CN111704687A - Application of polymer as anti-dripping flame retardant - Google Patents
Application of polymer as anti-dripping flame retardant Download PDFInfo
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- CN111704687A CN111704687A CN202010402984.1A CN202010402984A CN111704687A CN 111704687 A CN111704687 A CN 111704687A CN 202010402984 A CN202010402984 A CN 202010402984A CN 111704687 A CN111704687 A CN 111704687A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to an application of a polymer as an anti-dripping flame retardant, wherein the polymer comprises an esterification product of polyvinyl alcohol and a phosphorus flame retardant containing phosphate groups. The preparation method of the polymer comprises the following steps: and (2) carrying out esterification reaction on the polyvinyl alcohol and the phosphorus flame retardant containing phosphate groups in water at the temperature of 55-65 ℃ under the action of a catalyst, and obtaining the polymer after the reaction is completed. The anti-dripping flame retardant utilizes the polymers of polyvinyl alcohol and phosphorus flame retardant containing phosphate groups, the polymers have the characteristics of flame retardance and anti-dripping, and the polymers can be more stably coated on the surface of a fabric through a cross-linking structure between the polymers, so that the internal fabric is effectively protected while combustion is carried out, and the safety is improved.
Description
Technical Field
The invention relates to the field of flame retardants, in particular to an application of a polymer as an anti-dripping flame retardant.
Background
With the increasing living standard, the use amount of functional home textiles, special fibers and the like in the life of people is increasing, and more high-technology and functional products are popularized and utilized in the life. Aiming at the traditional chemical fiber products, the composite material has the advantages of high plasticity, high innovation and the like, but also has the dangers of inflammability, drip-melting property and the like, and brings great troubles to the daily life of people and even the military field.
In recent years, the flame retardant materials have been in a variety of forms, and various coatings and powder materials are in the field of vision. The finishing of the coating is relatively simple and easy, and is convenient to implement in actual operation, but the coating has the problems of fastness, thickness, flexibility and the like. While powder materials are generally used in melt spinning, uniformity of properties is achieved by controlling the distribution thereof, but the particle size and distribution thereof have a large influence on the physical properties of chemical filaments.
Chinese patent with application number 201410189580.3 discloses a preparation method of flame-retardant polyvinyl alcohol containing phosphorus-nitrogen polyelectrolyte complex. Dissolving polyethyleneimine in deionized water to obtain a solution with positive charges; dissolving phytic acid in deionized water to obtain a solution with negative charges; dripping the phytic acid solution with negative charges into the polyethyleneimine solution with positive charges to obtain a complex of the polyethyleneimine and the phytic acid; dissolving a complex of polyethyleneimine and phytic acid in a dilute sodium hydroxide solution to obtain a complex solution; and (3) dissolving polyvinyl alcohol in the complex solution, removing bubbles in a vacuum drying oven, and drying in an air drying oven to obtain the flame-retardant polyvinyl alcohol material of the complex of the polyethyleneimine and the phytic acid. In the flame-retardant polyvinyl alcohol material, the dosage of polyvinyl alcohol is less, and the flame-retardant polyvinyl alcohol material is used as a dispersing agent to improve the dispersibility of the phosphorus-nitrogen polyelectrolyte complex; and the flame-retardant polyvinyl alcohol material prepared by the method does not have the anti-dripping property.
Therefore, it is necessary to develop a flame retardant material having anti-dripping properties.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an application of a polymer as an anti-dripping flame retardant and a flame-retardant fabric.
The invention discloses application of a polymer as an anti-dripping flame retardant, wherein the polymer comprises an esterification product of polyvinyl alcohol and a phosphorus flame retardant containing phosphate groups.
Further, the molecular weight of polyvinyl alcohol was 70000-120000 g/mol. Preferably, the polymerization degree of the polyvinyl alcohol is 1700-1800, and the molecular weight is 74800-79200 g/mol.
