Elementary substance phosphorus-based flame retardant of high polymer material as well as preparation method and application of simple substance phosphorus-based flame retardant
By encapsulating elemental phosphorus with cyclodextrin-nitrogen-based supramolecular polymers to form a composite flame retardant, the problems of large addition amounts, poor compatibility, and high toxicity of existing elemental phosphorus-based flame retardants are solved, achieving a highly efficient and environmentally friendly flame retardant effect, suitable for epoxy resins, polyurethanes, and other polymer materials.
Patent Information
- Application Number
- CN202511003294.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-21
- Publication Date
- 2025-11-07
AI Technical Summary
Existing elemental phosphorus-based flame retardants require large amounts, have poor compatibility, and produce significant smoke and toxicity, affecting the overall performance and environmental safety of polymer materials.
A composite flame retardant with acid, carbon, and gas sources is formed by controllable coating of elemental phosphorus with cyclodextrin-nitrogen supramolecular polymers, including amorphous red phosphorus, black phosphorus, purple phosphorus, and cellulose phosphorus, composed of cyclodextrin and nitrides. A high-efficiency flame retardant is prepared by a simple preparation process.
It achieves low additive content, high flame retardant efficiency, good compatibility and environmental protection characteristics, and is suitable for flame retardant treatment of a variety of polymer materials.
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Figure CN120904528A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of flame retardants, in particular to a single-element phosphorus-based flame retardant for high polymer materials, a preparation method and application thereof. BACKGROUND
[0002] With the rapid development of modern industry, high polymer materials have been widely used in many fields such as construction, electronics, transportation, aerospace, etc. due to their light weight, corrosion resistance, easy processing and other characteristics. However, most high polymer materials are composed of elements such as carbon and hydrogen, which are flammable and can quickly spread when a fire occurs, not only causing huge property losses, but also posing a serious threat to people's life safety due to the large amount of toxic smoke generated. Therefore, improving the flame retardant performance of high polymer materials has become an important research direction in the field of high polymer materials.
[0003] Single-element phosphorus-based flame retardants occupy an important position in the flame retardant market due to their unique flame-retardant mechanism and good flame-retardant effect. Single-element phosphorus can generate phosphorus-containing compounds during combustion, which can inhibit the combustion reaction by capturing free radicals, promoting the dehydration and carbonization of high polymer materials, etc. However, there are many problems with commercially available single-element phosphorus-based flame retardants: first, to achieve the desired flame-retardant effect, a large amount of flame retardant (usually more than 10%) is often added, which can significantly change the physical and chemical properties of the high polymer material, such as reducing the mechanical properties of the material and affecting its processing performance; second, the compatibility of single-element phosphorus-based flame retardants with high polymer material substrates is poor, which can easily agglomerate and migrate within the material, resulting in uneven flame-retardant effect and negative impact on the overall performance of the material; third, traditional single-element phosphorus-based flame retardants release a large amount of smoke and toxic gases such as phosphorus oxides and nitrogen oxides during combustion, which can cause serious harm to the environment and human health. Therefore, it is urgent to develop a new single-element phosphorus-based flame retardant that is efficient, low in addition amount, has good compatibility and is environmentally friendly. SUMMARY
[0004] The present application provides a single-element phosphorus-based flame retardant for high polymer materials, a preparation method and application thereof. Through innovative formula design and preparation process, the problems of large addition amount, poor compatibility, large smoke and toxicity of existing flame retardants are solved. At the same time, a simple and easy-to-operate preparation method suitable for large-scale production is provided. The application of the flame retardant in the field of flame retardant for various high polymer materials is also specified to meet the needs of different industries for the flame-retardant performance of high polymer materials.
[0005] To solve the above technical problems, in a first aspect, the embodiments of the present application provide a single-element phosphorus-based flame retardant for high polymer materials, comprising: single-element phosphorus and cyclodextrin-nitrogen-based supramolecular polymer; the single-element phosphorus comprises one or more of amorphous red phosphorus, black phosphorus, purple phosphorus and fibrous phosphorus; the cyclodextrin-nitrogen-based supramolecular polymer is polymerized from cyclodextrin and nitride; wherein the cyclodextrin comprises one or more of 2-carboxymethyl-β-cyclodextrin, 6-carboxymethyl-β-cyclodextrin and 2-carboxymethyl-γ-cyclodextrin; and the nitride is one or more of melamine, dicyandiamide, piperazine, ethylenediamine, butanediamine, hexanediamine and phenylenediamine.
