CN113929951A - Flame-retardant material with layered brick-wall structure and preparation method thereof - Google Patents
Flame-retardant material with layered brick-wall structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame retardant material with a layered brick-wall structure and a preparation method thereof, relating to the technical field of flame retardant materials, wherein the flame retardant material comprises lamellar inorganic nano materials and polymers, and the lamellar inorganic nano materials are orderly arranged in the polymers; the flame retardant material prepared by the invention has obviously improved flame retardant property, and can reduce the oxygen transmission rate to 7.98cm3/m2/day/0.1MPa。
Description
Technical Field
The invention relates to the technical field of flame retardant materials, in particular to a flame retardant material with a layered brick-wall structure and a preparation method thereof.
Background
Polymer materials have been found to be widely used in various fields due to their many advantages, such as light weight, good chemical stability, corrosion resistance, easy processing, etc. In recent years, energy conservation and environmental protection are vigorously advocated by the nation, and in order to reduce energy consumption, novel building exterior walls are usually covered by adopting heat-insulating flame-retardant polymer foam materials. However, due to the organic composition of the common polymer materials, the flammability is high, which limits the application of the polymer materials in some occasions requiring fire-proof and flame-retardant properties. In order to ensure the safety of human and property, it has become an important issue to improve the fire safety of polymer materials.
In designing flame retardant polymeric materials, it is generally contemplated to add flame retardants to the system. The flame retardant can be broadly classified into organic flame retardants and inorganic flame retardants, wherein the organic flame retardants are mainly halogen-based and halogen-free. For halogen flame retardants, the dosage is less, the flame retardant efficiency is high, the applicability is wide, but more smoke and corrosive gas are generated in the combustion process, and the environment is damaged when the halogen flame retardants are harmful to human bodies; the halogen-free flame retardant, such as phosphorus flame retardant and nitrogen flame retardant, is not as applicable as halogen-containing flame retardant, but has better safety. Inorganic flame retardants, such as aluminum hydroxide, magnesium hydroxide, and the like, are less harmful and have good smoke suppression, but have low flame retardant efficiency and are therefore generally highly filled, which is generally detrimental to the mechanical properties and processability of polymeric flame retardant materials. Therefore, the environment-friendly flame-retardant material prepared by the simple process has a very wide application prospect.
With the intensive research on the polymer flame retardant material, the lamellar inorganic nano material is also concerned to be applied to the flame retardant material. When the lamellar inorganic nano materials are orderly arranged in the vertical direction of the flame retardant material and present a lamellar brick-wall structure, the structure has good barrier effect on oxygen, and combustion-supporting gas is difficult to enter the material; the internal thermal decomposition combustible gas is difficult to release to the outside to maintain combustion, and further the flame retardant effect is achieved. The biggest difficulty of the materials is how to arrange the lamellar inorganic nano materials in order by a simple preparation process and obtain a lamellar brick-wall structure.
Disclosure of Invention
The invention aims to provide a flame-retardant material with a layered brick-wall structure and a preparation method thereof, which are used for solving the problems in the prior art and remarkably improving the flame-retardant property of the flame-retardant material.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a flame retardant material with a layered brick-wall structure, which comprises lamellar inorganic nano materials and a polymer, wherein the lamellar inorganic nano materials are orderly arranged in the polymer.
Further, the lamellar inorganic nano-material is at least one of montmorillonite, mica, laponite, boron nitride, graphene derivatives and lamellar double hydroxide; the polymer is polyvinyl alcohol, polyethylene imine, polyacrylamide, chitosan, sodium carboxymethyl cellulose, polydopamine, polyvinyl amine, polyamic acid salt or polyimide.
