CN116178795A - Multifunctional phosphorus-nickel doped graphite-like carbon nitride nano sheet, preparation method thereof and ABS material - Google Patents
Multifunctional phosphorus-nickel doped graphite-like carbon nitride nano sheet, preparation method thereof and ABS material Download PDFInfo
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Abstract
The invention discloses a multifunctional phosphorus-nickel doped graphite carbon nitride (Ni-P-C) 3 N 4 ) Nanosheets, preparation method thereof and ABS material, wherein Ni-P-C 3 N 4 The nano-sheet can effectively improve the dispersibility of the nano-sheet in an ABS material by adopting phosphorus-nickel co-doping, and the nano-sheet can simultaneously improve the thermal stability, the mechanical property, the flame retardance and the smoke suppression of a polymer material by adding the nano-sheet into the ABS material, and uniformly disperse Ni-P-C in a composite material 3 N 4 Binding g-C 3 N 4 The physical barrier effect of the nano-sheet and the catalytic carbonizing effect of phosphorus and nickel elements can effectively improve the heat resistance and carbonization of ABS under the condition of low addition amountAbility and mechanical strength. The high-performance ABS polymer composite material prepared by the invention has wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and relates to a multifunctional phosphorus-nickel doped graphite-like carbon nitride nanosheet, a preparation method thereof and an ABS material.
Background
Acrylonitrile-butadiene-styrene (ABS) copolymers are widely used in electronics, automobiles, aviation, etc. fields due to their light weight, good thermal stability, high mechanical properties, and excellent chemical stability. However, ABS is flammable, and releases a lot of heat and smoke during combustion, and much work has been done on the development of flame retardance of ABS.
The introduction of flame retardants is an efficient and simple method of preparing flame retardant polymers. The halogen-containing compound has high flame retardant efficiency and is widely applied to the preparation of flame retardant polymer materials. In recent years, some halogenated flame retardants have been disabled due to their potential harm to the environment and humans, resulting in various halogen-free alternatives such as phosphorus (P), nitrogen (N), and metal compounds. However, these common flame retardants often impart flame retardancy to polymers at the expense of mechanical properties. In order to avoid this drawback, many nanomaterials (e.g., graphene, clay, boron nitride, carbon nanotubes, etc.) having flame retardant and reinforcing effects have been developed in recent years. However, most reported flame retardant ABS composite materials have poor smoke suppression and low thermal stability. Therefore, development of multifunctional nano additives to improve mechanical properties, thermal stability, flame retardance and smoke suppression of ABS is particularly urgent.
Graphite-like carbon nitride (g-C) 3 N 4 ) As a two-dimensional (2D) nanoplatelet, it shows great potential in enhancing the flame retardancy of polymeric materials due to its high thermal stability, excellent chemical stability and excellent barrier effect. Similar to other nanomaterials, g-C 3 N 4 Flame retardants are required to be doped to improve their flame retardant efficiency and interface interactions with the polymer matrix. Phosphoric acid doped g-C as reported 3 N 4 Polyaniline (g-C) 3 N 4 Preparation of/PANI@PA) hybrid material and application thereof in intumescent flame retardant epoxy coating, and zinc phytate grafted g-C for epoxy resin (EP) 3 N 4 (g-C 3 N 4 PAZn) flame retardant, etc., g-C, although some encouraging progress has been made 3 N 4 Is required to be further improved and is based on g-C 3 N 4 The properties of flame retardant ABS have not been satisfactory.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a multifunctional phosphorus-nickel doped graphite-like carbon nitride (Ni-P-C) 3 N 4 ) The nano sheet can improve the mechanical property, the thermal stability, the flame retardance and the smoke suppression of ABS at the same time.
