阅读说明：本技术 具有类石墨结构的超分子阻燃剂网络及其制备方法和应用 (Supramolecular flame retardant network with graphite-like structure and preparation method and application thereof ) 是由 彭治汉 姬贵晨 郭承鑫 赵勇帅 李颖颖 陈帅 义芝兴 于 2020-12-28 设计创作，主要内容包括：本发明涉及一种具有类石墨结构的超分子阻燃剂网络及其制备方法和应用,制备方法是将含均三嗪结构的有机胺与氰尿酸在溶剂中反应,反应温度为30～150℃,得到目标产物；或者,将含均三嗪结构的有机胺与氰尿酸在固相条件下控制温度在150～350℃反应得到目标产物；本发明的超分子阻燃剂网络不仅在层内由共价键和氢键连接,层间也由范德华力紧密控制,具有长程有序结构；由本发明的阻燃剂网络制备的阻燃高分子材料在燃烧初期,类石墨结构会发生相对滑移,形成紧密的烟气屏蔽层,同时,高分子材料内部积聚的热量也可以沿着共价键和氢键以及层间长程有序结构快速传递,有效提高了阻燃高分子材料的灼热丝起燃温度,降低了燃烧的烟密度。(The invention relates to a supramolecular flame retardant network with a graphite-like structure and a preparation method and application thereof, wherein the preparation method comprises the steps of reacting organic amine containing an s-triazine structure with cyanuric acid in a solvent at the reaction temperature of 30-150 ℃ to obtain a target product; or reacting organic amine containing an s-triazine structure with cyanuric acid under a solid phase condition at a temperature of 150-350 ℃ to obtain a target product; the supramolecular flame retardant network is not only connected by covalent bonds and hydrogen bonds in layers, but also tightly controlled by van der Waals force among layers, and has a long-range ordered structure; in the flame-retardant polymer material prepared by the flame retardant network, the graphite-like structure can relatively slide at the initial combustion stage to form a compact smoke shielding layer, and meanwhile, heat accumulated in the polymer material can also be rapidly transferred along covalent bonds, hydrogen bonds and an interlayer long-range ordered structure, so that the glow wire ignition temperature of the flame-retardant polymer material is effectively improved, and the combustion smoke density is reduced.)

1. Supramolecular flame retardant network with graphite-like structure, characterized by: the layers of the supermolecule flame retardant network with the graphite-like structure are connected by Van der Waals force, the layers are connected by covalent bonds and hydrogen bonds, and the supermolecule flame retardant network has a long-range ordered structure;

each layer plane has the following chemical structure:

the interlayer structure is as follows:

the number of layers of the supermolecule flame retardant network with the graphite-like structure is 2-15.

2. The supramolecular flame retardant network with a graphite-like structure of claim 1, wherein the supramolecular flame retardant network with a graphite-like structure has no melting point and decomposition temperature greater than 400 ℃.

3. The preparation method of the supramolecular flame retardant network with the graphite-like structure is characterized by comprising the following steps of: organic amine containing an s-triazine structure and cyanuric acid are subjected to chemical reaction under certain conditions to prepare the supermolecule flame retardant network with the graphite-like structure.

4. The method according to claim 3, wherein the organic amine having an s-triazine structure has the following chemical formula:

wherein n is a positive integer greater than or equal to 1.

5. The preparation method according to claim 3, wherein the mass ratio of the organic amine containing the s-triazine structure to the cyanuric acid is 1: 0.1-10.

6. The production method according to claim 3, wherein the reaction of the organic amine having an s-triazine structure with cyanuric acid is carried out in a solvent; the solvent is more than one of water, C1-C6 fatty alcohol, acetone, acetic acid, glycol, glycerol, dioxane, tetrahydrofuran, pyridine and acetonitrile; the reaction temperature is 30-150 ℃, and the reaction time is 0.5-4 hours.