The invention also provides a preparation method of the flame retardant material with the layered brick-wall structure, the flame retardant material is prepared by a vacuum filtration assisted deposition method, and the preparation method comprises the following steps:
(1) preparing lamellar inorganic nano colloid:
dispersing the lamellar inorganic nano material in pure water to obtain a suspension, centrifuging to collect supernatant, and evaporating to remove part of water to ensure that the mass concentration of the obtained lamellar inorganic nano colloid is 1.0-3.2%;
(2) preparing a polymer into a polymer solution with a certain concentration, which specifically comprises the following steps: when the polymer is polyamic acid salt or polyimide, preparing a polymer solution with the mass concentration of 10%; when the polymer is polyvinyl alcohol, polyethyleneimine, polyacrylamide, chitosan, sodium carboxymethylcellulose, polydopamine or polyvinyl amine, the polymer is prepared into a polymer solution with the mass concentration of 5%;
(3) mixing the lamellar inorganic nano colloid with the polymer solution to obtain a composite glue solution, pouring the composite glue solution into a Buchner funnel or a sand core funnel, performing vacuum filtration to obtain a filter cake, orderly arranging the lamellar inorganic nano materials in the filter cake under the action of pressure, and drying the filter cake to obtain the flame retardant material with the lamellar brick-wall structure.
The invention also provides a preparation method of the flame retardant material with the laminated brick-wall structure, which comprises the following steps:
(1) preparing lamellar inorganic nano colloid:
dispersing the lamellar inorganic nano material in pure water to obtain a suspension, centrifuging to collect supernatant, and evaporating to remove part of water to ensure that the mass concentration of the obtained lamellar inorganic nano colloid is 1.0-3.2%;
(2) preparing a polymer into a polymer solution with a certain concentration, which specifically comprises the following steps: when the polymer is polyamic acid salt or polyimide, preparing a polymer solution with the mass concentration of 10%; when the polymer is polyvinyl alcohol, polyethyleneimine, polyacrylamide, chitosan, sodium carboxymethylcellulose, polydopamine or polyvinyl amine, the polymer is prepared into a polymer solution with the mass concentration of 5%;
(3) coating or immersing the lamellar inorganic nano colloid and the polymer solution on a substrate material to obtain a flame-retardant material wet material, and drying the flame-retardant material wet material to prepare the flame-retardant material with the lamellar brick-wall structure.
Further, the step (3) adopts a gravity-induced deposition method, and specifically comprises the following steps: and (3) mixing the lamellar inorganic nano colloid and the polymer solution according to the mass ratio of the lamellar inorganic nano material to the polymer of 1:1, obtaining a composite glue solution, then coating or immersing the composite glue solution on a substrate material subjected to surface treatment to obtain a flame-retardant material wet material, and then drying the flame-retardant material wet material to obtain the flame-retardant material with a laminated brick-wall structure. The thickness of the used lamellar inorganic nano material is only between one and several nanometers, and the length and width of the lamellar inorganic nano material are several micrometers, so that the center of gravity of the lamellar inorganic nano material is at the center. When the projection of the gravity center in the vertical direction falls on the supporting surface of the object, the object keeps balance, and the larger the supporting surface is, the stronger the capability of keeping balance is. Thus, during gravity-induced deposition, as the solvent evaporates, the lamellar inorganic nanomaterials tend to align more in a "lay-flat" manner, which maximizes support area and equilibrium stability, thereby resulting in a lamellar brick-wall structure.
Further, the step (3) adopts a layer-by-layer self-assembly method, which specifically comprises the following steps: coating one or two surfaces of the substrate material subjected to surface treatment with the lamellar inorganic nano colloid to enable the lamellar inorganic nano material to deposit a layer on the substrate material, pouring the coated lamellar inorganic nano colloid cleanly, washing with clear water, drying, then coating the polymer solution to enable the polymer to deposit a layer, pouring the coated polymer solution cleanly, washing with clear water, and drying; repeating the above operations alternately for not less than 10 times, and then drying to obtain the flame retardant material with a layered brick-wall structure.
Further, the coating is spray coating with a spray gun.
Further, the surface treatment adopts plasma surface treatment, corona treatment or alkali solution corrosion treatment.
Further, the substrate material is polyethylene terephthalate (PET), Polyimide (PI), polypropylene (PP), Polyethylene (PE), polyvinyl alcohol (PVA), ethylene vinyl alcohol (EVOH), Polyurethane (PU) foam, or Polystyrene (PS) foam.
