparative example 1 50 0.5
Comparative example 2 45 0.8
Comparative example 3 53 0.8
TABLE 1
As can be seen from the data in Table 1, the multilayer composite films prepared in examples 1 to 3 have higher tensile strength and smaller shrinkage deformation at 200 ℃ than comparative examples 1 to 2; therefore, the mechanical strength and the high-temperature resistance of the composite film can be enhanced by coating the composite film with the modified polyimide slurry prepared by the scheme; in the comparative examples 1-2, the preparation steps are respectively simplified, and the mechanical strength and the high temperature resistance of the composite membrane are finally reduced, so that the preparation process of the technical scheme is the best scheme, and the generated beneficial effect is optimal.
Performing a water treatment test on each group of multilayer composite membranes, wherein detection data are shown in the following table 2;
taking sewage in a certain sewage tank, detecting the content of suspended matters, phosphorus and ions in the sewage, averagely dividing the sewage into 6 groups, filtering the sewage by using the multilayer composite membrane prepared in the embodiment 1-3 and the comparative example 1-3, detecting the content of pollutants in each group of treated sewage, and obtaining detection results shown in the following table 2;
the content of each pollutant in the sewage sample before treatment; 500mg/l suspended matter, 5.3mg/l phosphorus, 1.3mg/l copper ion and 1.5mg/l lead ion;
suspended substance, mg/l Phosphorus, mg/l Copper ion, mg/l Lead ion, mg/l
Example 1 10 0.25 ＜0.001 ＜0.001
Example 2 9 0.22 ＜0.001 ＜0.001
Example 3 10 0.20 ＜0.001 ＜0.001
Comparative example 1 45 0.37 ＜0.001 0.004
Comparative example 2 60 0.48 0.003 0.001
Comparative example 3 45 0.30 0.007 0.002
TABLE 2
As can be seen from the data in Table 2, the multilayer composite membrane prepared in the embodiments 1-3 has a good treatment effect on sewage, wherein the contents of copper ions and lead ions are reduced to below 0.001mg/l, and the discharge standard is reached; the contents of phosphorus, suspended matters, copper and lead ions in the sewage treated by the composite membrane prepared in the comparative example 1-3 are all higher than the treatment effects of the example 1-3; therefore, the multilayer composite film prepared by the technical scheme has the optimal treatment effect.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A multilayer composite film based on polyimide modification is characterized in that; the multilayer composite membrane comprises a base membrane and a filtering and adsorbing layer; a filter core layer is arranged between the base membrane and the filtering adsorption layer;
the filtering and adsorbing layer is formed by coating modified polyimide slurry;
the modified polyimide slurry is mainly prepared by reacting polyimide, polycaprolactone, dimethylacetamide, dopamine hydrochloride, ferroferric oxide particles and a catalyst;
the preparation method comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating and melting polycaprolactone, dissolving the polycaprolactone in a dimethylacetamide solvent, adding diisocyanate and a catalyst, stirring, heating to 90-105 ℃, and reacting to obtain a reaction solution A; dissolving dopamine hydrochloride in a dimethylacetamide solvent, adding triethylamine, mixing and stirring, adding the mixture into the reaction solution A, keeping the temperature at 47-53 ℃, reacting, precipitating and drying to obtain modified polycaprolactone, melting, adding ferroferric oxide particles, uniformly stirring, and naturally drying to obtain a modifier;
s2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 80-90 ℃, reacting, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modification-based multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring and adsorbing; evaporating the solvent, roasting and drying to obtain the pretreated filler; mixing the pretreated filler with the binder, uniformly coating the mixture on the surface of a base film, and carrying out ventilation drying to form a filter core layer;
uniformly coating modified polyimide slurry on the surface of the filter element layer, and heating and curing to form a filtering adsorption layer; and preparing the multilayer composite film based on polyimide modification.
2. The polyimide modification-based multilayer composite film according to claim 1, wherein: the base film is a multilayer composite film consisting of one or more of a polyethylene film, a polypropylene film and a polyimide film, and the aperture of the multilayer composite film is 1-150 nm.
3. The polyimide modification-based multilayer composite film according to claim 1, wherein: the filter element layer is formed by coating filler and binder; the filler is any one or more of activated carbon, multi-level magnesium silicate and molecular sieve; the binder is any one or more of water-based polyacrylate, polyvinyl alcohol and ethylene-vinyl acetate copolymer.
4. The polyimide modification-based multilayer composite film according to claim 1, wherein: the catalyst is any one or more of stannous octoate, dibutyltin dilaurate, dialkyl tin dimaleate and dithiol alkyl tin.
5. The polyimide modification-based multilayer composite film according to claim 1, wherein; the preparation method comprises the following steps;
(1) Preparing modified polyimide slurry:
s1, heating polycaprolactone to 60-70 ℃, melting for 15-20min, dissolving in a dimethylacetamide solvent, adding diisocyanate and a catalyst, stirring, heating to 90-105 ℃, and reacting for 2-3h to obtain a reaction solution A; dissolving dopamine hydrochloride in a dimethylacetamide solvent, adding triethylamine, mixing and stirring, adding the mixture into the reaction solution A, keeping the temperature at 47-53 ℃, reacting for 5-7 hours, precipitating, drying to obtain modified polycaprolactone, melting, adding ferroferric oxide particles, uniformly stirring, and naturally drying to obtain a modifier;
s2, performing surface carboxylation modification treatment on polyimide, dispersing the polyimide in water, adding the modifier prepared in the step S1 and concentrated sulfuric acid, stirring, heating to 80-90 ℃, reacting for 30-40min, and naturally drying to obtain modified polyimide slurry;
(2) Preparing a polyimide modification-based multilayer composite film:
taking a base film, wiping the surface of the base film clean, and carrying out high-voltage corona with the current value of 1-3A; dissolving aluminum sulfate in a solvent, adding a filler, uniformly stirring, and adsorbing for 2-3h; evaporating the solvent, roasting and drying to obtain the pretreated filler; mixing the pretreated filler and the binder in a mass ratio of 20;
uniformly coating modified polyimide slurry on the surface of the filter element layer, and heating and curing to form a filtering adsorption layer; and preparing the multilayer composite film based on polyimide modification.
6. The polyimide modification-based multilayer composite film according to claim 5, wherein; the temperature rise and solidification process in the step (2) comprises the steps of preserving heat for 2-3h at the temperature of 80-100 ℃ and preserving heat for 1-2h at the temperature of 120-160 ℃;
keeping the temperature at 200-220 ℃ for 0.5-2h; keeping the temperature at 270-300 ℃ for 0.5-1.5h.
7. The polyimide modification-based multilayer composite film according to claim 5, wherein; the thickness of the filter element layer is 5-20 μm; the thickness of the filtering and adsorbing layer is 1-3 μm.
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