7. The method according to claim 3, wherein the reaction of the organic amine having an s-triazine structure with cyanuric acid is carried out under solid phase conditions; the reaction temperature is 150-350 ℃, and the reaction time is 1-6 hours.

8. Use of the supramolecular flame retardant network with graphite-like structure according to claim 1 or 2, characterized by: adding the supramolecular flame retardant network into a high polymer material matrix to prepare a flame-retardant high polymer material;

the addition amount of the supramolecular flame retardant network is 5-20% of the mass of the high polymer material;

the high polymer material is resin, rubber or fiber.

9. Use according to claim 8, wherein the resin is a polyolefin resin, polyamide, polyester, phenolic resin, epoxy resin or unsaturated polyester resin, the rubber is a synthetic rubber or natural rubber and the fibres are synthetic fibres or natural fibres.

10. Use of the supramolecular flame retardant network with graphite-like structure according to claim 1 or 2, characterized by: preparing the supramolecular flame retardant network into glue, and coating the glue on the surface of a high polymer material to prepare a flame-retardant high polymer material;

the mass of the supramolecular flame retardant network accounts for 20-50% of the total mass of the glue;

the high polymer material is fabric, wood, paper or a rubber and plastic plate; the glue is polyacrylic glue, polyurethane glue, styrene-acrylic glue or butyronitrile glue.

Technical Field

The invention belongs to the technical field of preparation and application of flame retardants, and relates to a supramolecular flame retardant network with a graphite-like structure, and a preparation method and application thereof.

Background

The current flame retardant and the application technology thereof are only limited to the flame retardant concept of molecular structure design and synthesis of the flame retardant, cross-linking, carbon formation, layered materials and the like. The layered material is a good flame retardant, and the prominent representatives of the layered material are nano montmorillonite, layered double-metal oxide, molybdenum disulfide, expanded graphite, graphene and the like. The layered material additives can inhibit the release of combustible gas in the combustion process of high molecules, thereby improving the thermal stability and the flame retardant property of the material. Although different layered materials have various characteristics, the flame retardant purpose is generally achieved through the following four ways, namely, barrier effect, migration effect, catalytic char formation effect and free radical capture effect. The research results in this direction are also quite abundant. For example, in the literature (Flame recovery and harrowing behavor of polystyrene-organic montmorillonite nanocomposites [ J ]. Polymers for Advanced Technologies,2013,24 (3)), a Flame retardant functionalized montmorillonite is synthesized, which is then added to a polystyrene matrix to make a Flame retardant composite. The research result shows that the functionalized intercalation causes the peak value of heat release and the total heat release of the polystyrene to be obviously reduced, but has less influence on the thermal degradation of the material.

However, layered materials also suffer from significant disadvantages, for example, their barrier effect is highly dependent on good dispersion, and once the dispersion is incomplete, the barrier effect is greatly diminished. Secondly, the layered material can only have an ordered structure in a single layer, and the layers of the layered material are in a disordered staggered structure, so that the structure is not beneficial to the rapid heat transfer and obstruction, and the flame retardant property of the layered material is weakened to a certain extent.

Disclosure of Invention

In order to solve the defects of the flame retardant technology of the existing layered material, the flame retardant mechanism of montmorillonite, clay, expanded graphite, graphene and the like utilizes the irregular dispersion of nano layers to play a barrier effect, and the flame retardant technology which is orderly arranged among the layers and slides in a certain temperature area is not involved, so that the barrier efficiency of the structure is relatively low, the rapid heat transfer and barrier are not facilitated, and the flame retardant and smoke suppression efficiency is not ideal. The invention aims to provide a supramolecular flame retardant network with a graphite-like structure, and a preparation method and application thereof.

In order to achieve the purpose, the scheme is as follows:

the supermolecule flame retardant network with the graphite-like structure is connected by Van der Waals force between layers and connected by covalent bonds and hydrogen bonds in the layers, and has a long-range ordered structure;

each layer plane has the following chemical structure:

the interlayer structure is as follows:

the number of layers of the supermolecule flame retardant network with the graphite-like structure is 2-15.