Further, the drying is performed by the first stage of drying at 50 ℃ for 2h, the second stage of drying at 70 ℃ for 1h, and the third stage of drying at 80-250 ℃ for 0.5-3h, wherein when PI is used as a polymer (cement) and PI is used as a substrate material, the third stage of drying at 250 ℃ for 0.5 h; when PAAS is used as a polymer (cement) and PI is used as a substrate material, the temperature is raised to 150 ℃ in the third stage and the drying is carried out for 1 h; and when polyvinyl alcohol, polyethyleneimine, polyacrylamide, chitosan, sodium carboxymethylcellulose, polydopamine or polyvinylamine is used as a polymer (cement) and PET, PI, PP, PE, PVA, EVOH, PU foam or PS foam is used as a substrate material, heating to 80 ℃ in the third stage, and drying for 3 hours.
The invention discloses the following technical effects:
the invention utilizes lamellar inorganic nano materials to fill polymers, and the lamellar inorganic nano materials are orderly arranged in the flame retardant material in a lying mode through a specific preparation process, thereby obtaining the flame retardant material with a lamellar brick-wall structure. Due to the orderly arranged lamellar inorganic nano materials, in the process of material combustion, external oxygen is effectively prevented from entering the interior of the material to support combustion, and meanwhile, combustible gas thermally decomposed in the interior of the material is difficult to escape from the exterior to maintain combustion, so that the flame retardant property is remarkably improved.
The flame retardant material has good flame retardant property; the preparation process is a liquid process, and the preparation method is simple and easy to implement; the added lamellar inorganic nano material can adopt natural minerals with wide sources and low price, and can also adopt artificially synthesized lamellar materials to regulate and control the size, the composition and the functions; the method disclosed by the invention is suitable for various polymers as flame-retardant material base materials, and can improve the flame-retardant performance of various film materials, block materials and foam materials. The preparation process mainly adopts the modes of coating, immersing, spraying and the like, and the adopted equipment is simple, is suitable for large-scale industrial manufacture, and has important practical application significance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic view of a flame retardant material with a layered brick-wall structure, which is prepared in example 1 and uses polyimide as a substrate material, wherein 1 is a PI molecular chain in the flame retardant material, and 2 is a lamellar inorganic nano material montmorillonite;
FIG. 2 is a scanning electron microscope image of the cross section of the flame retardant material with a laminated brick-wall structure prepared in example 1 and using polyimide as a substrate material;
FIG. 3 is a scanning electron microscope image of the cross section of the flame retardant material with a laminated brick-wall structure prepared in example 3 and using polyimide as a substrate material.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the following examples, the Kapton film sources were: new Stannless sin material Co. The source of the PE film was: guangzhou City Chanhong packaging products Co. The sources of PET film were: hengda Automation technology (Tazhou) Inc.
Example 1
This example is a preparation example of a polyimide-based flame retardant material with a layered brick-wall structure prepared by gravity-induced deposition, prepared by the following steps:
(1) preparing an exfoliated sodium montmorillonite colloid: taking 6g of sodium-based montmorillonite and 500mL of ultrapure water in a 1000mL beaker, performing ultrasonic treatment for 1h by using a high-power ultrasonic generator (900W) (the program is set to be ultrasonic on for 1min, and the circulation is closed for 1 min) to obtain a suspension, and separating the non-peeled montmorillonite by using a high-speed centrifuge, wherein the rotating speed of the centrifuge is set to be 10000rpm, and the centrifugation time is 7 minutes. Collecting supernatant, placing in a 500mL eggplant-shaped bottle, and evaporating part of water by using a rotary evaporator to obtain stripped montmorillonite colloid with the mass fraction of 3.2%;
(2) preparation of Polyamic acid: 2.3172g (10.1965mmol) of DABA and 44mL of DMAC are put into a 100mL three-neck flask, nitrogen is introduced, after diamine is completely dissolved, 3.0000g (10.1965mmol) of BPDA is added, and the mixture is stirred for 10 to 12 hours at the temperature of 5 ℃, so that uniform and viscous polyamic acid solution is obtained;
(3) preparation of polyamic acid salt: adding 2.8mL of triethylamine to the polyamic acid solution in step (2), and continuing stirring for 3-5 hours to obtain a polyamic acid salt solution with a mass concentration of 0.1 g/mL.