The technical scheme adopted by the invention is as follows:
a preparation method of a multifunctional phosphorus-nickel doped graphite-like carbon nitride nano-sheet comprises the following steps:
1) Placing urea into a crucible with a cover, calcining in a muffle furnace, cooling to room temperature, and grinding to obtain blocky g-C 3 N 4 A powder;
2) Lump g-C 3 N 4 Stirring the powder in 25% sulfuric acid solution for at least 48 hr to form suspension, centrifuging to remove supernatant, adding distilled water, centrifuging again to remove supernatant, repeatedly adding distilled water and centrifuging until supernatant becomes neutral, drying the solid product, and grinding to obtain g-C 3 N 4 A nanosheet;
3) Toluene and g-C 3 N 4 Putting the nano-sheet into a three-neck round bottom flask, carrying out ultrasonic treatment for at least 10 minutes, adding phosphorus oxychloride and triethylamine, stirring at room temperature for at least 30 minutes, heating the mixture to 60 ℃, stirring for 3 hours, filtering to obtain a crude product, washing with ethanol for a plurality of times, drying,obtaining phosphorus graft C 3 N 4 I.e. P-C 3 N 4 A nanosheet;
4) P-C 3 N 4 Dispersing the nano-sheets in distilled water, adding nickel nitrate aqueous solution after ultrasonic treatment, stirring for at least 2 hours, and filtering and collecting to obtain Ni-P-C 3 N 4 The nano-sheet is washed by ethanol and then dried.
In the technical scheme, in the step 1), the calcination is carried out by heating to 420-450 ℃ at a heating rate of 5 ℃/min, preserving heat for 2-8 h at the temperature, heating to 510-540 ℃ and preserving heat for 3-6 h to complete the reaction.
Further, the centrifugation in step 2) is carried out at a rotational speed of 8000 rpm for a period of 3 minutes.
Further, toluene, g-C as described in step 3) 3 N 4 The dosage ratio of the nanosheets, the phosphorus oxychloride and the triethylamine is 100ml to 3g to 0.5g to 3g.
Further, P-C in step 4) 3 N 4 And nickel nitrate in the weight ratio of 100 to 3-15.
Further, the drying is: drying at 60℃for 24h.
An ABS nanocomposite material, the raw materials of which contain the multifunctional phosphorus-nickel doped graphite-like carbon nitride nano-sheets.
Further, ni-P-C in the material 3 N 4 The nano-sheet accounts for 0.1 to 15 weight percent.
The beneficial effects of the invention are as follows:
the invention provides a multifunctional P/Ni modified g-C 3 N 4 The nano sheet can be added into ABS material to improve heat stability, mechanical property, flame retardance and smoke suppression of polymer material, and uniformly dispersed Ni-P-C in composite material 3 N 4 Binding g-C 3 N 4 The physical barrier effect of the nano-sheet and the catalytic carbonizing effect of phosphorus and nickel elements can effectively improve the heat resistance, carbonization capacity and mechanical strength of ABS under the condition of low addition. 2.0wt% of Ni-P-C relative to pure ABS 3 N 4 ABS/Ni-P-CN2 composite materialIncreases in TTI by 12s, decreases PHRR and PSPR by 32.4% and 33.8%, respectively, and Ni-P-C 3 N 4 The introduction of (3) also increases the tensile strength of the material by 24.3% and the initial degradation temperature by 15 ℃. The invention can prepare high-performance polymer composite material and has wide industrial application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a block g-C of the present invention 3 N 4 、g-C 3 N 4 Nanoplatelets, P-C 3 N 4 And Ni-P-C 3 N 4 FT-IR (a) and XPS (b) spectra, ni-P-C 3 N 4 High resolution C1s (C), N1s (d), O1s (e), P2P (f) and Ni2P (g) XPS spectra, ni-P-C 3 N 4 (h) TEM micrograph of (C) and Ni-P-C 3 N 4 (i) STEM-HAADF image and corresponding element map of C, N, O, P, ni in the selected region.
FIG. 2 is a TEM image of an ABS/CN2 (a, b) and ABS/Ni-P-CN2 (c, d) composite of the present invention.
FIG. 3 is an XRD pattern for ABS and ABS composites of the invention.
FIG. 4 shows the stress-strain curve (a) and the tensile property parameter (b) of ABS and the ABS composite material of the invention.
