CN114507380A - MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof - Google Patents

MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof Download PDF

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CN114507380A
CN114507380A CN202210076969.1A CN202210076969A CN114507380A CN 114507380 A CN114507380 A CN 114507380A CN 202210076969 A CN202210076969 A CN 202210076969A CN 114507380 A CN114507380 A CN 114507380A
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flame retardant
intumescent flame
nitrogen single
mxene
phosphorus
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CN114507380B (en
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赖学军
陈奕燊
曾幸荣
李红强
刘宇翔
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South China University of Technology SCUT
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Abstract

The invention discloses an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and a preparation method and application thereof. The preparation method of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps: 1) carrying out nucleophilic substitution reaction of hexachlorotriphosphazene and 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane; 2) firstly, carrying out in-situ modification reaction on MXene nanosheets, and then carrying out nucleophilic substitution reaction on the MXene nanosheets and cyanuric chloride; 3) mixing the products of the step 1) and the step 2) and then reacting with ethylenediamine. The phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets has the advantages of high flame retardant efficiency, good thermal stability and good compatibility with a polymer matrix, the flame retardant performance and the thermal stability of polypropylene can be effectively improved by only adding a small amount of phosphorus-nitrogen single-component intumescent flame retardant, and the preparation method is simple and is suitable for large-scale production and application.

Description

MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof
Technical Field
The invention relates to the technical field of intumescent flame retardants, in particular to an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and a preparation method and application thereof.
Background
The Intumescent Flame Retardant (IFR) is a halogen-free environment-friendly flame retardant, does not need antimony oxide as a synergistic flame retardant, and is widely used for flame-retardant polymer (polypropylene, polyethylene, epoxy resin and the like) materials. Conventional IFR is generally a multi-component system, consisting of two or more compounds that act synergistically to form an intumescent, flame retardant carbon layer. However, due to the poor compatibility of the flame retardant component with the polymer matrix, migration, precipitation, agglomeration and other problems inevitably occur in the actual production and use processes, so that not only is it difficult to maintain effective flame retardant performance for a long time, but also the thermal stability and mechanical properties of the polymer material are affected.
The phosphorus-nitrogen single-component intumescent flame retardant is an intumescent flame retardant integrating an acid source, a carbon source and a gas source, and can effectively solve the problem of poor compatibility of multi-component IFR. However, the existing phosphorus-nitrogen single-component intumescent flame retardant generally has the problem of low flame retardant efficiency, and the application of the phosphorus-nitrogen single-component intumescent flame retardant is severely limited. In order to improve the flame retardant efficiency of the phosphorus-nitrogen single-component intumescent flame retardant, researchers have proposed a plurality of methods, mainly including introducing a flame retardant synergist, introducing flame retardant elements such as silicon and boron, and coating ammonium polyphosphate with a char-forming agent, which can improve the flame retardant efficiency of the phosphorus-nitrogen single-component intumescent flame retardant to a certain extent, but still are difficult to meet the increasing practical application requirements.
Therefore, the development of the phosphorus-nitrogen single-component intumescent flame retardant which has high flame retardant efficiency, good thermal stability and good compatibility with a polymer matrix is of great significance.
Disclosure of Invention
The invention aims to provide an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets comprises the following steps:
1) dispersing hexachlorotriphosphazene and 1-oxo-4-hydroxymethyl-2, 6, 7-trioxo-1-phosphabicyclo [2,2,2] octane in an aprotic polar solvent, adding an acid-binding agent, and performing nucleophilic substitution reaction to obtain a reaction solution A;
2) dispersing MXene nanosheets and aminopropylalkoxysilane in an aprotic polar solvent, carrying out in-situ modification reaction under a protective atmosphere, adding cyanuric chloride and an acid-binding agent, and carrying out nucleophilic substitution reaction under the protective atmosphere to obtain a reaction solution B;
3) and mixing the reaction liquid A and the reaction liquid B, adding ethylenediamine and an acid-binding agent, and reacting to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Preferably, the preparation method of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps:
1) dispersing hexachlorotriphosphazene and 1-oxo-4-hydroxymethyl-2, 6, 7-trioxo-1-phosphabicyclo [2,2,2] octane in an aprotic polar solvent, slowly adding an acid-binding agent, and carrying out nucleophilic substitution reaction to obtain a reaction solution A;
2) dispersing MXene nanosheets and aminopropylalkoxysilane in an aprotic polar solvent, carrying out in-situ modification reaction under a protective atmosphere, adding cyanuric chloride and an acid-binding agent, and carrying out nucleophilic substitution reaction under the protective atmosphere to obtain a reaction solution B;
3) and mixing the reaction liquid A and the reaction liquid B, slowly adding ethylenediamine and an acid-binding agent, reacting, filtering, washing and drying the filtered solid to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Preferably, the mole ratio of the hexachlorotriphosphazene, the 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane and the cyanuric chloride is 1: 2-4: 0.1-1.