(4) Preparing a composite glue solution: 15.6mL (0.5g) of montmorillonite colloid in the step (1) and 9.4mL of ultrapure water are taken to be put in a 100mL three-necked bottle, and the montmorillonite colloid is diluted to the mass fraction of 2%. And (3) dropwise adding 5mL (0.5g) of polyamic acid salt in the step (3), and continuously stirring for 3 hours to obtain a composite glue solution, wherein the mass ratio of montmorillonite to polyamic acid salt is 1: 1.
(5) Polyimide substrate surface treatment: and (3) coating the polyamic acid solution in the step (2) on a clean glass plate by using a scraper coating method, controlling the thickness of the glue solution to be 150-. An approximately 30 μm PI-based film was obtained. And coating a potassium hydroxide solution with the mass fraction of 20% on one surface of the PI base film, standing for 40min, pouring clean alkali liquor, thoroughly washing with ultrapure water, and drying for later use.
(6) Preparing a composite film by gravity-induced deposition: and (3) coating the composite glue solution in the step (4) on the surface-treated PI, controlling the thickness of the glue solution to be 500 microns, then placing the glue solution into a temperature-programmed oven, heating to 50 ℃ and keeping for 2 hours, heating to 70 ℃ and keeping for 1 hour, heating to 150 ℃ and keeping for 1 hour, and heating to 250 ℃ and keeping for 0.5 hour. Finally obtaining the polyimide-based flame-retardant material with a layered brick-wall structure.
Example 2
This example is a preparation example of a cellulose acetate sodium-based flame retardant material with a layered brick-wall structure prepared by gravity-induced deposition, prepared by the following steps:
(1) preparation of exfoliated mica colloids: taking 6g of sodium-based mica and 500mL of ultrapure water in a 1000mL beaker, continuously stirring for 24h by using mechanical stirring (800rpm) to obtain a suspension, and separating the non-peeled montmorillonite by using a high-speed centrifuge, wherein the rotation speed of the centrifuge is set to 10000rpm, and the centrifugation time is 7 minutes. Collecting supernatant, placing in a 500mL eggplant-shaped bottle, and evaporating part of water by using a rotary evaporator to obtain stripped mica colloid with the mass fraction of 3.2%;
(2) preparing a sodium acetate solution: 5.0g of sodium acetate is taken into a 250mL single-neck bottle, 100mL of ultrapure water is added, and stirring is continuously carried out for 4h at the temperature of 60 ℃ to obtain a sodium acetate solution with the mass concentration of 5%.
(4) Preparing a composite glue solution: 15.6mL (0.5g) of the mica colloid in (1) and 9.4mL of ultrapure water were taken in a 100mL three-necked flask, and the mica colloid was diluted to a mass fraction of 2%. And (3) dropwise adding 10mL (0.5g) of the sodium acetate solution in the step (3), and continuously stirring for 3 hours to obtain a composite glue solution, wherein the ratio of mica to the sodium acetate is 1: 1.
(5) PE substrate surface treatment: and (3) cleaning and drying two surfaces of the PE film by using water, and treating one surface of the PE film for 25min by using plasma.
(6) Preparing a composite film by gravity-induced deposition: fixing the film in the step (5) by using a flange, coating the composite colloid in the step (4) on the PE film subjected to surface treatment, controlling the thickness of the colloid solution to be 500 micrometers, then placing the PE film into a program temperature control oven, heating to 50 ℃ and keeping for 2 hours, heating to 70 ℃ and keeping for 1 hour, and heating to 80 ℃ and keeping for 3 hours. Finally obtaining the cellulose acetate sodium-based flame-retardant material with a layered brick-wall structure.