FIG. 5 is a graph of N for an ABS composite in accordance with the present invention 2 TGA (a) and DTG (b) curves under conditions.
FIG. 6 is a heat radiation power of 35kW/m 2 In the process, the heat release rate (a) and the smoke yield (b) of the ABS and the ABS composite material in the invention are curves, and the reduction amplitude of the heat release rate (c) and the smoke yield (d) is reduced.
FIG. 7 is a digital photograph and a scanning electron micrograph of carbon residue after cone calorimetric test, ABS (a), ABS/CN2 (b), ABS/P-CN2 (c) and ABS/Ni-P-CN2 (d).
FIG. 8 is an IR spectrum of ABS/CN2, ABS/P-CN2 and ABS/Ni-P-CN2 carbon residue in the present invention.
Detailed Description
The invention will be further described with reference to the drawings and the specific preferred embodiments, but the scope of the invention is not limited thereby.
Urea, phosphorus oxychloride and sulfuric acid used in the following examples were supplied by Shanghai chemical reagent Co., ltd (Shanghai, china). Nickel nitrate hexahydrate (Ni (NO) 3 ) 3 ·6H 2 O) was purchased from shanghai alaa Ding Shenghua technologies limited (shanghai, china). ABS resin (model: DG-417) is supplied by Tianjin Dazhu chemical Co., ltd. All reagents were commercially available and used as received unless otherwise indicated.
Example 1
Ni-P-C 3 N 4 The synthesis of the nanoplatelets comprises:
the first step: block g-C 3 N 4 Is to be manufactured according to the following steps
10g of urea was placed in a covered crucible and calcined in a muffle furnace, heated to 430℃at a heating rate of 5℃per minute, incubated at 430℃for 4h, then heated to 520℃and incubated for another 4h to complete the reaction. After cooling to room temperature, pale yellow g-C is obtained by grinding 3 N 4 And (3) powder.
And a second step of: g-C 3 N 4 Stripping of nanoplatelets
1.0g of block g-C 3 N 4 The powder was stirred in 25% sulfuric acid solution for 48 hours to form a bright yellow suspension. The suspension was centrifuged at 8000 rpm for 3 minutes and the supernatant was discarded. Then, a certain amount of distilled water was added and centrifuged again, and the supernatant was removed. The above steps are repeated until the supernatant becomes neutral. Finally, the solid product is dried in a vacuum oven at 60 ℃ for 24 hours, and g-C is obtained after grinding 3 N 4 A nano-sheet.
And a third step of: phosphorus graft C 3 N 4 (P-C 3 N 4 ) Preparation of nanosheets
100ml toluene and 3g C 3 N 4 The nanoplatelets were placed in a 300ml three-necked round bottom flask and sonicated for 10 minutes. Then, 0.5g of phosphorus oxychloride and 3g of triethylamine are added and the mixture is stirred atStirred at room temperature for 30 minutes. The mixture was heated to 60 ℃ and stirred for 3 hours. Thereafter, the crude product was obtained by filtration and washed several times with ethanol. Drying at 60deg.C for 24 hr to obtain P-C 3 N 4 A nano-sheet.
Fourth step: ni/P doped C 3 N 4 (Ni-P-C 3 N 4 ) Preparation of nanosheets
Will 1g P-C 3 N 4 And 30mL of distilled water were placed in a 50mL flask and sonicated for 15 minutes 3 times. Then, an aqueous solution of nickel nitrate was added thereto and stirred for 2 hours. Filtering and collecting Ni-P-C 3 N 4 The nanoplatelets are subsequently washed with ethanol and dried at 60 ℃ for 24h.
Comparative example 1
The steps in this example include only the first and second steps of example 1, resulting in g-C 3 N 4 A nano-sheet.
Comparative example 2
The steps in this example include only the first, second and third steps of example 1, and P-C is obtained 3 N 4 A nano-sheet.