The supermolecule flame retardant network with the graphite-like structure is connected by covalent bonds and hydrogen bonds in layers, is tightly controlled by Van der Waals force among the layers, has a long-range ordered structure, has good thermal conductivity, has the thermal conductivity in the interlayer direction of more than or equal to 2.5W/(m.K), and has interlayer slip characteristics through observation of an electron microscope or an atomic force microscope.

As a preferred technical scheme:

the supermolecule flame retardant network with the graphite-like structure is white or light yellow powder in macroscopic appearance, has no melting point and has the decomposition temperature of more than 400 ℃.

The invention also provides a preparation method of the supramolecular flame retardant network with the graphite-like structure, which comprises the step of carrying out chemical reaction on organic amine containing the s-triazine structure and cyanuric acid under a certain condition to prepare the supramolecular flame retardant network with the graphite-like structure.

According to the organic amine containing the triazine structure, a large number of amine groups existing on the periphery of the molecule can form a supermolecular structure network with hydrogen bonds as main bonding force with isomerized hydroxyl or carbonyl on the periphery of cyanuric acid molecules. The tightly combined supermolecular structure network not only ensures the stability in the layer, but also averages the density of the electron cloud in the layer in a single-double bond interval coupling mode, thereby forming the electron cloud delocalization in a large range. The electron cloud delocalization between the layers is mutually overlapped, and under the leading action of dispersion, a long-range ordered interlayer stacking structure which takes Van der Waals force as main constraint is further formed between the layers. This long range ordered structure facilitates rapid heat transfer along the delocalized direction of the electrons between the layers by brownian motion of the electrons. In addition, the single layer can not move randomly and can not be disintegrated due to the restraint of Van der Waals force between layers, and the single layer has slip characteristics.

As a preferred technical scheme:

the preparation method is characterized in that the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

wherein n is a positive integer greater than or equal to 1.

According to the preparation method, the mass ratio of the organic amine containing the s-triazine structure to the cyanuric acid is 1: 0.1-10.

The production method as described above, characterized in that the reaction of the organic amine containing an s-triazine structure with cyanuric acid is carried out in a solvent; the solvent is more than one of water, C1-C6 fatty alcohol, acetone, acetic acid, glycol, glycerol, dioxane, tetrahydrofuran, pyridine and acetonitrile; the reaction temperature is 30-150 ℃, and the reaction time is 0.5-4 hours; and after the reaction is finished, filtering and collecting a filter cake, and then drying and crushing to obtain the target product.

The preparation method is characterized in that the reaction of the organic amine containing the s-triazine structure and the cyanuric acid is carried out under the solid-phase condition; the reaction temperature is 150-350 ℃, and the reaction time is 1-6 hours; and cooling after the reaction is finished to obtain the target product.

The invention also provides an application of the supramolecular flame retardant network with the graphite-like structure, wherein the supramolecular flame retardant network is added into a high polymer material matrix to prepare a flame-retardant high polymer material, wherein the addition amount of the supramolecular flame retardant network is 5-20% of the mass of the high polymer material;

the high polymer material is resin, rubber or fiber.

As a preferred technical scheme:

in the above-mentioned applications, the resin is a polyolefin resin, a polyamide, a polyester, a phenol resin, an epoxy resin or an unsaturated polyester resin, the rubber is a synthetic rubber or a natural rubber, and the fiber is a synthetic fiber or a natural fiber.

The invention also provides an application of the supramolecular flame retardant network with the graphite-like structure, wherein the supramolecular flame retardant network is prepared into glue and coated on the surface of a high polymer material to prepare a flame-retardant high polymer material, wherein the mass of the supramolecular flame retardant network accounts for 20-50% of the total mass of the glue;

the high polymer material is a fabric, a wood, a paper or a rubber-plastic plate, and the glue is polyacrylic glue, polyurethane glue, styrene-acrylic glue or butyronitrile glue.

