CN112357897A - Preparation method and application of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane - Google Patents
Preparation method and application of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane Download PDFInfo
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- CN112357897A CN112357897A CN202011236773.1A CN202011236773A CN112357897A CN 112357897 A CN112357897 A CN 112357897A CN 202011236773 A CN202011236773 A CN 202011236773A CN 112357897 A CN112357897 A CN 112357897A
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- Prior art keywords
- phosphorus
- retardant
- doped carbon
- carbon nitride
- flame
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 69
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- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 claims description 8
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
Abstract
The invention provides a preparation method of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane, belonging to the field of nano materials. The method comprises the steps of uniformly mixing a nitrogen-rich compound and a phosphorus-containing compound, and obtaining the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles by a one-step calcination method. The method not only enables the phosphorus atoms to be successfully doped into the heptazine structure, promotes the flame retardant material prepared by the method to form a cross-linked network in the combustion process, and enhances the retention of phosphorus elements in a condensed phase. The invention also provides the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nano particle prepared by the method, the material has high overall thermal stability, and the residual carbon rate of the material can be fully improved when the material is used as a flame-retardant material additive. The invention also provides flame-retardant waterborne polyurethane prepared from the material and a preparation method thereof, and the method can ensure that the finally prepared material has high phosphorus content and stable material properties by doping a proper amount of phosphorus-doped carbon nitride two-dimensional nano particles through in-situ emulsification.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a preparation method and application of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane.
Background
The waterborne polyurethane has excellent performance and mature process, and is widely applied to production and life. However, due to the general flammability and extremely easy ignition and combustion of polymer materials, and even the generation of toxic gases during combustion, there is a great potential fire risk, and such safety hazards make the development of waterborne polyurethane composites with fire-proof and flame-retardant capabilities very important. At present, the additive flame retardant is simple to prepare, is easy for industrial expanded production, and is widely applied in the field of flame-retardant polymer composite materials.
Triazine-based flame retardants are one of the most important varieties of nitrogen-based flame retardants, and triazine-based derived heptazine-based compounds such as graphite-like phase two-dimensional carbon nitride have excellent thermal and chemical stability. The inert combustion gas generated by the thermal decomposition of the nitrogen flame retardant comprises ammonia gas, nitrogen gas, oxynitride, water vapor, carbon dioxide and the like, and the gases have low toxicity and low corrosivity, can dilute the oxygen concentration on the surface of the polymer and the concentration of combustible gas in combustion, and destroy the continuous combustion condition, thereby achieving the flame-retardant effect. However, in the aspect of modifying the traditional heptazinyl flame retardant to further improve the flame retardant performance, the problem that the heptazinyl flame retardant does not have the effect of obviously increasing the quantity of carbon residues in condensed phase flame retardant is faced.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a preparation method of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane. The method is characterized in that phosphorus is doped into a carbon nitride framework to form a P-N bond and a P-N bond, so that the content of P in the material is increased, and the carbon nitride obtains a condensed phase flame retardant effect.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane comprises the following steps:
(1) stirring and uniformly mixing the nitrogen-rich compound and the phosphorus-containing compound to obtain a mixed precursor; the mass ratio of the nitrogen-rich compound to the phosphorus-containing compound is 1: 0.01-0.5;
(2) heating the mixed precursor obtained in the step (1) to 350-600 ℃, and preserving heat for 0.1-5 hours to obtain blocky doped carbon;
(3) and (3) crushing the blocky doped carbon obtained in the step (2) to obtain the phosphorus-doped carbon nitride two-dimensional nano particles for preparing the flame-retardant waterborne polyurethane.
According to the preparation method of the phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing the flame-retardant waterborne polyurethane, provided by the invention, the nitrogen-rich compound and the phosphorus-containing compound are uniformly mixed, the heating and calcining method is adopted to prepare the massive phosphorus-doped carbon nitride, and the massive phosphorus-doped carbon nitride is fully crushed to obtain the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles, so that phosphorus atoms are successfully doped into a heptazine structure to form a P-N bond and a P ═ N bond, the formation of a cross-linked network and the retention of phosphorus elements in a condensed phase of the flame-retardant material prepared by the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles are promoted, and the thermal stability and the carbon residue rate of the.