Example 3
This example is a preparation example of a polyimide-based flame retardant material with a layered brick-wall structure prepared by a layer-by-layer self-assembly method, and the preparation example comprises the following steps:
(1) preparation of exfoliated Layered Double Hydroxide (LDH) colloids: 5.1280g of magnesium nitrate hexahydrate and 3.7513g of aluminum nitrate nonahydrate were placed in a 250mL single-neck flask, and 100mL of ultrapure water was added thereto, followed by stirring to completely dissolve both (the concentrations of both were 0.2mol/L and 0.1 mol/L). Another 250mL single-neck bottle was charged with 6.0032g of urea and 100mL of ultrapure water, and the mixture was dissolved with stirring (concentration: 1.0 mol/L). Then, the former is slowly dropped into the latter, and after continuously stirring for 0.5h, the mixture is poured into a hydrothermal reaction kettle. Then the mixture is put into an oven and crystallized for 24 hours at 130 ℃. A milky white suspension was obtained, which was washed three times with ultrapure water and ethanol, respectively. Centrifugation (10000rpm, 6min) was then used to obtain a white precipitate, which was dispersed with 400mL of ultrapure water to give an LDH colloid at a mass concentration of about 1.0%.
(2) Preparation of Polyamic acid: 2.3172g (10.1965mmol) of DABA and 44mL of DMAc are put into a 100mL three-neck flask, nitrogen is introduced, 3.0000g (10.1965mmol) of BPDA is added after diamine is completely dissolved, and stirring is carried out for 10-12 hours at the temperature of 5 ℃, so as to obtain uniform and viscous polyamic acid solution;
(3) preparation of polyamic acid salt: 2.8mL of triethylamine was added to the polyamic acid solution in step (2), and stirring was continued for 3 to 5 hours to obtain a polyamic acid salt solution having a concentration of 0.1 g/mL.
(4) Polyimide substrate surface treatment: cleaning two sides of the Kapton film with water, coating a sodium hydroxide solution with the mass concentration of 10% on one side, standing for 25min, pouring clean alkali liquor, thoroughly cleaning with ultrapure water, drying, and fixing the Kapton film on a glass sheet.
(5) Fixing the glass sheet in the step (4) on a rotary spin coater, dripping the polyamic acid salt solution in the step (3) on PI of the glass sheet, spin-coating the solution uniformly (1600rpm, 10s), and drying; then coating the colloid in the step (1) on the surface, standing for 10min, pouring clean colloid, washing with ultrapure water and drying; alternately repeating the above two steps for 15 times, placing into a temperature-programmed oven, heating to 100 deg.C, holding for 1h, heating to 150 deg.C, holding for 1h, and heating to 250 deg.C, holding for 0.5 h. Finally obtaining the polyimide-based flame-retardant material with a layered brick-wall structure.
Example 4
This example is a preparation example of a polyvinyl alcohol-based flame retardant material with a laminated brick-wall structure prepared by a spray gun spray deposition method, and the preparation example comprises the following steps:
(1) preparation of exfoliated laponite colloids: 1g of the laponite is put into a 250mL beaker, 100mL of ultrapure water is put into the beaker, and then ultrasonic dispersion is carried out for 0.5h, so as to obtain the transparent laponite colloid.
(2) Preparing a polyvinyl alcohol solution: 5.0g of polyvinyl alcohol is put into a 250mL single-neck bottle, 100mL of ultrapure water is added, and the stirring is continued for 0.5h at 90 ℃ to obtain a sodium acetate solution with the mass concentration of 5%.
(4) PET surface treatment: and (3) cleaning and drying two surfaces of the PET film by using water, and treating one surface of the PET film for 25min by using corona.
(5) Putting the colloid in the step (1) into a spray gun spray can, uniformly spraying the colloid on the PET film surface subjected to surface treatment in the step (4), and drying; putting the polyvinyl alcohol solution in the step (3) into a spray can, uniformly spraying the polyvinyl alcohol solution, and drying; and alternately repeating the two steps for 30 times, putting the mixture into a temperature-programmed oven, heating to 50 ℃ for 2 hours, heating to 70 ℃ for 1 hour, and heating to 80 ℃ for 3 hours. Finally obtaining the polyvinyl alcohol-based flame-retardant material with a layered brick-wall structure.
Example 5
The embodiment is a preparation example of the chitosan-based flame retardant material with a laminated brick-wall structure prepared by a vacuum filtration assisted deposition method, and the preparation example comprises the following steps:
(1) preparing an exfoliated graphene oxide colloid: and (3) putting 1g of graphene oxide into a 250mL beaker, putting 100mL of ultrapure water, and dispersing for 0.5h by using ultrasonic waves to obtain the graphene oxide colloid.