The principle of the invention is as follows:

when the flame-retardant high polymer material prepared by the supermolecule flame retardant network with the graphite-like structure is combusted, relative slippage can occur between layers, so that the area of the layered network is rapidly increased at the initial combustion stage of the high polymer material, a compact smoke shielding layer and a heat blocking layer are formed, and meanwhile, heat led into the high polymer material due to combustion can be rapidly transferred along covalent bonds, hydrogen bonds and an interlayer long-range ordered structure, so that the accumulation of heat in the high polymer material is effectively reduced, the combustion process is delayed, the flammability of the high polymer material is reduced, the flame retardant property of the flame-retardant high polymer material is improved, and the smoke density during combustion is reduced. When the flame-retardant glowing filament is added into resin and rubber, the ignition temperature of the glowing filament is improved by more than 50 ℃ and the smoke density is reduced by more than 15 percent compared with the same high polymer material without the flame-retardant glowing filament, and when the flame-retardant glowing filament is added into fiber, the limit oxygen index is more than 28 percent and the smoke density is reduced by more than 15 percent. The supramolecular flame retardant network is prepared into glue to be coated on the surface of a high polymer material to prepare the flame-retardant high polymer material, the combustion damage length in the vertical direction is less than 3cm, the combustion damage length in the horizontal direction is less than 2.5cm, and the smoke density is reduced by more than 15%.

Has the advantages that:

(1) the supermolecule flame retardant network structure has a special supermolecule network structure, has good thermal conductivity, has the thermal conductivity in the interlayer direction more than or equal to 2.5W/(m.K), and has interlayer slip characteristics;

(2) the preparation method of the supramolecular flame retardant network structure has the advantages of simple and convenient process, good applicability, low production cost and easy popularization, and can use a solution method or a solid phase method;

(3) the application of the supramolecular flame retardant network with the graphite-like structure is to prepare the supramolecular flame retardant network with the graphite-like structure into a flame-retardant high polymer material, when the flame-retardant high polymer material is combusted, relative slippage can occur between layers of the graphite-like structure, so that the area of a layered network is rapidly increased at the initial combustion stage of the high polymer material to form a compact smoke shielding layer and a heat blocking layer, and meanwhile, heat led into the high polymer material due to combustion can be rapidly transferred along a covalent bond, a hydrogen bond and an interlayer long-range ordered structure, thereby effectively reducing the aggregation of heat in the high polymer material, further delaying the combustion process and reducing the flammability, improving the flame retardance of the flame-retardant high polymer material and reducing the smoke density during combustion;

(4) the flame-retardant high polymer material prepared by the application of the supramolecular flame retardant network with the graphite-like structure has a good flame-retardant effect.

Detailed Description

The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

The performance index testing method comprises the following steps:

the method for testing the ignition temperature of the glow wire comprises the following steps: GB/T5169.13-2006;

the testing method of the limiting oxygen index comprises the following steps: GB/T5454-1997;

the method for testing the combustion damage length in the vertical direction and the horizontal direction comprises the following steps: reference GB/T2408-;

the smoke density test method comprises the following steps: GB 8323-1987;

the method for testing the decomposition temperature comprises the following steps: GB/T6425-2008;

the method for testing the thermal conductivity in the interlayer direction comprises the following steps: reference is made to GB/T10297-.

The layers of the supermolecule flame retardant network with a graphite-like structure are connected by Van der Waals force, the layers are connected by covalent bonds and hydrogen bonds, and the supermolecule flame retardant network has a long-range ordered structure; each layer plane has the following chemical structure:

the interlayer structure is as follows:

the number of layers of the supermolecule flame retardant network with the graphite-like structure is 2-15.

Example 1

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (water) according to a mass ratio of 1:1, wherein the reaction temperature is 95 ℃, and the reaction time is 4 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 4.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 10; no melting point, and the decomposition temperature is 460 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 3.5W/(m · K).