[0006] In some example embodiments, the flame retardant is prepared by using the cyclodextrin-nitrogen-based supramolecular polymer to controllably coat the single-element phosphorus.
[0007] In some example embodiments, the flame retardant is a composite flame retardant taking the single-element phosphorus as an acid source, the cyclodextrin as a carbon source and the nitride as a gas source.
[0008] In some example embodiments, the mass ratio of the single-element phosphorus in the flame retardant is 40% to 90%.
[0009] In some example embodiments, the mass ratio of the cyclodextrin-nitrogen-based supramolecular polymer in the flame retardant is 10% to 60%.
[0010] In some example embodiments, the mass ratio of the cyclodextrin-nitrogen-based supramolecular polymer in the flame retardant is 10% to 60%.
[0011] In some example embodiments, the cyclodextrin and the nitride are mixed in a mass ratio of 1:5 to 5:1, and are polymerized in N,N-dimethylformamide or an aqueous sodium hydroxide solution under normal pressure at a temperature of 50 to 150°C for 3 to 24 hours to prepare the cyclodextrin-nitrogen-based supramolecular polymer.
[0012] In some example embodiments, the single-element phosphorus is dispersed in N-methylpyrrolidone or dimethyl sulfoxide, and the prepared cyclodextrin-nitrogen-based supramolecular polymer is added, and the reaction is carried out at a temperature of 20 to 100°C and a stirring speed of 100 to 800 rpm for 1 to 12 hours to achieve controllable coating of the single-element phosphorus. After filtration, washing and drying, the single-element phosphorus-based flame retardant is obtained.
[0013] In a third aspect, the embodiments of the present application further provide a high polymer material, comprising an epoxy resin, a polyurethane, a polyamide and a single-element phosphorus-based flame retardant for high polymer materials as described in the above embodiments, and the mass ratio of the single-element phosphorus-based flame retardant in the high polymer material is 0.1% to 10%.
[0014] In a fourth aspect, the embodiments of the present application further provide an application of the elemental phosphorus-based flame retardant of the high polymer material in the field of flame retardation of the high polymer material.
[0015] The technical solutions provided by the embodiments of the present application have at least the following advantages:
[0016] The present application provides a kind of high polymer material's elemental phosphorus-based flame retardant and preparation method and application, the elemental phosphorus-based flame retardant includes: elemental phosphorus and cyclodextrin-nitrogen-based supramolecular polymer;Elemental phosphorus includes one or more of amorphous red phosphorus, black phosphorus, purple phosphorus, fibrous phosphorus;Cyclodextrin-nitrogen-based supramolecular polymer is polymerized by cyclodextrin and nitride;Wherein, cyclodextrin includes one or more of 2-carboxymethyl-β-cyclodextrin, 6-carboxymethyl-β-cyclodextrin, 2-carboxymethyl-γ-cyclodextrin;Nitride is melamine, dicyandiamide, piperazine, ethylenediamine, butanediamine, hexanediamine, phenylenediamine one or more.
[0017] The present application provides a kind of high polymer material's elemental phosphorus-based flame retardant and preparation method and application, the elemental phosphorus-based flame retardant is composed of elemental phosphorus and cyclodextrin-nitrogen-based supramolecular polymer, forms acid source, carbon source, gas source composite flame retardant system;Prepared by cyclodextrin-nitrogen-based supramolecular polymer controllable coating to elemental phosphorus, simple and rapid process;The flame retardant has high flame retardant efficiency, low addition amount, good compatibility and other advantages, is suitable for the flame retardation treatment of various high polymer materials such as epoxy resin, polyurethane. BRIEF DESCRIPTION OF DRAWINGS
[0018] One or more embodiments are illustrated by way of example in the drawings that are for illustrative purposes only, and not for the limitation of embodiments, unless specifically stated otherwise, the drawings in the drawings do not constitute proportional limit.
[0019] Figure 1 A flowchart of the preparation method of the elemental phosphorus-based flame retardant of the high polymer material provided by the embodiments of the present application. DETAILED DESCRIPTION
[0020] As known from the background art, there are many problems in the current commercial elemental phosphorus-based flame retardant, therefore, it is urgent to develop a new type of elemental phosphorus-based flame retardant with high efficiency, low addition amount, good compatibility and environmental protection characteristics.