Further, the phosphorus-based flame retardant containing a phosphoric group is selected from phytic acid and/or pyrophosphoric acid. Preferably, the phosphorus-based flame retardant containing a phosphoric acid group is phytic acid.
Further, the preparation method of the polymer comprises the following steps:
polyvinyl alcohol and phosphorus flame retardant containing phosphate group are subjected to esterification reaction in water at 55-65 ℃ under the action of a catalyst, and polymerization is obtained after the reaction is completed.
Further, the reaction time was 4 h.
Further, after the reaction is completed, cooling the reaction liquid to room temperature, adding a precipitating agent to precipitate a polymer, and filtering to obtain a white product, namely the esterification product of the polyvinyl alcohol and the phosphorus flame retardant containing the phosphate group.
In the process of preparing the polymer, the solvent of the reaction solution is water instead of organic solvent commonly used in the conventional reaction, so that the production hazard and the influence on the environment are reduced, a water absorbent is not required to be added, and the reaction condition is reduced.
And (3) adding water to the white product for dissolving, filtering, and drying the filtrate in a freeze dryer to obtain a white product with a three-dimensional porous structure, wherein the product can be used as a flame-retardant anti-dripping material.
Further, the molar ratio of the phosphorus flame retardant containing phosphoric acid groups to hydroxyl groups in the polyvinyl alcohol is 1:4-6, i.e., the mass ratio is 1: 0.3-0.5. Since polyvinyl alcohol is a macromolecular polymer, the content of polyvinyl alcohol in the finally formed polymer is high at the above molar ratio, which is a main component.
Furthermore, the molar ratio of the catalyst to the hydroxyl groups in the polyvinyl alcohol is 1:5-13, i.e. the mass ratio is 1: 1.8-4.6.
Further, the catalyst is 4-dimethylaminopyridine.
In the preparation process, hydroxyl in the polyvinyl alcohol and phosphate groups in the phosphorus flame retardant containing the phosphate groups are subjected to esterification reaction, so that the phosphorus flame retardant containing the phosphate groups is grafted to a polymer chain segment of the polyvinyl alcohol, the crosslinking among different polyvinyl alcohol chains is realized, the melting point and the decomposition temperature of the polymer relative to the polyvinyl alcohol are improved, and the flame retardant synergistic effect is increased. The proportion of hydroxyl in the polyvinyl alcohol and the phosphorus flame retardant containing phosphoric acid groups is controlled, the grafting rate of the polyvinyl alcohol can be adjusted, and the flame retardant property and the anti-dripping property of the finally prepared polymer are further changed. In the above polymerization product, polyvinyl alcohol is used as a main component to provide the polymer with anti-dripping performance, and the phosphorus flame retardant containing phosphoric acid groups provides flame retardant performance, and the proportion of the polyvinyl alcohol to the phosphorus flame retardant is in a proper range to ensure that the polymerization product has both anti-dripping performance and flame retardant performance.
Furthermore, the anti-dripping flame retardant also comprises graphene oxide, and the mass ratio of the polymer to the graphene oxide is 5-15: 0.02-0.05. The addition of the graphene oxide can improve the smoke suppression performance of the anti-dripping flame retardant.
Further, when the anti-dripping flame retardant is applied, the fabric is dried after the water solution of the anti-dripping flame retardant is coated on the surface of the fabric; or the anti-dripping flame retardant is filled in the gaps of the articles needing anti-dripping treatment.
Furthermore, when the polymer is coated on a fabric or filled in gaps of an article needing anti-dripping treatment, the crosslinked polyvinyl alcohol can form a compact film after combustion so as to form a compact film on the surface of the fabric or in the gaps of the article, thereby inhibiting the combustion of flame, increasing the carbon forming property, achieving the anti-dripping effect, and simultaneously, the phosphorus flame retardant containing phosphoric acid groups in the polymer has the flame retardant effect.