Preferably, the ratio of the total molar weight of the hexachlorotriphosphazene and the cyanuric chloride to the molar weight of the ethylenediamine is 1: 1-2.
Preferably, the molar ratio of the 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane to the acid-binding agent in the step 1) is 1: 1-1.5.
Preferably, the nucleophilic substitution reaction in step 1) is carried out at 50-80 ℃ for 4-7 h.
Preferably, the MXene nanosheets are at least one of titanium carbide nanosheets, titanium nitride nanosheets, titanium carbonitride nanosheets, zirconium carbide nanosheets, molybdenum carbide nanosheets and vanadium carbide nanosheets.
Preferably, the MXene nanosheets have a lamella diameter of 0.5-10 μm and a lamella spacing of 1-7 nm.
Preferably, the aminopropylalkoxysilane is at least one of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropyltrimethoxysilane.
Preferably, the mass ratio of the MXene nanosheets to the aminopropylalkoxysilane in the step 2) is 1: 0.5-10.
Preferably, the molar ratio of the aminopropylalkoxysilane to the cyanuric chloride in the step 2) is 0.8-1: 1.
Preferably, the molar ratio of the aminopropylalkoxysilane to the acid-binding agent in the step 2) is 1: 1-1.5.
Preferably, the in-situ modification reaction in the step 2) is carried out at 0-30 ℃, and the reaction time is 4-7 h.
Preferably, the nucleophilic substitution reaction in the step 2) is carried out at 0-30 ℃, and the reaction time is 3-5 h.
Preferably, the molar ratio of the ethylenediamine to the acid-binding agent in the step 3) is 1: 1-2.
Preferably, the reaction in the step 3) is carried out at the temperature of 80-105 ℃, and the reaction time is 2-5 h.
Preferably, the aprotic polar solvent is at least one of acetonitrile, dimethyl sulfoxide, N-dimethylacetamide, 1, 4-dioxane, and hexamethylphosphoric triamide.
Preferably, the acid-binding agent is at least one of triethylamine, pyridine, N-diisopropylethylamine and 4-dimethylaminopyridine.
An MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant is prepared by the method.
A flame-retardant polypropylene material comprises 15-30 wt% of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
The preparation method of the flame-retardant polypropylene material comprises the following steps: adding polypropylene into an open type hot mill, carrying out hot milling at the temperature of 175-185 ℃ by using double rollers, adding the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant, mixing, transferring the material into a flat vulcanizing instrument, preheating at the temperature of 175-185 ℃ for 3-7 min, carrying out hot pressing for 5-10 min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The principle of the invention is as follows: the invention adopts hexachlorotriphosphazene and 1-oxo-4-hydroxymethyl-2, 6, 7-trioxo-1-phosphabicyclo [2,2]Octane is used as a main raw material to construct a macromolecular main chain structure of the phosphorus-nitrogen single-component intumescent flame retardant, the structure has the characteristic of high phosphorus content, and an intumescent carbon protective layer can be efficiently formed by quickly carrying out intramolecular carbon formation reaction in the combustion process; by utilizing the coupling effect of aminopropyl alkoxy silane, the MXene nanosheets are modified into a phosphorus-nitrogen single-component intumescent flame retardant structure, so that the interlayer spacing of the MXene nanosheets is enlarged, the specific surface area of the MXene nanosheets is increased, the surface polarity of the MXene nanosheets is reduced, and the compatibility of the MXene nanosheets and polypropylene is improved; by controlling the reaction conditions of the aprotic polar solvent, nitrogen and the like, the MXene nanosheets are ensured to be uniformly dispersed in the chemical modification process, and O & lt + & gt is avoided2 -And OH free radicals attack MXene nano-sheets, so that the problem that MXene is easily oxidized and loses efficacy in the chemical modification process is solved; the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets fully exerts the synergistic flame retardant effect between the phosphorus-nitrogen single-component intumescent flame retardant and the MXene, and rich transition metal Lewis acid active sites on the MXene nanosheets can catalyze polypropylene and flame retardantThe agent generates carbonization reactions such as dehydration, cyclization, crosslinking and the like to promote the formation of a high-quality expanded carbon protective layer, and MXene can adsorb H, OH and O2 -The free radicals inhibit the polypropylene combustion and degradation processes initiated by the free radicals.