[0021] To solve the above technical problems, the application provides a single-element phosphorus-based flame retardant for a polymer material, a preparation method and application thereof. The single-element phosphorus-based flame retardant comprises single-element phosphorus and cyclodextrin-nitrogen-based supramolecular polymer. The single-element phosphorus comprises one or more of amorphous red phosphorus, black phosphorus, purple phosphorus and fibrous phosphorus. The cyclodextrin-nitrogen-based supramolecular polymer is polymerized from cyclodextrin and nitride. The cyclodextrin comprises one or more of 2-carboxymethyl-β-cyclodextrin, 6-carboxymethyl-β-cyclodextrin and 2-carboxymethyl-γ-cyclodextrin. The nitride comprises one or more of melamine, dicyandiamide, piperazine, ethylenediamine, butanediamine, hexanediamine and phenylenediamine. The application provides a single-element phosphorus-based flame retardant for a polymer material, a preparation method and application thereof. Through innovative formula design and preparation process, the problems of large addition amount, poor compatibility, large smoke and toxicity of the existing flame retardant are solved. A preparation method which is simple to operate and suitable for large-scale production is provided. The application of the flame retardant in the field of flame retardation of various polymer materials is also specified to meet the demand of different industries for the flame retardation performance of polymer materials.
[0022] The embodiments of the application will be described in detail below with reference to the accompanying drawings. However, those skilled in the art can understand that, in the embodiments of the application, many technical details are proposed to enable the reader to better understand the application. However, the technical solutions claimed by the application can be implemented even without these technical details and various changes and modifications based on the following embodiments.
[0023] The application provides a single-element phosphorus-based flame retardant for a polymer material, comprising the following steps: single-element phosphorus and cyclodextrin-nitrogen-based supramolecular polymer; the single-element phosphorus comprises one or more of amorphous red phosphorus, black phosphorus, purple phosphorus and fibrous phosphorus; the cyclodextrin-nitrogen-based supramolecular polymer is polymerized from cyclodextrin and nitride; the cyclodextrin comprises one or more of 2-carboxymethyl-β-cyclodextrin, 6-carboxymethyl-β-cyclodextrin and 2-carboxymethyl-γ-cyclodextrin; and the nitride comprises one or more of melamine, dicyandiamide, piperazine, ethylenediamine, butanediamine, hexanediamine and phenylenediamine.
[0024] In some embodiments, the flame retardant is prepared by using cyclodextrin-nitrogen-based supramolecular polymer to controllably coat the single-element phosphorus. The prepared flame retardant is a composite flame retardant with single-element phosphorus as an acid source, cyclodextrin as a carbon source and nitride as a gas source.
[0025] In some embodiments, the mass ratio of the single-element phosphorus in the flame retardant is 40% to 90%, and the mass ratio of the cyclodextrin-nitrogen-based supramolecular polymer in the flame retardant is 10% to 60%.
[0026] Referring to Figure 1 The application also provides a preparation method of a single-element phosphorus-based flame retardant for a polymer material, comprising the following steps:
[0027] Step S1, mixing cyclodextrin and nitride to prepare cyclodextrin-nitrogen-based supramolecular polymer.
[0028] Step S2, after dispersing elemental phosphorus, adding the prepared cyclodextrin-nitrogen-based supramolecular polymer to react to prepare elemental phosphorus-based flame retardant.
[0029] In some embodiments, in step S1, the cyclodextrin and the nitride are mixed in a mass ratio of 1:5 to 5:1, and are subjected to polymerization reaction in N,N-dimethylformamide or aqueous sodium hydroxide solution at a temperature of 50-150°C and under normal pressure for 3-24h to prepare the cyclodextrin-nitrogen-based supramolecular polymer.
[0030] In some embodiments, in step S2, the elemental phosphorus is dispersed in N-methylpyrrolidone or dimethyl sulfoxide, and the prepared cyclodextrin-nitrogen-based supramolecular polymer is added to react at a temperature of 20-100°C and a stirring speed of 100-800rpm for 1-12h to achieve controllable coating of the elemental phosphorus, and the elemental phosphorus-based flame retardant is obtained after filtration, washing and drying.
[0031] In addition, the embodiments of the present application also provide a high polymer material, which comprises epoxy resin, polyurethane, polyamide and the elemental phosphorus-based flame retardant of the high polymer material according to the above embodiments, and the mass ratio of the elemental phosphorus-based flame retardant in the high polymer material is 0.1% to 10%.
[0032] The embodiments of the present application also provide an application of the elemental phosphorus-based flame retardant of the high polymer material according to the above embodiments in the field of high polymer material flame retardation.