In the heating process of the polymer, the highest cracking starting temperature is 210 ℃, and at 210 ℃, polyvinyl alcohol chain segments in the polymer are decomposed; at 440 ℃, the phytic acid segment is decomposed, and the residues are phosphorus oxide and residual carbon.
The polymer of the invention has good water solubility, the concentration of the aqueous solution can exceed 100g/L, the limiting oxygen index is more than 45, the polymer can not be ignited in air and can realize self-extinguishing, and after complete combustion, the residue is in a carbon film shape, has no molten drop phenomenon and has no scattered carbon dust.
The invention also provides a flame-retardant fabric, wherein the surface of the flame-retardant fabric is coated with the anti-dripping flame retardant, the anti-dripping flame retardant comprises a polymer, and the polymer comprises esterification products of polyvinyl alcohol and phosphorus flame retardant containing phosphate groups.
Further, the surface of the flame-retardant fabric is coated with a mixture of a polymer and graphene oxide.
Further, the preparation method of the flame-retardant fabric comprises the following steps:
(1) dissolving an anti-dripping flame retardant in water to obtain a flame retardant liquid, wherein the concentration of an esterification product of polyvinyl alcohol and a phosphorus flame retardant containing phosphate in the flame retardant liquid is 1-20 g/L;
(2) and coating the flame-retardant liquid on the surface of the fabric, and drying to obtain the flame-retardant fabric.
Further, in the step (1), the anti-dripping flame retardant further comprises graphene oxide, wherein the concentration of the graphene oxide in the flame retardant liquid is 0.001-0.005%.
Further, in the step (2), after the flame retardant liquid is coated, the weight gain of the flame retardant fabric is 5-40%.
By the scheme, the invention at least has the following advantages:
the invention discloses an application of a polyvinyl alcohol-based compound in preparation of an anti-dripping flame retardant, wherein the polymer has better flame retardant performance and anti-dripping performance, and can provide better comfort and water absorption due to the existence of partial hydroxyl functional groups.
After the anti-dripping flame retardant is coated on the fabric, the combustion performance of the fabric can be effectively improved, the anti-dripping performance of the fabric is simultaneously endowed, and better comfort is provided. The modified fabric can realize self-extinguishing in air, and can form a carbon film shape after complete combustion, thereby preventing various hazards caused by fragments after combustion.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a thermogravimetric test curve of the flame retardant material prepared in example 1;
FIG. 2 is a photograph of a flame retardant material prepared in example 1 showing a test for combustion performance;
FIG. 3 is a photograph of a flame retardancy test of a flame retardant material prepared in polyester fabric coating example 2;
fig. 4 is a photograph of a product after the flame retardant material prepared in example 2 was completely burned by coating the polyester fabric.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Step 1: heating and dissolving 20 parts by mass of polyvinyl alcohol (the molecular weight of the polyvinyl alcohol is 74800-79200 g/mol) in 180 parts by mass of deionized water, and then adding 40 parts by mass of phytic acid and 10 parts by mass of 4-dimethylaminopyridine catalyst to obtain a mixed solution.
Step 2: and (4) placing the reaction bottle containing the mixed solution into an oil bath pot, and stirring until the mixed solution is completely dissolved uniformly. Then, the obtained reaction solution was heated to 60 ℃ and stirred continuously to react for 4 hours.
And step 3: and cooling the reaction liquid to room temperature, adding a proper amount of ethanol to separate out a polymerization product, and filtering to obtain a white product.
And 4, step 4: and dissolving the obtained white product in water, filtering, and drying the filtrate in a freeze dryer to obtain the white three-dimensional structure flame-retardant material, wherein the material has a plurality of porous structures.
The flame retardant material prepared above was subjected to a thermal weight loss test, and the results are shown in fig. 1. As can be seen from the figure, the thermal weight loss curve comprises two stages of thermal decomposition, the highest cracking starting temperature is 210 ℃, and at 210 ℃, the polyvinyl alcohol chain segment in the polymer is decomposed; at 440 ℃, the phytic acid segment decomposed, the residue was phosphorus oxide and carbon residue, and the final residual was 38.7%.