FIG. 1a shows a block g-C 3 N 4 、g-C 3 N 4 Nanoplatelets, P-C 3 N 4 And Ni-P-C 3 N 4 Is a FT-IR spectrum of (2). Block g-C 3 N 4 And g-C 3 N 4 The nanosheets are 3200 cm and 810cm -1 The position shows characteristic absorption peak, belonging to NH 2 And a triazine ring. In addition to the above absorption peaks, P-C 3 N 4 And Ni-P-C 3 N 4 Are all 1190cm -1 The p=o peak is shown, indicating g-C 3 N 4 Phosphorus doping of the nanoplatelets. FIG. 1b shows a block g-C 3 N 4 、g-C 3 N 4 Nanoplatelets, P-C 3 N 4 And Ni-P-C 3 N 4 Is a full scan spectrum of XPS of (C). Block g-C 3 N 4 Consists of carbon (43.51 wt%), nitrogen (52.07 wt%) and oxygen (4.42 wt%) elements, the presence of oxygen being due to surface oxidation in air. With block g-C 3 N 4 In contrast, g-C due to acidification 3 N 4 Oxygen content of nanoplateletsAnd (3) increasing. Notably, carbon, nitrogen, oxygen, phosphorus and nickel can be found in Ni-P-C 3 N 4 Is found in XPS spectra of (c). Ni-P-C 3 N 4 XPS spectra of high resolution C1s, N1s, O1s, P2P and Ni2P are shown in FIGS. 1C-1 g. Ni-P-C 3 N 4 The C1s spectrum of (C1 s) is divided into four peaks. The peaks at 284.72, 285.43, 288.40 and 289.35eV are attributed to C-C/C-H, C-O-C/C-OH, N-c=n and n=c (N) -NH, respectively, demonstrating g-C 3 N 4 Is present. The N1s spectrum has three peaks, each belonging to sp in the C-n=c group 2 Bonded N atom (398.76 eV), sp in N- (C) 3 structure 3 The bonded N atoms (399.53 eV) and the N atoms in the C-N-H group (400.51 eV). The O1s spectrum shows a peak of C-O-C/C-OH at 531.92 eV. In addition, the peak of P-O appears at 132.83eV, ni2P 3/2 And Ni2p 1/2 The peaks of (2) are concentrated at 856.44 and 872.11eV. Quantitative results of the XPS spectrum are shown in Table 1, and these results indicate Ni-P-C 3 N 4 Is a successful preparation of (a).
Table 1 quantitative comparison of the elements detected from XPS spectra (in wt.%)
FIGS. 1h and 1i show Ni-P-C 3 N 4 TEM and STEM-HAADF images, and corresponding elemental maps of the selected region. In Ni-P-C 3 N 4 The flaky g-C can be clearly observed in the TEM micrograph of (C) 3 N 4 And P and Ni atoms are uniformly dispersed on the surface of the sheet.
The g-C prepared by adding the above examples in ABS preparation by melt blending using a Thermo Hakker rheometer (temperature: 200 ℃ C., time: 12 minutes, rotor speed: 50 rpm) 3 N 4 、P-C 3 N 4 And Ni-P-C 3 N 4 Obtaining the ABS nanocomposite. The nanocomposite was then placed in a mold, preheated at 180 ℃ for 6 minutes, and pressed at 12MPa for 8 minutes to prepare a template for subsequent testing. Containing 0.2 and 2.0wt% g-C 3 N 4 、P-C 3 N 4 And Ni-P-C 3 N 4 The nanocomposites of (C) are denoted ABS/CN0.2, ABS/CN2, ABS/P-CN0.2, ABS/P-CN2, ABS/Ni-P-CN0.2 and ABS/Ni-P-CN2, respectively.