Adding the prepared supramolecular flame retardant network with a graphite-like structure into polyethylene to prepare flame-retardant polyethylene; compared with polyethylene without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant polyethylene is improved by 100 ℃, the smoke density is reduced by 24 percent, wherein the addition amount of the supermolecule flame retardant network is 5 percent of the mass of the polyethylene.

Example 2

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (methanol) according to a mass ratio of 1:0.1, wherein the reaction temperature is 30 ℃, and the reaction time is 4 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 1.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 15; no melting point, and the decomposition temperature of 472 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network having a graphite-like structure is 4.0W/(m · K).

Adding the prepared supermolecule flame retardant network with the graphite-like structure into polyamide 66 to prepare flame-retardant polyamide 66; compared with polyamide 66 without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant polyamide 66 is improved by 125 ℃, the smoke density is reduced by 24 percent, wherein the addition amount of the supermolecule flame retardant network is 10 percent of the mass of the polyamide 66.

Example 3

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (n-propanol) according to a mass ratio of 1:3.5, wherein the reaction temperature is 75 ℃, and the reaction time is 0.5 hour, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 5.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 7; no melting point, and the decomposition temperature is 451 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 3.2W/(m · K).

Adding the prepared supermolecule flame retardant network with the graphite-like structure into butylene terephthalate to prepare flame-retardant butylene terephthalate; compared with the polybutylene terephthalate without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant polybutylene terephthalate is improved by 75 ℃, the smoke density is reduced by 26 percent, wherein the addition amount of the supermolecule flame retardant network is 20 percent of the mass of the polybutylene terephthalate.

Example 4

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (n-hexanol) according to a mass ratio of 1:6, wherein the reaction temperature is 140 ℃, and the reaction time is 3 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 2.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 3; no melting point, and the decomposition temperature is 411 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 2.8W/(m · K).

Adding the prepared supermolecule flame retardant network with the graphite-like structure into phenolic resin to prepare flame-retardant phenolic resin; compared with the phenolic resin without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant phenolic resin is increased by 50 ℃, the smoke density is reduced by 17%, wherein the addition amount of the supermolecule flame retardant network is 8% of the mass of the phenolic resin.

Example 5

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (acetone) according to a mass ratio of 1:8, wherein the reaction temperature is 40 ℃, and the reaction time is 2 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 3.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 4; no melting point, and the decomposition temperature of 423 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 2.9W/(m · K).

Adding the prepared supramolecular flame retardant network with a graphite-like structure into E51 epoxy resin to prepare flame-retardant E51 epoxy resin; compared with the E51 epoxy resin without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant E51 epoxy resin is improved by 50 ℃, the smoke density is reduced by 22%, wherein the addition amount of the supramolecular flame retardant network is 12% of the mass of the E51 epoxy resin.

Example 6

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (acetic acid) according to a mass ratio of 1:10, wherein the reaction temperature is 100 ℃, and the reaction time is 1.5 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 2.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 2; no melting point, and the decomposition temperature is 409 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 2.5W/(m · K).

Adding the prepared supermolecule flame retardant network with a graphite-like structure into maleic anhydride type unsaturated polyester to prepare flame-retardant maleic anhydride type unsaturated polyester; the glowing filament ignition temperature of the prepared flame-retardant maleic anhydride type unsaturated polyester is improved by 50 ℃ and the smoke density is reduced by 26% compared with the maleic anhydride type unsaturated polyester without the flame retardant, wherein the addition amount of the supramolecular flame retardant network is 18% of the mass of the maleic anhydride type unsaturated polyester.

Example 7

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (ethylene glycol) according to a mass ratio of 1:1.5, wherein the reaction temperature is 135 ℃, and the reaction time is 1 hour, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 1.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 9; no melting point, and the decomposition temperature is 468 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 3.4W/(m · K).

Adding the prepared supermolecule flame retardant network with the graphite-like structure into ethylene propylene rubber to prepare flame-retardant ethylene propylene rubber; compared with ethylene propylene rubber without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant ethylene propylene rubber is increased by 100 ℃, the smoke density is reduced by 15%, wherein the addition amount of the supermolecule flame retardant network is 20% of the mass of the ethylene propylene rubber.