The flame retardant material prepared above was subjected to a limited oxygen test, and the results are shown in table 1.
TABLE 1 Limited oxygen test results for flame retardant materials
| Oxygen concentration (%) | 27.1 | 30.3 | 33.1 | 35.9 | 39.4 | 42.1 | 45.2 | 46.0 | 47.1 |
| Whether or not to burn | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Is that |
The result shows that the flame retardant material can be combusted at the beginning of oxygen index of 46-47%, and the flame retardant material can be considered to have excellent flame retardant effect by far exceeding the limit oxygen index of 27% of the national flame retardant standard. Wherein, the flame retardant material does not generate molten drop phenomenon in the combustion process.
FIGS. 2a and b are photographs of the flame retardant material prepared in example 1 after burning and during burning, and it can be seen from the photographs that no molten drops are generated during the burning of the flame retardant material, and the flame retardant material can be self-extinguished and has good anti-molten drop properties.
Example 2
Step 1: the flame retardant material prepared in example 1 was dissolved in deionized water under heating to a concentration of 5 g.L-1The solution of (1).
Step 2: and (3) adding graphene oxide into the solution obtained in the step (1), and stirring the solution uniformly to obtain the flame retardant liquid.
And step 3: and (3) coating the flame retardant liquid in the step (2) on the surface of the fabric, placing the fabric in an oven for drying, and repeating the step (3) for 5 times to obtain the flame retardant fabric. The resulting flame-retardant fabric was weighed to obtain a mass growth rate of 10%.
The prepared flame-retardant fabric was subjected to a limiting oxygen test, and the results are shown in table 2.
Table 2 limiting oxygen test results for flame retardant fabrics
| Oxygen concentration (%) | 19.1 | 20.2 | 21.2 | 22.3 | 23.1 | 24.0 | 25.2 | 26.1 |
| Whether or not to burn | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Is that | Is that | Is that |
Meanwhile, the fabric which is not finished by the flame retardant liquid is used as a control, and the limit oxygen concentration is 19.2%. The results in table 2 show that at 10% coating amount, the limit oxygen index of the treated fabric can reach more than 23.1%, and the flame retardant property of the fabric can be improved. The sample failed to ignite in an air atmosphere and quickly self-extinguished after leaving the continuous fire source.
In step 3, the limiting oxygen index can reach 27% when the mass growth rate of the fabric is changed to 30%.
The flame-retardant fabric prepared by the method is ignited, and self-extinguishes within 1-2 seconds after being continuously ignited for 5 seconds, so that the smoke amount is small, no molten drop phenomenon exists in the combustion process, and the extinguished part presents a black block shape. The flame-retardant rubber is continuously placed in flame, and after complete combustion, the bottom end of the flame-retardant rubber is in a black film structure and has better adhesion.
Fig. 3a-c are photographs of the flame retardant material prepared in example 2 coated with the polyester fabric before, during and after combustion in sequence, and it can be seen from the photographs that no molten drop is generated during the combustion process of the polyester fabric, the polyester fabric can be self-extinguished, and the polyester fabric has good anti-molten drop performance.
FIG. 4 is a photograph of the flame retardant material prepared in example 2, which was coated with a polyester fabric, after completely burning, and it can be seen that the fabric was formed into a carbon film shape without generation of debris after completely burning.
Example 3
A flame retardant fabric was prepared according to the method of example 2 except that step 2 was omitted. The prepared flame-retardant fabric still has the anti-dripping performance, the limited oxygen index test is almost not different from the test without addition, but the smoke generation amount is higher than that of the flame-retardant fabric in the example 2.