(2) Preparing a chitosan solution: and (3) adding 5.0g of chitosan into a 250mL single-neck bottle, adding 100mL of acetic acid solution with the mass fraction of 1%, and continuously stirring for 5h at room temperature to obtain a chitosan solution with the mass concentration of 5%.
(3) Preparing a composite glue solution: taking 50mL (0.5g) of the graphene oxide colloid in the step (1), dropwise adding 10mL (0.5g) of the chitosan solution in the step (2), and continuously stirring for 3 hours to obtain a composite glue solution, wherein the ratio of the graphene oxide to the chitosan is 1: 1.
(4) And (4) pouring the composite glue solution in the step (3) into a sand core funnel, and performing vacuum filtration to obtain a filter cake. And then putting the filter cake into a temperature-programmed oven, heating to 50 ℃ for 2h, heating to 70 ℃ for 1h, and heating to 80 ℃ for 3 h. Finally obtaining the chitosan-based flame retardant material with a layered brick-wall structure.
Comparative example 1
The only difference from example 1 is that in step (6), the temperature was raised to 250 ℃ for 4 hours without gradient temperature rise.
A schematic structural view of a fire retardant material having a layered brick-wall structure is shown in fig. 1; example 1 a cross-sectional scanning electron micrograph of a flame retardant material with a layered brick-wall structure prepared using gravity induced deposition is shown in figure 2; example 3 a cross-sectional scanning electron micrograph of a flame retardant material having a layered brick-wall structure prepared using a layer-by-layer self-assembly method is shown in fig. 3; table 1 shows the limiting oxygen index of the flame retardant materials having a laminated brick-wall structure prepared in examples 1 to 5 and comparative example 1.
As can be seen from table 1, the flame retardant materials with a laminated brick-wall structure prepared in examples 1 to 5 have a lower oxygen transmission rate than a pure polyimide film, which indicates that the flame retardant materials have a better oxygen barrier effect, and this is due to the laminated brick-wall structure, so that oxygen can be effectively blocked from entering the interior of the material, and it can be inferred that the combustible gas inside the material is also difficult to escape from the exterior. Therefore, the limit oxygen index of the flame-retardant material is improved, and the flame-retardant property is obviously improved. In addition, the gradient temperature rise drying in the drying process is beneficial to forming a stable layered brick-wall structure. Although the lamellar inorganic nano-materials tend to be arranged in a 'flat-lying' manner under the action of gravity, if the lamellar inorganic nano-materials are directly heated to the final temperature without adopting gradient heating, the solvent is volatilized too fast at the moment, the lamellar inorganic nano-materials are not in time to deposit, and a non 'flat-lying' state, namely a defect area, can appear. The presence of the defect region hinders the enhancement of the barrier properties of the material and thus also the flame retardant properties thereof.
TABLE 1
Note: PI-1 represents Kapton, PI-2 represents a PI film prepared by taking DABA and BPDA as monomers, and S1-S5 respectively represent the flame retardant materials with the layered brick-wall structure prepared in the embodiments 1-5; s6 represents the flame retardant material having a layered brick-wall structure prepared in comparative example 1;
OTR is Oxygen Transmission Rate (Oxygen Transmission Rate);
LOI is the Limiting Oxygen Index (Limiting Oxygen Index).
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A fire retardant material having a layered brick-wall structure comprising lamellar inorganic nanomaterials and a polymer, wherein the lamellar inorganic nanomaterials are ordered within the polymer.
2. The flame retardant material of claim 1 wherein the platelet-layered inorganic nanomaterial is at least one of montmorillonite, mica, laponite, boron nitride, graphene derivatives, and layered double hydroxides; the polymer is polyvinyl alcohol, polyethylene imine, polyacrylamide, chitosan, sodium carboxymethyl cellulose, polydopamine, polyvinyl amine, polyamic acid salt or polyimide.