Preferably, the nitrogen-rich compound comprises at least one of melamine, cyanuric acid, dicyandiamide, cyanamide, urea, melamine cyanuric acid, guanidine hydrochloride, thiourea and cyanuric chloride. The nitrogen-rich compound has rich source and high nitrogen content, and can be effectively used as a precursor of a carbon nitride framework.
Preferably, the phosphorus-containing compound comprises at least one of diammonium phosphate, phytic acid, red phosphorus, black phosphorus, 2-aminoethylphosphonic acid, hexachlorotriphosphazene, melamine polyphosphate, sodium pyrophosphate, sodium hypophosphite and phosphoric acid. The phosphorus-containing compound precursor and the carbon precursor can be effectively mixed, and phosphorus elements are fully embedded into the carbon nitride framework in the heating and calcining process, so that the thermal stability of the material is provided.
Preferably, the frequency of stirring and mixing in the step (1) is 10-300 Hz, and the time is 0.1-10 min.
Preferably, the frequency of the pulverization in the step (3) is 10-300 Hz, and the time is 0.1-10 min. The precursor and the generated blocky doped carbon are stirred and crushed by the defined parameters, so that the uniformity and the size of the material can be effectively controlled.
Preferably, the heating rate of the step (2) is 1-20 ℃/min. The carbon precursor framework can be effectively protected to be complete through a proper temperature rise rate, and meanwhile, the stable formation of P-N bonds and P-N bonds in the material can be ensured.
The invention also aims to provide the phosphorus-doped carbon nitride two-dimensional nanoparticles prepared by the preparation method for the phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing the flame-retardant waterborne polyurethane.
The phosphorus-doped carbon nitride two-dimensional nano particles provided by the invention are rich in P-N bonds and P ═ N bonds, high in material stability and high in phosphorus content, and when the phosphorus-doped carbon nitride two-dimensional nano particles are used for flame-retardant materials, the residual carbon rate and the thermal stability of the materials can be fully improved.
The invention also aims to provide flame-retardant waterborne polyurethane prepared from the phosphorus-doped carbon nitride two-dimensional nanoparticles.
The flame-retardant waterborne polyurethane provided by the invention contains phosphorus-doped carbon nitride two-dimensional nanoparticles as an additive, so that the phosphorus content is obviously improved, and compared with the traditional heptazine-based flame retardant which does not have the effect of obviously increasing the quantity of carbon residues in condensed phase flame retardance, the flame-retardant waterborne polyurethane provided by the invention has high thermal stability in the use process and can effectively increase the quantity of carbon residues.
The invention also aims to provide a preparation method of the flame-retardant waterborne polyurethane.
The preparation method of the flame-retardant waterborne polyurethane comprises the following steps:
(a) mixing polycarbonate diol, polytetramethylene glycol, polyether diol and isophorone diisocyanate under the protection of atmosphere, heating for reaction, and cooling to obtain a mixture A;
(b) adding dimethylolpropionic acid, 1, 6-hexanediol, trimethylolpropane and dibutyltin dilaurate into the mixture A obtained in the step (a), heating for reaction, and cooling to obtain a mixture B;
(c) adding water to the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles, performing ultrasonic treatment, and uniformly dispersing to obtain a phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticle aqueous solution;
(d) and (3) adding triethylamine into the mixture B obtained in the step (B), dispersing for 10-20 min, adding the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticle aqueous solution obtained in the step (C), reacting in situ to obtain a dispersion liquid C, and drying and molding the dispersion liquid C to obtain the flame-retardant waterborne polyurethane.
According to the preparation method of the flame-retardant waterborne polyurethane provided by the invention, the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles are emulsified in situ to be uniformly dispersed in the product, so that the operation is simple and convenient, and the industrial large-scale production can be realized.
Preferably, the heating reaction in the step (a) is carried out at the temperature of 85-95 ℃ for 1.5-2.5 h.
Preferably, the heating reaction in the step (b) is carried out at the temperature of 75-85 ℃ for 2.5-3.5 h.
Preferably, the mass fraction of the solid content in the dispersion liquid in the step (d) is 25-35%; the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles in the solid content have a mass fraction of 2-4%. By properly adding the phosphorus-doped carbon nitride two-dimensional nano particles, the stability of the waterborne polyurethane can be maintained, and the carbon content and the flame retardant property of the material can be improved.