The invention has the beneficial effects that: the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets has the advantages of high flame retardant efficiency, good thermal stability and good compatibility with a polymer matrix, the flame retardant performance and the thermal stability of polypropylene can be effectively improved by only adding a small amount of phosphorus-nitrogen single-component intumescent flame retardant, and the preparation method is simple and is suitable for large-scale production and application.
Specifically, the method comprises the following steps:
1) the phosphorus-nitrogen single-component intumescent flame retardant is modified by the MXene nanosheets, the defects that the MXene nanosheets are easy to oxidize and poor in compatibility with polymers are overcome, the characteristics of transition metal catalytic carbonization and free radical adsorption of the MXene nanosheets can be fully exerted, and the polymers and the phosphorus-nitrogen single-component intumescent flame retardant can be more efficiently promoted to form a high-quality intumescent carbon protective layer;
2) the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets has high phosphorus content (up to 20 wt%), can catalyze the rapid formation of a phosphorus-containing intumescent carbon layer, and further can timely block the transmission of combustion heat and oxygen to a polymer base material;
3) the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets has high thermal stability, and can meet the processing and forming temperature of most polymer materials;
4) the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets has high flame retardant efficiency, and the flame retardant performance and the thermal stability of polypropylene can be effectively improved by only adding a small amount of the phosphorus-nitrogen single-component intumescent flame retardant.
Drawings
Fig. 1 is an SEM image of the MXene nanosheet modified phosphorus-nitrogen single component intumescent flame retardant of example 1.
FIG. 2 is an FTIR chart of hexachlorotriphosphazene, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane and MXene nanosheet modified phosphorus-nitrogen single component intumescent flame retardant of example 1.
FIG. 3 is the thermogravimetric loss curve of the phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets in example 1 in air and nitrogen.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps:
1) adding 17.38g (0.05mol) of hexachlorotriphosphazene and 18.05g (0.1mol) of 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane into 250mL of acetonitrile, uniformly stirring at 55 ℃, slowly dropwise adding 7.91g (0.1mol) of pyridine, and stirring at constant temperature of 55 ℃ for 7 hours to obtain a reaction solution A;
2) adding 0.56g of titanium carbide nanosheet (with the lamella diameter being about 2 microns and the interlayer spacing being about 7nm) and 1.11g (0.005mol) of 3-aminopropyltriethoxysilane into 250mL of acetonitrile, stirring at constant temperature of 30 ℃ for 7h under the protection of nitrogen, adding 0.92g (0.005mol) of cyanuric chloride and 0.40g (0.005mol) of pyridine, and stirring at constant temperature of 30 ℃ for 3h under the protection of nitrogen to obtain a reaction solution B;
3) and (2) mixing the reaction liquid A and the reaction liquid B, uniformly stirring at 100 ℃, then slowly dropwise adding a mixed liquid consisting of 6.60g (0.11mol) of ethylenediamine and 17.4g (0.22mol) of pyridine under the protection of nitrogen, stirring at constant temperature of 100 ℃ for 5 hours after dropwise adding is finished, filtering, washing the filtered solid with water, and drying at 80 ℃ for 12 hours to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Testing the performance of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets:
1) the Scanning Electron Microscope (SEM) image of the MXene nanosheet modified phosphorus-nitrogen single component intumescent flame retardant of this example is shown in fig. 1.
As can be seen from fig. 1: the particle size of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets is about 1 μm, the surface is rough, and the MXene nanosheets are embedded in the flame retardant.
2) The Fourier infrared spectrum (FTIR) chart of the phosphorus-nitrogen single-component intumescent flame retardant modified by hexachlorotriphosphazene, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane and MXene nanosheet in the embodiment is shown in FIG. 2.