FIG. 2 shows TEM images of ABS/CN2 and ABS/Ni-P-CN2 composites. g-C without surface functionalization 3 N 4 The nanoplatelets tend to agglomerate in the ABS matrix, resulting in poor dispersibility (see fig. 2a and 2 b). In contrast, ni-P-C 3 N 4 Uniformly distributed in the ABS, large agglomerates are not seen (see FIG. 2C), since the Ni/P doping alters C 3 N 4 The functional groups and the molecular polarity of the surface are more beneficial to Ni-P-C 3 N 4 Dispersion in the ABS matrix. As shown in FIG. 2d, most of Ni-P-C 3 N 4 The nanoplatelets are exfoliated in a matrix as grey or black lines. Obviously, modification of phosphoric acid enhances Ni-P-C 3 N 4 Interface interaction between nano sheet and ABS, thus obviously improving Ni-P-C 3 N 4 Is a dispersion of (a) a polymer. Further investigation of functionalized g-C by XRD 3 N 4 Dispersion in ABS matrix (as in fig. 3), no g-C was found in XRD patterns of ABS/CN2, ABS/P-CN2 and ABS/Ni-P-CN2 nanocomposites 3 N 4 Characteristic diffraction peaks of nanoplatelets. This is probably due to g-C 3 N 4 Is very weak and overlaps with the peak of ABS. The above results fully demonstrate that Ni-P-C 3 N 4 The nanoplatelets are uniformly distributed in the ABS matrix.
The mechanical properties, in particular the mechanical strength, of polymer composites often determine their industrial application. Thus, g-C was studied 3 N 4 、P-C 3 N 4 And Ni-P-C 3 N 4 The effect on the mechanical properties of the ABS is shown in FIG. 4. As shown in fig. 4a and 4b, the tensile strength (σ) and elongation at break or ductility (epsilon) of pure ABS were 58.5MPa and 26.5%, respectively. When g-C 3 N 4 When the mass fraction of (C) is 2wt%, sigma of ABS/CN2 is increased by 10.2%, and epsilon is reduced by 41.9% relative to ABS. In addition, 2wt% of P-C is introduced 3 N 4 The sigma of the ABS/P-CN2 can be increased by 20.0 percent, and the epsilon can be reduced by 54.0 percent. Notably, in all samples, there was 2wt%Ni-P-C 3 N 4 The ABS/Ni-P-CN2 of (C) exhibits the highest sigma (72.7 MPa), and exhibits excellent mechanical strength. Obviously, ni/P co-doping improves Ni-P-C 3 N 4 Interfacial interactions between nanoplatelets and ABS, thus Ni-P-C 3 N 4 Can be well dispersed in a matrix and can be used as reinforcing filler of ABS. Ni-P-C 3 N 4 The outstanding reinforcing effect of (c) makes it superior to many conventional flame retardants such as halogen-based and phosphorus-based compounds.
The thermal stability of ABS and its nanocomposites was investigated by TGA technique, and the curves and data are shown in fig. 5 and table 2.
Table 2N 2 Thermal stability data of ABS and composite material thereof under atmosphere
a T i and b T max Respectively, the temperature at which 5wt% loss and maximum weight loss occur.
All ABS composites are in N 2 Shows similar degradation processes under the conditions. Initial degradation temperature of raw ABS (T i ) And a maximum mass loss temperature (T max ) 378 deg.c and 417 deg.c, respectively. Functional g-C 3 N 4 Is introduced to result in T of ABS composite material i And T max And (3) increasing. For example, T of ABS/P-CN2 i And T max The temperature is increased by 10 ℃, and the T of the ABS/Ni-P-CN2 i And T max 15℃was added. T (T) i And T max The increase in (2) is mainly due to g-C 3 N 4 Physical barrier effect of nanoplatelets on ABS thermal decomposition. Notably, T of the ABS/Ni-P-CN i And T max Are higher than both ABS/CN and ABS/P-CN because of Ni-P-C 3 N 4 The dispersibility in the ABS matrix is better. Further, the carbon residue of ABS at 600℃was only 1.47wt%. With 2.0wt% Ni-P-C 3 N 4 The carbon residue of ABS/Ni-P-CN2 increased to 5.18wt% at 600℃and was 2.5 times that of ABS. Ni-P-C 3 N 4 Promoting effect on ABS carbonization is better than g-C 3 N 4 And P-C 3 N 4 The ABS/Ni-P-CN composite material has higher carbon residue rate. It can be seen that Ni-P-C was added 3 N 4 Can simultaneously improve the thermal stability and the char formation capability of the ABS.