The invention has the beneficial effects that the invention provides a preparation method of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane. The nitrogen-rich compound and the phosphorus-containing compound are uniformly mixed, and are heated, calcined and then crushed to obtain the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nano particle, so that phosphorus atoms are successfully doped into a heptazine structure to form a P-N bond and a P ═ N bond, and the formation of a cross-linked network and the retention of phosphorus elements in a condensed phase of the flame-retardant material prepared by the method are promoted in the combustion process. The invention also provides the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nano particle prepared by the method, the material has high overall thermal stability, and the residual carbon rate of the material can be fully improved when the material is used as a flame-retardant material additive. The invention also provides flame-retardant waterborne polyurethane prepared from the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles, and the product has high phosphorus content and high residual carbon number in use. The invention also provides a preparation method of the flame-retardant waterborne polyurethane, and the method can ensure that the finally prepared material has high phosphorus content and stable material properties by doping a proper amount of phosphorus-doped carbon nitride nano particles through in-situ emulsification.
Drawings
FIG. 1 is an X-ray photoelectron spectrum (XPS) of a phosphorus-doped carbon nitride two-dimensional nanoparticle prepared according to the present invention;
FIG. 2 is an X-ray powder diffraction pattern (XRD) of the phosphorus-doped carbon nitride two-dimensional nanoparticles prepared according to the present invention; wherein a is undoped modified carbon nitride and b is phosphorus-doped carbon nitride two-dimensional nano-particle
FIG. 3 is an infrared spectrum (IR) of the phosphorus-doped carbon nitride two-dimensional nanoparticles prepared according to the present invention; wherein a is undoped modified carbon nitride and b is phosphorus-doped carbon nitride two-dimensional nano-particle
FIG. 4 is a Transmission Electron Microscope (TEM) image of the phosphorus-doped carbon nitride two-dimensional nanoparticles prepared according to the present invention.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents and instruments designed for the practice of the present invention and the comparative examples are common reagents and instruments unless otherwise specified.
Example 1
One embodiment of the preparation method of the phosphorus-doped carbon nitride two-dimensional nanoparticles comprises the following steps:
(1) stirring thiourea and 2-amino ethyl phosphonic acid for 3min at the frequency of 50Hz, and uniformly mixing to obtain a mixed precursor; the mass ratio of the thiourea to the 2-aminoethylphosphonic acid is 1: 0.2;
(2) putting the mixed precursor obtained in the step (1) into a ceramic crucible, sealing, heating to 400 ℃ in a muffle furnace at a speed of 15 ℃/min, preserving heat for 3h, and naturally cooling to obtain blocky doped carbon;
(3) and (3) crushing the blocky doped carbon obtained in the step (2) for 50s in a high-speed crusher at the frequency of 50Hz to obtain the phosphorus-doped carbon nitride two-dimensional nano particles.
The phosphorus-doped carbon nitride two-dimensional nano particle is used for preparing flame-retardant waterborne polyurethane, and the preparation method comprises the following steps:
(a) placing 5.4g of polycarbonate diol, 1.5g of polytetramethylene glycol, 1.95g of polyether diol and 14.151g of isophorone diisocyanate in a three-neck flask under the protection of nitrogen atmosphere, mixing, heating to 90 ℃, stirring for reacting for 2 hours, and cooling to 40 ℃ to obtain a mixture A;
(b) adding 1.35g of dimethylolpropionic acid, 3.357g of 1, 6-hexanediol, 0.821g of trimethylolpropane and 0.0489g of dibutyltin dilaurate into the mixture A obtained in the step (a), heating to 80 ℃, reacting for 3 hours, and cooling to room temperature to obtain a mixture B;
(c) adding water into 0.6g of phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles, carrying out ultrasonic treatment, and after uniformly dispersing to obtain a phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticle aqueous solution;
(d) adding 1.2g of triethylamine into the mixture B obtained in the step (B), dispersing for 15min, adding the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticle aqueous solution obtained in the step (C), reacting in situ to obtain a dispersion liquid C, and drying and molding the dispersion liquid C to obtain the flame-retardant waterborne polyurethane; the mass fraction of the solid content in the dispersion liquid is 30%; the mass fraction of the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles in the solid content is 3%.