As can be seen from fig. 2: phosphonitrilic chloride trimer in 1246cm-1The peak of the stretching vibration which belongs to P ═ N appears at 600cm-1The characteristic peak appeared in the (B) is attributed to P-Cl; 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2]Octane at 2965cm-1And 2910cm-1In the presence of-CH3Peak of stretching vibration at 1018cm-1A characteristic peak belonging to P-O-C appears; the characteristic absorption peaks of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant of the embodiment mainly include: 2965cm-1And 2910cm-1Of (C is a-CH)3Peak of telescopic vibration, 1246cm-11018cm in the characteristic peak of P ═ N belonging to the phosphazene ring structure-1Characteristic peak of P-O-C; therefore, the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment has the characteristic peaks belonging to a phosphazene ring structure and a caged phosphate structure, and the P-Cl characteristic peak of hexachlorotriphosphazene has completely disappeared, which indicates that Cl on the phosphazene ring has been completely replaced, and indicates that the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets has been successfully prepared.
3) The thermogravimetric curve of the phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets in air and nitrogen is shown in FIG. 3.
As can be seen from fig. 3: the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets has the initial degradation temperatures of 330 ℃ in air and nitrogen, and the mass residue rates of 27% and 40% in air and nitrogen at 800 ℃, which shows that the phosphorus-nitrogen single-component intumescent flame retardant has excellent thermal stability and can meet the processing and forming conditions of most polymer materials.
The preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 80 parts by mass of polypropylene into an open type hot mixing machine, carrying out hot mixing at the temperature of 180 ℃ by two rollers, adding 20 parts by mass of phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 185 ℃ for 5min, carrying out hot pressing for 6min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property tests of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 2:
an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps:
1) adding 17.38g (0.05mol) of hexachlorotriphosphazene and 36.10g (0.2mol) of 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane into 250mL of 1, 4-dioxane, uniformly stirring at 80 ℃, slowly dropwise adding 22.26g (0.22mol) of triethylamine, and stirring at constant temperature of 80 ℃ for 6h to obtain a reaction solution A;
2) adding 1.03g of titanium carbonitride nanosheets (with the lamella diameter being about 5 micrometers and the interlayer spacing being about 3nm) and 10.32g (0.05mol) of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane into 250mL of 1, 4-dioxane, stirring at the constant temperature of 25 ℃ for 6 hours under the protection of nitrogen, adding 9.22g (0.05mol) of cyanuric chloride and 5.57g (0.055mol) of triethylamine, and stirring at the constant temperature of 25 ℃ for 4 hours under the protection of nitrogen to obtain a reaction solution B;
3) and (2) mixing the reaction liquid A and the reaction liquid B, uniformly stirring at 105 ℃, then slowly dropwise adding a mixed liquid consisting of 6.00g (0.1mol) of ethylenediamine and 18.21g (0.18mol) of triethylamine under the protection of nitrogen, stirring at a constant temperature of 105 ℃ for 2 hours after dropwise adding is finished, filtering, washing the filtered solid with water, and drying at 80 ℃ for 12 hours to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Testing the performance of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant (the testing method is the same as that in example 1):
through tests, the appearance, the composition and the thermal stability of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment are highly similar to those of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment 1.
The preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 80 parts by mass of polypropylene into an open type hot mixing machine, carrying out hot mixing at the temperature of 185 ℃ by two rollers, adding 20 parts by mass of phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 180 ℃ for 3min, carrying out hot pressing for 10min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant performance and thermal stability test of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 3:
an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps:
1) adding 17.38g (0.05mol) of hexachlorotriphosphazene and 27.08g (0.15mol) of 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane into 250mL of N, N-dimethylacetamide, uniformly stirring at 65 ℃, slowly dropwise adding 23.27g (0.18mol) of N, N-diisopropylethylamine, and stirring at constant temperature of 65 ℃ for 4h to obtain a reaction solution A;
2) adding 0.90g of titanium nitride nanosheets (with the lamella diameter being about 0.5 mu m and the interlayer spacing being about 2nm) and 4.48g (0.025mol) of 3-aminopropyltrimethoxysilane into 250mL of N, N-dimethylacetamide, stirring at the constant temperature of 0 ℃ for 5 hours under the protection of nitrogen, then adding 5.53g (0.03mol) of cyanuric chloride and 4.52g (0.035mol) of N, N-diisopropylethylamine, and stirring at the constant temperature of 0 ℃ for 5 hours under the protection of nitrogen to obtain a reaction solution B;
3) and (2) mixing the reaction liquid A and the reaction liquid B, uniformly stirring at 80 ℃, then slowly dropwise adding a mixed liquid consisting of 7.21g (0.12mol) of ethylenediamine and 9.49g (0.12mol) of triethylamine under the protection of nitrogen, stirring at a constant temperature of 80 ℃ for 3 hours after dropwise adding is finished, filtering, washing the filtered solid with water, and drying at 80 ℃ for 12 hours to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Testing the performance of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant (the testing method is the same as that in example 1):
through tests, the appearance morphology, the composition structure and the thermal stability of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheet of the embodiment are highly close to those of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheet of the embodiment 1.
The preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 80 parts by mass of polypropylene into an open type hot mixing machine, carrying out hot mixing at the temperature of 175 ℃ by two rollers, adding 20 parts by mass of the phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 175 ℃ for 7min, carrying out hot pressing for 5min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property tests of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 4:
an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps:
1) adding 17.38g (0.05mol) of hexachlorotriphosphazene and 18.05g (0.1mol) of 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane into 250mL of dimethyl sulfoxide, uniformly stirring at 75 ℃, slowly dropwise adding 18.33g (0.15mol) of 4-dimethylaminopyridine, and stirring at constant temperature of 75 ℃ for 5 hours after dropwise adding to obtain a reaction solution A;
2) adding 1.31g of vanadium carbide nanosheet (with the lamella diameter being about 10 micrometers and the interlayer spacing being about 1nm) and 1.31g (0.008mol) of 3-aminopropylmethyldimethoxysilane into 250mL of dimethyl sulfoxide, stirring at the constant temperature of 15 ℃ for 4 hours under the protection of nitrogen, adding 1.84g (0.01mol) of cyanuric chloride and 1.47g (0.012mol) of 4-dimethylaminopyridine, and stirring at the constant temperature of 15 ℃ for 5 hours under the protection of nitrogen to obtain a reaction solution B;
3) and (2) mixing the reaction liquid A and the reaction liquid B, uniformly stirring at 90 ℃, then slowly dropwise adding a mixed liquid consisting of 6.49g (0.108mol) of ethylenediamine and 10.68g (0.135mol) of pyridine under the protection of nitrogen, stirring at a constant temperature of 90 ℃ for 4 hours after dropwise adding is finished, filtering, washing the filtered solid with water, and drying at 80 ℃ for 12 hours to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Testing the performance of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant (the testing method is the same as that in example 1):
through tests, the appearance, the composition and the thermal stability of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment are highly similar to those of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment 1.
The preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 80 parts by mass of polypropylene into an open type hot mixing machine, carrying out hot mixing at the temperature of 175 ℃ by two rollers, adding 20 parts by mass of phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 180 ℃ for 4min, carrying out hot pressing for 9min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant performance and thermal stability test of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 5:
an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps:
1) adding 17.38g (0.05mol) of hexachlorotriphosphazene and 36.10g (0.2mol) of 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane into 250mL of hexamethyl phosphoric triamide, stirring uniformly at 50 ℃, slowly dropwise adding 28.33g (0.28mol) of pyridine, and stirring at constant temperature of 50 ℃ for 5 hours to obtain a reaction solution A;
2) adding 1.09g of molybdenum carbide nanosheet (with the lamella diameter being about 1 micron and the interlayer spacing being about 6nm) and 6.53g (0.04mol) of 3-aminopropylmethyldimethoxysilane into 250mL of hexamethylphosphoric triamide, stirring at the constant temperature of 10 ℃ for 5h under the protection of nitrogen, adding 7.38g (0.04mol) of cyanuric chloride and 4.86g (0.048mol) of triethylamine, and stirring at the constant temperature of 10 ℃ for 4h under the protection of nitrogen to obtain a reaction solution B;
3) and (2) mixing the reaction liquid A and the reaction liquid B, uniformly stirring at 95 ℃, then slowly dropwise adding a mixed liquid consisting of 6.49g (0.108mol) of ethylenediamine and 13.66g (0.135mol) of triethylamine under the protection of nitrogen, stirring at a constant temperature of 95 ℃ for 3 hours after dropwise adding is finished, filtering, washing the filtered solid with water, and drying at 80 ℃ for 12 hours to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Testing the performance of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant (the testing method is the same as that in example 1):
through tests, the appearance, the composition and the thermal stability of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment are highly similar to those of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment 1.
The preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 80 parts by mass of polypropylene into an open type hot refining machine, carrying out hot refining at the temperature of 180 ℃ through double rollers, adding 20 parts by mass of phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing instrument, preheating at 180 ℃ for 6min, carrying out hot pressing for 8min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property tests of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 6:
an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps:
1) adding 17.38g (0.05mol) of hexachlorotriphosphazene and 22.56g (0.125mol) of 1-oxo-4-hydroxymethyl-2, 6, 7-trioxo-1-phosphabicyclo [2,2,2] octane into 250mL of acetonitrile, uniformly stirring at 60 ℃, slowly dropwise adding 15.18g (0.15mol) of triethylamine, and stirring at constant temperature of 60 ℃ for 7 hours to obtain a reaction solution A;
2) adding 1.44g of zirconium carbide nanosheet (with the lamella diameter of about 3 microns and the interlayer spacing of about 5nm) and 0.72g (0.004mol) of 3-aminopropyltrimethoxysilane into 250mL of 1, 4-dioxane, stirring at the constant temperature of 0 ℃ for 7 hours under the protection of nitrogen, adding 0.92g (0.005mol) of cyanuric chloride and 0.61g (0.005mol) of 4-dimethylaminopyridine, and stirring at the constant temperature of 0 ℃ for 3 hours under the protection of nitrogen to obtain a reaction solution B;
3) and (2) mixing the reaction liquid A and the reaction liquid B, uniformly stirring at 85 ℃, then slowly dropwise adding a mixed liquid consisting of 5.29g (0.088mol) of ethylenediamine and 10.44g (0.132mol) of pyridine under the protection of nitrogen, stirring at constant temperature of 85 ℃ for 5 hours after dropwise adding is finished, filtering, washing the filtered solid with water, and drying at 80 ℃ for 12 hours to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Testing the performance of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant (the testing method is the same as that in example 1):
through tests, the appearance, the composition and the thermal stability of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment are highly similar to those of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment 1.
The preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 80 parts by mass of polypropylene into an open type hot mixing machine, carrying out hot mixing at the temperature of 180 ℃ by two rollers, adding 20 parts by mass of phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 185 ℃ for 5min, carrying out hot pressing for 7min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property tests of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 7:
an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant comprises the following steps:
1) adding 17.38g (0.05mol) of hexachlorotriphosphazene and 36.10g (0.2mol) of 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane into 250mL of N, N-dimethylacetamide, uniformly stirring at 70 ℃, slowly dropwise adding 32.31g (0.25mol) of N, N-diisopropylethylamine, and stirring at constant temperature of 70 ℃ for 6h after dropwise adding is finished to obtain a reaction solution A;
2) adding 0.65g of titanium carbide nanosheets (with the lamella diameter being about 4 microns and the interlayer spacing being about 4nm) and 2.58g (0.0125mol) of 3-aminopropyltriethoxysilane into 250mL of hexamethylphosphoric triamide, stirring at the constant temperature of 15 ℃ for 6h under the protection of nitrogen, adding 2.77g (0.015mol) of cyanuric chloride and 1.19g (0.015mol) of pyridine, and stirring at the constant temperature of 15 ℃ for 4h under the protection of nitrogen to obtain a reaction solution B;
3) and (2) mixing the reaction liquid A and the reaction liquid B, uniformly stirring at 100 ℃, then slowly dropwise adding a mixed liquid consisting of 6.25g (0.104mol) of ethylenediamine and 12.34g (0.156mol) of pyridine under the protection of nitrogen, stirring at constant temperature of 100 ℃ for 3 hours after dropwise adding is finished, filtering, washing the filtered solid with water, and drying at 80 ℃ for 12 hours to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
Testing the performance of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant (the testing method is the same as that in example 1):
through tests, the appearance, the composition and the thermal stability of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment are highly similar to those of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets of the embodiment 1.
The preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 80 parts by mass of polypropylene into an open type hot mixing machine, carrying out hot mixing at the temperature of 175 ℃ by two rollers, adding 20 parts by mass of phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 185 ℃ for 6min, carrying out hot pressing for 6min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property tests of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 8:
the preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 70 parts by mass of polypropylene into an open type hot melting machine, carrying out hot melting at the temperature of 180 ℃ through double rollers, adding 30 parts by mass of the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant of the embodiment 1 after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 185 ℃ for 5min, carrying out hot pressing for 6min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property tests of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 9:
the preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 75 parts by mass of polypropylene into an open type hot melting machine, carrying out hot melting at the temperature of 180 ℃ through two rollers, adding 25 parts by mass of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets in the embodiment 1 after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 185 ℃ for 5min, carrying out hot pressing for 6min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property tests of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Example 10:
the preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 85 parts by mass of polypropylene into an open type hot melting machine, carrying out hot melting at the temperature of 180 ℃ through double rollers, adding 15 parts by mass of the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets in the example 1 after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing machine, preheating at 185 ℃ for 5min, carrying out hot pressing for 6min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property tests of the flame retardant polypropylene material of this example are shown in tables 1 and 2.