Example 8

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (glycerol) according to a mass ratio of 1:4.5, wherein the reaction temperature is 150 ℃, and the reaction time is 2 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 3.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 5; no melting point, and the decomposition temperature of 435 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network having a graphite-like structure was 3.0W/(m · K).

Adding the prepared supramolecular flame retardant network with the graphite-like structure into natural rubber to prepare flame-retardant rubber; compared with natural rubber without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant rubber is increased by 75 ℃, the smoke density is reduced by 16%, wherein the addition amount of the supramolecular flame retardant network is 20% of the mass of the natural rubber.

Example 9

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (dioxane) according to a mass ratio of 1:3, wherein the reaction temperature is 80 ℃, and the reaction time is 3.5 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 5.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 7; no melting point, and the decomposition temperature is 452 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 3.2W/(m · K).

Adding the prepared supramolecular flame retardant network with the graphite-like structure into PET fibers to prepare flame-retardant PET fibers; the limit oxygen index of the prepared flame-retardant PET fiber is 31%, the smoke density is reduced by 20%, and the addition amount of the supramolecular flame retardant network is 5% of the mass of the PET fiber.

Example 10

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (tetrahydrofuran) according to a mass ratio of 1:4, wherein the reaction temperature is 60 ℃, and the reaction time is 4 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 3.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 6; the material has no melting point and the decomposition temperature is 440 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 3.1W/(m · K).

Adding the prepared supramolecular flame retardant network with the graphite-like structure into cotton fibers to prepare flame-retardant cotton fibers; the limit oxygen index of the prepared flame-retardant cotton fiber is 29%, the smoke density is reduced by 29%, and the addition amount of the supramolecular flame retardant network is 5% of that of the cotton fiber.

Example 11

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (pyridine) according to a mass ratio of 1:5, wherein the reaction temperature is 90 ℃, and the reaction time is 2.5 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 3.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 5; the melting point is not existed, and the decomposition temperature is 438 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network having a graphite-like structure was 3.0W/(m · K).

Preparing the prepared supramolecular flame retardant network with a graphite-like structure into polyacrylic acid glue, coating the polyacrylic acid glue on the surface of the linen to prepare a flame-retardant high polymer material, and increasing the weight of the linen by 10% after coating; the burning damage length of the prepared flame-retardant linen in the vertical direction is 2cm, the burning damage length of the manufactured flame-retardant linen in the horizontal direction is 0.6cm, the smoke density is reduced by 21%, and the mass of the supramolecular flame retardant network accounts for 20% of the total mass of the glue.

Example 12

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (acetonitrile) according to a mass ratio of 1:2, wherein the reaction temperature is 72 ℃, and the reaction time is 2 hours, so as to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 4.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 8; no melting point, and the decomposition temperature is 455 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network having a graphite-like structure was 3.3W/(m · K).

Preparing the prepared supramolecular flame retardant network with a graphite-like structure into polyurethane glue, coating the polyurethane glue on the surface of wood to prepare flame-retardant wood, and increasing the weight of the coated wood by 20%; the burning damage length of the prepared flame-retardant wood in the vertical direction is 0cm, the burning damage length of the prepared flame-retardant wood in the horizontal direction is 0cm, the smoke density is reduced by 25%, and the mass of the supramolecular flame retardant network accounts for 35% of the total mass of the glue.

Example 13

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the steps of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a solvent (a mixture of ethanol and glycerol in a mass ratio of 1: 2) at a reaction temperature of 80 ℃ for 0.8 hour to prepare the supramolecular flame retardant network with the graphite-like structure; wherein, the chemical structural formula of the organic amine containing the s-triazine structure is as follows:

and n is 5.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 6; no melting point, and the decomposition temperature of 446 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 3.1W/(m · K).