Cone calorimeter was used at 35kW/m 2 The fire safety of ABS and its composites was evaluated at heat irradiation power and the results are shown in fig. 6 and table 3.
TABLE 3 Cone calorimetric test results of ABS and its composites
a TTI is ignition time, PHRR is peak heat release rate, THR is total heat release, AMRR is average mass loss rate, PSPR is peak smoke release rate, TSP is total smoke release
The TTI of pure ABS was 37s, indicating that it is easily burned in fire. g-C 3 N 4 And the addition of the derivative thereof improves the TTI of the ABS composite material. It can be seen that the TTI values of ABS/Ni-P-CN0.2 and ABS/Ni-P-CN2 increased to 47 and 49 seconds, respectively. The increase in TTI is mainly due to g-C 3 N 4 Physical barrier effect of nanoplatelets. As shown in FIG. 6a and Table 3, PHRR of pure ABS is as high as 752kW/m 2 While PHRR of ABS/Ni-P-CN0.2 and ABS/Ni-P-CN2 was reduced to 620 and 508kW/m 2 Reduced by 17.6% and 32.4% relative to ABS, respectively (see fig. 6 c). Also, the THR values of ABS/Ni-P-CN0.2 and ABS/Ni-P-CN2 were 7.6% and 9.5% lower, respectively, than that of ABS. As shown in FIG. 6C, ni-P-C at the same addition amount 3 N 4 The inhibition effect on ABS exotherm is superior to g-C 3 N 4 And P-C 3 N 4 . These results indicate that g-C 3 N 4 Together, phosphorus and nickel suppress the heat release of the ABS matrix during combustion. AMLR is typically used to reflect overall fire intensity as shown in table 3. Obviously, the introduction of functional g-C 3 N 4 AMLR of the ABS composite material is reduced. After addition of 2.0wt% Ni-P-C3N4, the AMLR of the ABS/Ni-P-CN2 was reduced by 25.3% compared to ABS. In summary, ni-P-C 3 N 4 The flame retardant property of ABS is obviously improved.
Dense smoke is one of the key factors responsible for death in fire, so g-C has also been studied in detail in the present invention 3 N 4 And the effect of its derivatives on the smoke generation of the ABS matrix, the results are shown in fig. 6b and 6d and table 3. PSPR and TSP of pure ABS are up to 0.296m 2 /s and 44.2m 2 (see Table 3). Functional g-C 3 N 4 The introduction of (2) significantly reduces the fuming amount of the ABS. For example, PSPR and TSP of ABS/Ni-P-CN2 were reduced by 33.8% and 35.1%, respectively, as compared to ABS. In addition, due to P/Ni co-doping, ni-P-C 3 N 4 Exhibit a specific g-C ratio 3 N 4 And P-C 3 N 4 Better smoke suppression (see figure 6 d). Thus, ni-P-C 3 N 4 Also plays a role of smoke suppressor in the combustion process.
As can be seen, ni-P-C 3 N 4 And simultaneously improves the flame resistance, flame retardance and smoke suppression of the ABS.
The morphology and composition of carbon residue obtained from cone calorimetric test was also studied to reveal functionalized g-C 3 N 4 Influence on the carbon residue formation of the ABS matrix. FIG. 7 shows digital photographs and SEM images of carbon residue of ABS, ABS/CN2, ABS/P-CN2 and ABS/Ni-P-CN2, EDX data are shown in Table 4. After the cone calorimetric test, the raw ABS was almost burned off, leaving a small amount of brittle and broken carbon residue (see fig. 7 a). At the same time, there are many micro cracks and holes on the surface of ABS carbon residue, as shown in the SEM image in fig. 7 a. With g-C 3 N 4 And the introduction of the derivative thereof, the compactness and the continuity of the ABS charcoal are improved (see figures 7b-7 d). Particularly, the carbon residue of ABS/Ni-P-CN2 presents a continuous structure with compact surface, which is beneficial to inhibiting heat release and fuming. Therefore, the significant improvement in flame retardancy and smoke suppression of ABS/Ni-P-CN2 is mainly due to the formation of such dense continuous char.