Example 2
One embodiment of the preparation method of the phosphorus-doped carbon nitride two-dimensional nanoparticles comprises the following steps:
(1) uniformly mixing melamine and sodium hypophosphite by stirring for 50s at the frequency of 50Hz to obtain a mixed precursor; the mass ratio of the melamine to the sodium hypophosphite is 1: 0.09;
(2) placing the mixed precursor obtained in the step (1) into a ceramic crucible, sealing, heating to 600 ℃ in a muffle furnace at a speed of 20 ℃/min, preserving heat for 2h, and naturally cooling to obtain blocky doped carbon;
(3) and (3) crushing the blocky doped carbon obtained in the step (2) in a high-speed crusher at the frequency of 50Hz for 1min to obtain the phosphorus-doped carbon nitride two-dimensional nano particles.
The preparation method of the flame-retardant waterborne polyurethane disclosed in the embodiment is the same as that of the embodiment 1.
Example 3
One embodiment of the preparation method of the phosphorus-doped carbon nitride two-dimensional nanoparticles comprises the following steps:
(1) uniformly mixing urea and phytic acid for 50 seconds under the frequency of 50Hz to obtain a mixed precursor; the mass ratio of the urea to the phytic acid is 1: 0.05;
(2) putting the mixed precursor obtained in the step (1) into a ceramic crucible, sealing, heating to 500 ℃ in a muffle furnace at a speed of 10 ℃/min, preserving heat for 2h, and naturally cooling to obtain blocky doped carbon;
(3) and (3) crushing the blocky doped carbon obtained in the step (2) in a high-speed crusher at the frequency of 50Hz for 2min to obtain the phosphorus-doped carbon nitride two-dimensional nano particles.
The preparation method of the flame-retardant waterborne polyurethane disclosed in the embodiment is the same as that of the embodiment 1.
Example 4
The present example is different from example 1 only in that the temperature increase rate in step (2) is 30 ℃/min.
Example 5
The present example is different from example 1 only in that the temperature increase rate in step (2) is 0.5 ℃/min.
Comparative example 1
The comparative example differs from example 1 only in that the incubation time in step (2) was 6 h.
Comparative example 2
The comparative example differs from example 1 only in that the incubation time in step (2) was 0.05 h.
Comparative example 3
The comparative example differs from example 1 only in that the heating temperature in step (2) was 200 ℃.
Comparative example 4
The comparative example differs from example 1 only in that the heating temperature in step (2) was 700 ℃.
Comparative example 5
The difference between the comparative example and the example 1 is only that the nitrogen-rich compound and the phosphorus-containing compound in the step (1) are hexachlorocyclotriphosphazene and phosphoric acid respectively, and the mass ratio of the nitrogen-rich compound to the phosphorus-containing compound is 1: 0.5.
In order to verify the performance of the flame-retardant waterborne polyurethane product prepared by the invention, the flame-retardant waterborne polyurethane prepared in examples 1-3 and a reference sample (the pure waterborne polyurethane without the phosphorus-doped carbon nitride two-dimensional nanoparticles) were subjected to a flame-retardant test, and the test results are shown in table 1. The carbon residue rate is tested by using a thermogravimetric analyzer; the limiting oxygen index is tested using the GB/T-2406 + 1993 standard method; the specific method of the flame retardant test is to incline the sample at 45 degrees and continuously ignite for 10s, and observe whether the sample is self-extinguished after being away from the fire.
TABLE 1
As can be seen from Table 1, the flame retardant waterborne polyurethane prepared by using the phosphorus-doped carbon nitride two-dimensional nanoparticles prepared by the method as the additive has the advantages of obviously improved carbon residue rate, improved thermal stability and excellent flame retardant property.
The two-dimensional nanoparticles of phosphorus-doped carbon nitride prepared in example 1 were subjected to X-ray photoelectron spectroscopy (XPS), and as a result, as shown in fig. 1, an obvious characteristic peak of P element was observed, indicating that P element was doped into the prepared two-dimensional nanoparticles of phosphorus-doped carbon nitride.