In conclusion, the polymer prepared by the invention has better flame retardant effect when being used for preparing the anti-dripping flame retardant and has anti-dripping performance. After the coating is coated on the fabric, the limit oxygen index of the fabric can be effectively improved, and the self-extinguishing state in the air is realized. Controlling the coating amount can adjust the limiting oxygen index of the fabric.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The application of the polymer as an anti-dripping flame retardant is characterized in that: the polymer comprises the esterification product of polyvinyl alcohol and phosphorus flame retardant containing phosphate group.
2. Use according to claim 1, characterized in that: the molecular weight of the polyvinyl alcohol is 70000-120000 g/mol.
3. Use according to claim 1, characterized in that: the phosphorus flame retardant containing phosphoric acid groups is selected from phytic acid and/or pyrophosphoric acid.
4. Use according to claim 1, characterized in that the preparation process of the polymer comprises the following steps:
and (2) carrying out esterification reaction on the polyvinyl alcohol and the phosphorus flame retardant containing phosphate groups in water at the temperature of 55-65 ℃ under the action of a catalyst, and obtaining the polymer after the reaction is completed.
5. Use according to claim 4, characterized in that: the molar ratio of the phosphorus flame retardant containing phosphoric acid groups to hydroxyl groups in polyvinyl alcohol is 1: 4-6.
6. Use according to claim 4, characterized in that: the molar ratio of the catalyst to the hydroxyl in the polyvinyl alcohol is 1: 5-13.
7. Use according to claim 4, characterized in that: the catalyst is 4-dimethylamino pyridine.
8. Use according to claim 1, characterized in that: the anti-dripping flame retardant also comprises graphene oxide, and the mass ratio of the polymer to the graphene oxide is 5-15: 0.02-0.05.
9. Use according to claim 1, characterized in that: coating the water solution of the anti-dripping flame retardant on the surface of the fabric and then drying the fabric;
or the anti-dripping flame retardant is filled in the gaps of the articles needing anti-dripping treatment.
10. The flame-retardant fabric is characterized in that the surface of the flame-retardant fabric is coated with an anti-dripping flame retardant, wherein the anti-dripping flame retardant comprises a polymer, and the polymer comprises an esterification product of polyvinyl alcohol and a phosphorus flame retardant containing phosphate groups.
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| CN112382829A (en) * | 2020-10-14 | 2021-02-19 | 江西银汇新能源有限公司 | Functionalized flexible membrane and preparation method and application thereof |
| CN112662101A (en) * | 2020-12-22 | 2021-04-16 | 同济大学 | Polyvinyl alcohol-organic phosphonic acid @ graphene-based membrane, multilayer film and preparation method thereof |
| CN117364487A (en) * | 2023-12-04 | 2024-01-09 | 江苏恒力化纤股份有限公司 | Preparation method of durable flame-retardant coating polyester/cotton blended fabric |
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| CN112382829A (en) * | 2020-10-14 | 2021-02-19 | 江西银汇新能源有限公司 | Functionalized flexible membrane and preparation method and application thereof |
| CN112382829B (en) * | 2020-10-14 | 2023-01-17 | 江西银汇新能源有限公司 | Functional flexible membrane and preparation method and application thereof |
| CN112662101A (en) * | 2020-12-22 | 2021-04-16 | 同济大学 | Polyvinyl alcohol-organic phosphonic acid @ graphene-based membrane, multilayer film and preparation method thereof |
| CN112662101B (en) * | 2020-12-22 | 2022-12-16 | 同济大学 | Polyvinyl alcohol-organic phosphonic acid @ graphene-based membrane, multilayer film and preparation method thereof |
| CN117364487A (en) * | 2023-12-04 | 2024-01-09 | 江苏恒力化纤股份有限公司 | Preparation method of durable flame-retardant coating polyester/cotton blended fabric |
| CN117364487B (en) * | 2023-12-04 | 2024-03-19 | 江苏恒力化纤股份有限公司 | Preparation method of durable flame-retardant coating polyester/cotton blended fabric |
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