TABLE 4 EDX data for ABS and its composite carbon residue
Table 4 lists EDX data for ABS and its composite carbon residue. The carbon and oxygen content of the pure ABS carbon residue were 68.86% and 31.14%, respectively. With 2wt% g-C 3 N 4 The C content increased to 71.64wt% and the N content reached 2.17wt%, indicating g-C 3 N 4 Mainly acts in the condensed phase to retard the decomposition of the ABS matrix. P-C 3 N 4 Substituted g-C 3 N 4 After that, the carbon content of the carbon was further increased, indicating the catalytic char formation of P. The carbon content of the ABS/Ni-P-CN2 residue is up to 77.19wt%. Meanwhile, 2.93wt% of P and 1.43wt% of Ni are contained in the carbon of ABS/Ni-P-CN2, and most of P and Ni are remained in the condensed phase, so that carbonization of the ABS matrix is promoted. FIG. 8 shows FT-IR spectra of ABS, ABS/CN2, ABS/P-CN2 and ABS/Ni-P-CN2 carbon residue. ABS carbon residue at 3440, 1600, 1260 and 970cm -1 Characteristic absorption peaks are shown, belonging to the O-H/N-H, C = C, C-O-C and C-C groups, respectively. For carbon residues of ABS/CN2, ABS/P-CN2 and ABS/Ni-P-CN2, additional peaks (-C.ident.N and-C=N) appear at 2200-2400 and 1410cm -1 Further indicates g-C 3 N 4 Remain in the coacervate phase to retard the decomposition of the matrix.
In summary, it can be seen that the invention prepares the ABS composite material with excellent flame resistance, flame retardance and smoke suppression performance by reacting g-C 3 N 4 The phosphorus and nitrogen co-doping can effectively improve the dispersivity of the polymer in ABS and pass through g-C 3 N 4 The physical barrier effect of the nano-sheet and the catalytic carbon forming effect of phosphorus and nickel elements effectively improve the heat resistance, carbonization capacity and mechanical strength of the final ABS composite material, and are beneficial to the industrial application and popularization of the final ABS composite material.
Claims (9)
1. The preparation method of the multifunctional phosphorus-nickel doped graphite-like carbon nitride nano sheet is characterized by comprising the following steps of:
1) Placing urea into a crucible with a cover, calcining in a muffle furnace, cooling to room temperature, and grinding to obtain blocky g-C 3 N 4 A powder;
2) Lump g-C 3 N 4 Stirring the powder in 25% sulfuric acid solution for at least 48 hr to form suspension, centrifuging to remove supernatant, adding distilled water, centrifuging again to remove supernatant, repeatedly adding distilled water and centrifuging until supernatant becomes neutral, drying the solid product, and grinding to obtain g-C 3 N 4 A nanosheet;
3) Toluene and g-C 3 N 4 Putting the nano-sheet into a three-neck round bottom flask, performing ultrasonic treatment for at least 10 minutes, adding phosphorus oxychloride and triethylamine, stirring at room temperature for at least 30 minutes, heating the mixture to 60 ℃, stirring for 3 hours, filtering to obtain a crude product, washing with ethanol for several times, and drying to obtain phosphorus grafting C 3 N 4 I.e. P-C 3 N 4 A nanosheet;
4) P-C 3 N 4 Dispersing the nano-sheets in distilled water, adding nickel nitrate aqueous solution after ultrasonic treatment, stirring for at least 2 hours, and filtering and collecting to obtain Ni-P-C 3 N 4 The nano-sheet is washed by ethanol and then dried.