[0033] According to the above technical solutions, the embodiments of the present application provide an elemental phosphorus-based flame retardant of a high polymer material and a preparation method and application thereof. The elemental phosphorus-based flame retardant comprises: elemental phosphorus and cyclodextrin-nitrogen-based supramolecular polymer; the elemental phosphorus comprises one or more of amorphous red phosphorus, black phosphorus, purple phosphorus and fibrous phosphorus; the cyclodextrin-nitrogen-based supramolecular polymer is polymerized from cyclodextrin and nitride; the cyclodextrin comprises one or more of 2-carboxymethyl-β-cyclodextrin, 6-carboxymethyl-β-cyclodextrin and 2-carboxymethyl-γ-cyclodextrin; and the nitride is one or more of melamine, dicyandiamide, piperazine, ethylenediamine, butanediamine, hexanediamine and phenylenediamine.
[0034] The application provides a single-element phosphorus-based flame retardant for high polymer materials, a preparation method and application thereof.
[0035] Those skilled in the art can understand that the above-mentioned embodiments are specific embodiments for realizing the application, and in actual application, various changes can be made in form and details without departing from the spirit and scope of the application. Any person skilled in the art can make respective changes and modifications without departing from the spirit and scope of the application, and therefore the protection scope of the application should be subject to the range defined by the claims.
Claims
1. A single substance phosphorus-based flame retardant for high molecular materials, characterized by, The application relates to a single-element phosphorus-based flame retardant, which comprises single-element phosphorus and a cyclodextrin-nitrogen-based supramolecular polymer. The single-element phosphorus comprises one or more of amorphous red phosphorus, black phosphorus, purple phosphorus and fibrous phosphorus. The cyclodextrin-nitrogen-based supramolecular polymer is polymerized from cyclodextrin and a nitride, wherein the cyclodextrin comprises one or more of 2-carboxymethyl-beta-cyclodextrin, 6-carboxymethyl-beta-cyclodextrin and 2-carboxymethyl-gamma-cyclodextrin; and the nitride is one or more of melamine, dicyandiamide, piperazine, ethylenediamine, butylenediamine and hexamethylenediamine. The single-element phosphorus-based flame retardant is prepared by controllably coating the single-element phosphorus with the cyclodextrin-nitrogen-based supramolecular polymer.
2. The elemental phosphorus-based flame retardant for high molecular materials according to claim 1, characterized by, The single-element phosphorus-based flame retardant is a composite flame retardant with single-element phosphorus as an acid source, cyclodextrin as a carbon source and a nitride as a gas source.
3. The elemental phosphorus-based flame retardant for high molecular materials according to claim 1, characterized by, The mass ratio of the single-element phosphorus in the flame retardant is 40% to 90%.
4. The elemental phosphorus-based flame retardant for high molecular materials according to claim 1, wherein The mass ratio of the cyclodextrin-nitrogen-based supramolecular polymer in the flame retardant is 10% to 60%.
5. The elemental phosphorus-based flame retardant for high molecular materials according to claim 1, wherein The application further discloses a preparation method of the single-element phosphorus-based flame retardant.
6. A method for producing a single substance phosphorus-based flame retardant of a high molecular material, characterized by, The cyclodextrin-nitrogen-based supramolecular polymer is prepared by mixing cyclodextrin and a nitride. The single-element phosphorus-based flame retardant is prepared by dispersing single-element phosphorus, adding the prepared cyclodextrin-nitrogen-based supramolecular polymer and reacting. The cyclodextrin-nitrogen-based supramolecular polymer is prepared by mixing cyclodextrin and a nitride in a mass ratio of 1:5 to 5:1, polymerizing in N,N-dimethylformamide or sodium hydroxide aqueous solution under normal pressure at a temperature of 50-150 DEG C for 3-24 hours.
7. The method for preparing the elemental phosphorus-based flame retardant of polymeric materials according to claim 6, characterized in that, The single-element phosphorus is dispersed in N-methylpyrrolidone or dimethyl sulfoxide, the prepared cyclodextrin-nitrogen-based supramolecular polymer is added, and the reaction is carried out at a temperature of 20-100 DEG C and a stirring speed of 100-800 rpm for 1-12 hours to realize the controllable coating of the single-element phosphorus.
8. The method for preparing the elemental phosphorus-based flame retardant of polymeric materials according to claim 6, characterized in that, The single-element phosphorus-based flame retardant is used in the single-element phosphorus-based flame retardant of epoxy resin, polyurethane, polyamide and the high polymer material as claimed in claim 1, and the mass ratio of the single-element phosphorus-based flame retardant in the high polymer material is 0.1% to 10%.
9. A high molecular material, characterized by, 10.The application of the single-element phosphorus-based flame retardant of the high polymer material as claimed in claim 1 in the field of high polymer material flame retardation.