The two-dimensional nanoparticles of phosphorus-doped carbon nitride prepared in example 2 were subjected to X-ray powder diffraction (XRD), and the results are shown in fig. 2, where a represents undoped modified carbon nitride and b represents the two-dimensional nanoparticles of phosphorus-doped carbon nitride, as can be seen from the spectrum of fig. 2. a has two characteristic peaks, one at 12.97 ° (corresponding to 100 planes) caused by in-plane repeat units; the other at 27.73 ° (corresponding to the 002 plane) is caused by the interlayer stacking of conjugated aromatic units. b is similar to the diffraction pattern of a, which shows that a good carbon nitride framework is reserved in the phosphorus doping process; the infrared test result is shown in fig. 3, and it can be seen from the infrared spectrum of fig. 3, wherein a represents undoped modified carbon nitride, and b represents phosphorus doped carbon nitride two-dimensional nanoparticles. The infrared spectra are not clearly distinguished due to overlapping strong a, b C-N vibration bands, but at 814cm-1The small low wavenumber shift occurring in the sharp bands around and around can be attributed to the movement of electron clouds in the C-N and C ═ N bonds caused by the doping of the heteroatom P; both of the above also indicate successful doping of the P element.
The two-dimensional nanoparticles of phosphorus-doped carbon nitride prepared in example 3 were subjected to Transmission Electron Microscopy (TEM) testing, and the results are shown in fig. 4. As can be seen from the figure, the nano particles are mainly two-dimensional plate-shaped, and the doping of the P element does not cause the damage of the carbon nitride material structure.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A preparation method of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane is characterized by comprising the following steps:
(1) stirring and uniformly mixing the nitrogen-rich compound and the phosphorus-containing compound to obtain a mixed precursor; the mass ratio of the nitrogen-rich compound to the phosphorus-containing compound is 1: 0.01-0.5;
(2) heating the mixed precursor obtained in the step (1) to 350-600 ℃, and preserving heat for 0.1-5 hours to obtain blocky doped carbon;
(3) and (3) crushing the blocky doped carbon obtained in the step (2) to obtain the phosphorus-doped carbon nitride two-dimensional nano particles.
2. The method for preparing phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant aqueous polyurethane according to claim 1, wherein the nitrogen-rich compound in step (1) comprises at least one of melamine, cyanuric acid, dicyandiamide, cyanamide, urea, melamine cyanuric acid, guanidine hydrochloride, thiourea and cyanuric chloride.
3. The method for preparing phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant aqueous polyurethane according to claim 1, wherein the phosphorus-containing compound of step (1) comprises at least one of diammonium phosphate, phytic acid, red phosphorus, black phosphorus, 2-aminoethylphosphonic acid, hexachlorotriphosphazene, melamine polyphosphate, sodium pyrophosphate, sodium hypophosphite and phosphoric acid.
4. The preparation method of the phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane according to claim 1, wherein the frequency of stirring and mixing in the step (1) is 10-300 Hz, and the time is 0.1-10 min; and (3) crushing at the frequency of 10-300 Hz for 0.1-10 min.
5. The preparation method of the phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane according to claim 1, wherein the heating rate in the step (2) is 1-20 ℃/min.
6. The phosphorus-doped carbon nitride two-dimensional nanoparticles prepared by the method for preparing the phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane as claimed in any one of claims 1 to 5.
7. A flame retardant aqueous polyurethane comprising the phosphorus-doped carbon nitride two-dimensional nanoparticle according to claim 6.
8. The method for preparing the flame-retardant aqueous polyurethane according to claim 7, comprising the steps of:
(a) mixing polycarbonate diol, polytetramethylene glycol, polyether diol and isophorone diisocyanate under the protection of atmosphere, heating for reaction, and cooling to obtain a mixture A;
(b) adding dimethylolpropionic acid, 1, 6-hexanediol, trimethylolpropane and dibutyltin dilaurate into the mixture A obtained in the step (a), heating for reaction, and cooling to obtain a mixture B;
(c) adding water to the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles, performing ultrasonic treatment, and uniformly dispersing to obtain a phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticle aqueous solution;
(d) and (3) adding triethylamine into the mixture B obtained in the step (B), dispersing for 10-20 min, adding the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticle aqueous solution obtained in the step (C), reacting in situ to obtain a dispersion liquid C, and drying and molding the dispersion liquid C to obtain the flame-retardant waterborne polyurethane.
9. The preparation method of the flame-retardant waterborne polyurethane as claimed in claim 8, wherein the temperature of the heating reaction in the step (a) is 85-95 ℃ and the time is 1.5-2.5 h; the heating reaction in the step (b) is carried out at the temperature of 75-85 ℃ for 2.5-3.5 h; the mass fraction of solid content in the dispersion liquid in the step (d) is 25-35%; the phosphorus-doped carbon nitride halogen-free flame-retardant two-dimensional nanoparticles in the solid content have a mass fraction of 2-4%.
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