Preparing the prepared supermolecule flame retardant network with a graphite-like structure into styrene-acrylic glue, coating the styrene-acrylic glue on the surface of paper to prepare flame-retardant paper, and increasing the weight of the coated paper by 8%; the burning damage length of the prepared flame-retardant paper in the vertical direction is 2.8cm, the burning damage length of the prepared flame-retardant paper in the horizontal direction is 2.2cm, the smoke density is reduced by 30%, and the mass of the supramolecular flame retardant network accounts for 40% of the total mass of the glue.

Example 14

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the step of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a mass ratio of 1:0.1 under a solid-phase condition, wherein the reaction temperature is 150 ℃, and the reaction time is 1 hour, so that the supramolecular flame retardant network with the graphite-like structure is prepared.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 15; no melting point, and the decomposition temperature is 470 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network having a graphite-like structure is 4.0W/(m · K).

Preparing the prepared supermolecule flame retardant network with the graphite-like structure into butyronitrile glue, coating the butyronitrile glue on the surface of a rubber-plastic plate to prepare a flame-retardant rubber-plastic plate, and increasing the weight of the coated rubber-plastic plate by 25%; the vertical direction burning damage length of the prepared flame-retardant rubber-plastic plate is 2cm, the horizontal direction burning damage length of the prepared flame-retardant rubber-plastic plate is 1.9cm, the smoke density is reduced by 18%, wherein the mass of the supramolecular flame retardant network accounts for 50% of the total mass of the glue.

Example 15

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the step of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a mass ratio of 1:5 under a solid-phase condition, wherein the reaction temperature is 250 ℃, and the reaction time is 4 hours, so that the supramolecular flame retardant network with the graphite-like structure is prepared.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 5; the melting point is not existed, and the decomposition temperature is 438 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network having a graphite-like structure was 3.0W/(m · K).

Adding the prepared supramolecular flame retardant network with the graphite-like structure into polyamide 6 to prepare flame-retardant polyamide 6; compared with polyamide 6 without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant polyamide 6 is increased by 75 ℃, the smoke density is reduced by 26%, wherein the addition amount of the supermolecule flame retardant network is 10% of the mass of the polyamide 6.

Example 16

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the step of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a mass ratio of 1:10 under a solid-phase condition, wherein the reaction temperature is 350 ℃, and the reaction time is 6 hours, so that the supramolecular flame retardant network with the graphite-like structure is prepared.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 2; no melting point, and the decomposition temperature is 406 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 2.5W/(m · K).

Adding the prepared supramolecular flame retardant network with a graphite-like structure into polyethylene terephthalate to prepare flame-retardant polyethylene terephthalate; compared with the polyethylene terephthalate without the flame retardant, the glow wire ignition temperature of the prepared flame-retardant polyethylene terephthalate is improved by 50 ℃, the smoke density is reduced by 20 percent, wherein the addition amount of the supramolecular flame retardant network is 20 percent of the mass of the polyethylene terephthalate.

Example 17

A preparation method of a supramolecular flame retardant network with a graphite-like structure comprises the step of carrying out chemical reaction on organic amine containing an s-triazine structure and cyanuric acid in a mass ratio of 1:1 under a solid-phase condition, wherein the reaction temperature is 200 ℃, and the reaction time is 4 hours, so that the supramolecular flame retardant network with the graphite-like structure is prepared.

The number of layers of the prepared supermolecule flame retardant network with the graphite-like structure is 10; no melting point, and the decomposition temperature is 458 ℃; the thermal conductivity in the interlayer direction of the supramolecular flame retardant network with a graphite-like structure is 3.5W/(m · K).

Adding the prepared supramolecular flame retardant network with the graphite-like structure into polyamide 6 fiber to prepare flame-retardant polyamide 6 fiber; the limit oxygen index of the prepared flame-retardant polyamide 6 fiber is 30%, the smoke density is reduced by 23%, and the addition amount of the supramolecular flame retardant network is 5% of the mass of the polyamide 6.