Comparative example 1:
a polypropylene material is prepared by the following steps:
adding polypropylene into an open type heat mill, carrying out heat milling at the temperature of 180 ℃ by two rollers, transferring the material into a flat vulcanizing instrument after the polypropylene is melted and wrapped, preheating at 185 ℃ for 5min, then carrying out hot pressing for 6min, and then transferring the material into a cold press to carry out cold pressing to room temperature, thus obtaining the polypropylene material.
The results of the flame retardant property and thermal stability property tests of the polypropylene material of this comparative example are shown in tables 1 and 2.
Comparative example 2:
the preparation method of the flame-retardant polypropylene material comprises the following steps:
adding 75 parts by mass of polypropylene into an open type hot refining machine, carrying out hot refining at the temperature of 180 ℃ by using double rollers, adding 16.7 parts by mass of ammonium polyphosphate and 8.3 parts by mass of pentaerythritol after the polypropylene is melted and wrapped on the rollers, mixing, transferring the material into a flat vulcanizing instrument, preheating at 185 ℃ for 5min, carrying out hot pressing for 6min, transferring the material into a cold press, and carrying out cold pressing to room temperature to obtain the flame-retardant polypropylene material.
The results of the flame retardant property and thermal stability property test of the flame retardant polypropylene material of the present comparative example are shown in tables 1 and 2.
And (4) performance testing:
the results of the flame retardant property and thermal stability test of the flame retardant polypropylene materials of examples 1-10, the polypropylene material of comparative example 1 and the flame retardant polypropylene material of comparative example 2 are shown in tables 1 and 2:
TABLE 1 flame retardancy and thermal stability test results I
Figure BDA0003484402640000111
Figure BDA0003484402640000121
TABLE 2 flame retardancy and thermal stability test results II
Figure BDA0003484402640000122
Note:
and (3) testing the combustion performance:
limiting Oxygen Index (LOI) test was performed according to ASTM D2863 with specimen dimensions of 120mm by 6.5mm by 3 mm;
vertical burning (UL-94) tests were performed according to ASTM D635 with specimen dimensions of 127mm by 12.7mm by 3.2 mm;
cone Calorimetry (CCT) tests were performed according to ISO 5660-1 with sample dimensions of 100mm by 4 mm;
thermogravimetric Test (TG): weighing 5-10 mg of sample, placing the sample in an alumina crucible, and measuring a thermal weight loss curve in an air atmosphere in a thermogravimetric analyzer, wherein the heating rate is 20 ℃/min, and the test temperature range is 30-800 ℃.
As can be seen from tables 1 and 2:
1) the test results of the embodiments 1 to 10 are combined, so that the phosphorus-nitrogen single-component intumescent flame retardant modified by the MXene nanosheets prepared under different process conditions by using different MXene nanosheets, aminopropyl alkoxysilane, an acid-binding agent and an aprotic polar solvent can effectively improve the flame retardant property and the thermal stability of PP;
2) by comparing the test results of the examples 1-10 and the comparative examples 1-2, it can be seen that after the MXene nanosheet-modified phosphorus-nitrogen single-component intumescent flame retardant is added independently in an amount of more than or equal to 20 wt%, the limiting oxygen index LOI of the flame-retardant PP is remarkably improved, the UL-94 grade is improved from NR to V-0, and meanwhile, the thermal stability is also remarkably improved;
3) as can be seen from the test results of the comparative examples 1 to 10 and the comparative examples 1 to 2, after the MXene nanosheet modified phosphorus nitrogen single-component intumescent flame retardant is added alone, the peak value of the heat release rate of the flame retardant PP is 728.1kW/m2Remarkably reduced to 88kW/m2～113kW/m2Meanwhile, the total heat release amount is from 130.8MJ/m2Remarkably reduced to 50MJ/m2～68MJ/m2The carbon residue after cone calorimetry test of comparative example 1 and comparative example 2 is only 0 and 3.3 wt%, while the flame retardant PP carbon residue of the present application reaches 20 wt% to 31 wt%;