2. The method for preparing a multifunctional phosphorus-nickel doped graphite-like carbon nitride nanosheet according to claim 1, wherein the calcination in step 1) is performed by heating to 420-450 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for 2-8 h at the temperature, heating to 510-540 ℃ and maintaining the temperature for 3-6 h to complete the reaction.
3. The method for preparing a multifunctional phosphorus-nickel doped graphite-like carbon nitride nanosheets according to claim 1, wherein the centrifugation in step 2) is performed at a rotational speed of 8000 rpm for 3 minutes.
4. The method for preparing multifunctional phosphorus-nickel doped graphite-like carbon nitride nano-sheet according to claim 1Characterized in that in step 3) toluene, g-C 3 N 4 The dosage ratio of the nanosheets, the phosphorus oxychloride and the triethylamine is 100ml to 3g to 0.5g to 3g.
5. The method for preparing the multifunctional phosphorus-nickel doped graphite-like carbon nitride nanosheets according to claim 1, wherein in step 4), P-C is 3 N 4 And nickel nitrate in the weight ratio of 100 to 3-15.
6. The method for preparing the multifunctional phosphorus-nickel doped graphite-like carbon nitride nanosheets according to claim 1, wherein the drying is: drying at 60℃for 24h.
7. Multifunctional phosphorus-nickel doped graphite-like carbon nitride nanosheets, characterized by being prepared by the method according to any one of claims 1-6.
8. An ABS nanocomposite, wherein the nanosheets of claim 7 are contained in a feedstock of the material.
9. The ABS nanocomposite of claim 8 wherein Ni-P-C of the material 3 N 4 The nano-sheet accounts for 0.1 to 15 weight percent.
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| CN202211000459.2A CN116178795A (en) | 2022-08-19 | 2022-08-19 | Multifunctional phosphorus-nickel doped graphite-like carbon nitride nano sheet, preparation method thereof and ABS material |
| PCT/CN2022/128470 WO2024036756A1 (en) | 2022-08-19 | 2022-10-30 | Multifunctional phosphorus and nickel doped graphite-like carbon nitride nanosheet, preparation method therefor, and abs material |
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| CN117484901A (en) * | 2024-01-03 | 2024-02-02 | 江苏康辉新材料科技有限公司 | Preparation method of phosphorus-modified carbon nitride flame-retardant modified BOPET film |
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| KR101640545B1 (en) * | 2015-03-27 | 2016-07-18 | 부산대학교 산학협력단 | Production method of catalyst-graphitic carbon nitride-reduced graphene oxide composite, the composite produced thereby, and an electrode using the same |
| EP3383529A4 (en) * | 2015-11-30 | 2019-11-27 | Adelaide Research And Innovation | Photocatalytic conversion of carbon dioxide and water into substituted or unsubstituted hydrocarbon(s) |
| CN105964288B (en) * | 2016-06-12 | 2018-03-06 | 常州大学 | A kind of preparation method of mesoporous carbonitride load nano nickel phosphide |
| CN108940340A (en) * | 2018-07-13 | 2018-12-07 | 启东创绿绿化工程有限公司 | A kind of g-C3N4/Ni2The preparation method of P composite material |
| CN109052344A (en) * | 2018-07-24 | 2018-12-21 | 江苏理工学院 | A kind of preparation method of graphite phase carbon nitride/nickel oxide composite material |
| CN109181207B (en) * | 2018-09-29 | 2021-01-29 | 台州学院 | Molybdenum-antimony brominated graphene oxide modified ABS composite flame-retardant material and preparation method thereof |
| CN111774084B (en) * | 2020-07-09 | 2023-02-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of phosphorus-doped carbon nitride-supported nickel efficient catalyst, product and application thereof |
| CN112588310A (en) * | 2020-12-02 | 2021-04-02 | 江苏大学 | Preparation method of visible light response nickel-phosphorized carbon nitride photocatalyst |
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| CN117484901B (en) * | 2024-01-03 | 2024-03-22 | 江苏康辉新材料科技有限公司 | Preparation method of phosphorus-modified carbon nitride flame-retardant modified BOPET film |
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