3. A method of preparing a fire retardant material having a layered brick-wall structure according to claim 1, wherein the fire retardant material is prepared by a vacuum filtration assisted deposition method comprising the steps of:
(1) preparing lamellar inorganic nano colloid:
dispersing the lamellar inorganic nano material in pure water to obtain a suspension, centrifuging to collect supernatant, and evaporating to remove part of water to ensure that the mass concentration of the obtained lamellar inorganic nano colloid is 1.0-3.2%;
(2) preparing a polymer into a polymer solution with a certain concentration, which specifically comprises the following steps: when the polymer is polyamic acid salt or polyimide, preparing a polymer solution with the mass concentration of 10%; when the polymer is polyvinyl alcohol, polyethyleneimine, polyacrylamide, chitosan, sodium carboxymethylcellulose, polydopamine or polyvinyl amine, the polymer is prepared into a polymer solution with the mass concentration of 5%;
(3) and mixing the layered inorganic nano colloid with the polymer solution to obtain a composite glue solution, pouring the composite glue solution into a Buchner funnel or a sand core funnel, performing vacuum filtration to obtain a filter cake, orderly arranging the layered inorganic nano materials in the filter cake under the action of pressure, and drying the filter cake to obtain the flame retardant material with a layered brick-wall structure.
4. A method of preparing a fire retardant material having a layered brick-wall structure according to claim 2, comprising the steps of:
(1) preparing lamellar inorganic nano colloid:
dispersing the lamellar inorganic nano material in pure water to obtain a suspension, centrifuging to collect supernatant, and evaporating to remove part of water to ensure that the mass concentration of the obtained lamellar inorganic nano colloid is 1.0-3.2%;
(2) preparing a polymer into a polymer solution with a certain concentration, which specifically comprises the following steps: when the polymer is polyamic acid salt or polyimide, preparing a polymer solution with the mass concentration of 10%; when the polymer is polyvinyl alcohol, polyethyleneimine, polyacrylamide, chitosan, sodium carboxymethylcellulose, polydopamine or polyvinyl amine, the polymer is prepared into a polymer solution with the mass concentration of 5%;
(3) and mixing the lamellar inorganic nano colloid with the polymer solution, coating the mixture on a substrate material to obtain a flame-retardant material wet material, and drying the flame-retardant material wet material to prepare the flame-retardant material with the lamellar brick-wall structure.
5. The method according to claim 4, wherein the step (3) is a gravity-induced deposition method, and comprises the following steps: and (3) mixing the lamellar inorganic nano colloid and the polymer solution according to the mass ratio of the lamellar inorganic nano material to the polymer of 1:1, obtaining a composite glue solution, then coating or immersing the composite glue solution on a substrate material subjected to surface treatment to obtain a flame-retardant material wet material, and then drying the flame-retardant material wet material to obtain the flame-retardant material with a laminated brick-wall structure.
6. The preparation method according to claim 4, wherein the step (3) adopts a layer-by-layer self-assembly method, and specifically comprises the following steps: coating one or two surfaces of the substrate material subjected to surface treatment with the lamellar inorganic nano colloid to enable the lamellar inorganic nano material to deposit a layer on the substrate material, pouring the coated lamellar inorganic nano colloid cleanly, washing with clear water, drying, then coating the polymer solution to enable the polymer to deposit a layer, pouring the coated polymer solution cleanly, washing with clear water, and drying; repeating the above operations alternately for not less than 10 times, and then drying to obtain the flame retardant material with a layered brick-wall structure.
7. The method of claim 6, wherein the coating is spray coating with a spray gun.
8. The production method according to any one of claims 4 to 7, wherein the surface treatment is a plasma surface treatment, a corona treatment or an alkali solution etching treatment.
9. The production method according to any one of claims 4 to 7, wherein the substrate material is polyethylene terephthalate, polyimide, polypropylene, polyethylene, polyvinyl alcohol, ethylene-vinyl alcohol, polyurethane foam, or polystyrene foam.
10. The preparation method according to any one of claims 4 to 7, wherein the drying is performed by drying at 50 ℃ for 2 hours, then drying at 70 ℃ for 1 hour, and then heating to 80-250 ℃ for drying for 0.5-3 hours.
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