the reasons for the above resultsThe method comprises the following steps: when heated and combusted, the phosphorus-nitrogen single-component intumescent flame retardant modified by MXene nanosheets has rich phosphazene ring structures and caged phosphate structures, and can rapidly generate reactions such as intramolecular dehydration, esterification, crosslinking, carbonization and the like to form an intumescent carbon protective layer, so that the transfer of heat, combustible gas and oxygen is effectively blocked; the MXene nanosheets can exert catalytic char formation characteristics and free radical adsorption characteristics, so that on one hand, the polypropylene and phosphorus-nitrogen single-component intumescent flame retardant is catalyzed to be carbonized on transition metal Lewis acid points of the nanosheets, and the formation of a high-quality intumescent carbon layer is promoted; on the other hand, can adsorb H, OH and O2 -Isoradicals, which inhibit the polypropylene combustion and degradation processes initiated by the free radicals; the MXene nanosheets and the phosphorus-nitrogen single-component intumescent flame retardant generate a high-efficiency synergistic flame retardant effect; compared with the prior art, the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant has a more efficient flame retardant effect and a more excellent flame retardant effect in a flame retardant polypropylene material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of an MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant is characterized by comprising the following steps:
1) dispersing hexachlorotriphosphazene and 1-oxo-4-hydroxymethyl-2, 6, 7-trioxo-1-phosphabicyclo [2,2,2] octane in an aprotic polar solvent, adding an acid-binding agent, and performing nucleophilic substitution reaction to obtain a reaction solution A;
2) dispersing MXene nanosheets and aminopropylalkoxysilane in an aprotic polar solvent, carrying out in-situ modification reaction under a protective atmosphere, adding cyanuric chloride and an acid-binding agent, and carrying out nucleophilic substitution reaction under the protective atmosphere to obtain a reaction solution B;
3) and mixing the reaction liquid A and the reaction liquid B, adding ethylenediamine and an acid-binding agent, and reacting to obtain the MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant.
2. The preparation method of the MXene nanosheet-modified phosphorus-nitrogen single-component intumescent flame retardant of claim 1, wherein: the mole ratio of the hexachlorotriphosphazene, the 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2,2,2] octane and the cyanuric chloride is 1: 2-4: 0.1-1; the ratio of the total molar weight of the hexachlorotriphosphazene and the cyanuric chloride to the molar weight of the ethylenediamine is 1: 1-2.
3. The preparation method of the MXene nanosheet-modified phosphorus-nitrogen single-component intumescent flame retardant of claim 1 or 2, characterized in that: the nucleophilic substitution reaction in the step 1) is carried out at 50-80 ℃, and the reaction time is 4-7 h.
4. The preparation method of the MXene nanosheet-modified phosphorus-nitrogen single-component intumescent flame retardant of claim 1, wherein: the MXene nanosheets are at least one of titanium carbide nanosheets, titanium nitride nanosheets, titanium carbonitride nanosheets, zirconium carbide nanosheets, molybdenum carbide nanosheets and vanadium carbide nanosheets.
5. The preparation method of the MXene nanosheet-modified phosphorus-nitrogen single-component intumescent flame retardant of any one of claims 1, 2, and 4, characterized in that: the aminopropyl alkoxy silane is at least one of N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, 3-aminopropyl triethoxy silane, 3-aminopropyl methyl dimethoxy silane and 3-aminopropyl trimethoxy silane.
6. The preparation method of the MXene nanosheet-modified phosphorus-nitrogen single-component intumescent flame retardant of any one of claims 1, 2, and 4, characterized in that: step 2) the in-situ modification reaction is carried out at 0-30 ℃, and the reaction time is 4-7 h; the nucleophilic substitution reaction in the step 2) is carried out at the temperature of 0-30 ℃, and the reaction time is 3-5 h.
7. The preparation method of the MXene nanosheet-modified phosphorus-nitrogen single-component intumescent flame retardant of any one of claims 1, 2, and 4, characterized in that: the reaction in the step 3) is carried out at the temperature of 80-105 ℃, and the reaction time is 2-5 h.
8. The preparation method of the MXene nanosheet-modified phosphorus-nitrogen single-component intumescent flame retardant of any one of claims 1, 2, and 4, characterized in that: the aprotic polar solvent is at least one of acetonitrile, dimethyl sulfoxide, N-dimethylacetamide, 1, 4-dioxane and hexamethylphosphoric triamide; the acid-binding agent is at least one of triethylamine, pyridine, N-diisopropylethylamine and 4-dimethylaminopyridine.
9. An MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant which is characterized by being prepared by the method of any one of claims 1-8.
10. A flame retardant polypropylene material, characterized by comprising 15-30 wt% of the MXene nanosheet modified phosphorus-nitrogen single component intumescent flame retardant of claim 9.
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