CN113214116B - Preparation of phosphorus-nitrogen type flame retardant and application of phosphorus-nitrogen type flame retardant in anti-aging flame-retardant composite material - Google Patents
Preparation of phosphorus-nitrogen type flame retardant and application of phosphorus-nitrogen type flame retardant in anti-aging flame-retardant composite material Download PDFInfo
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- CN113214116B CN113214116B CN202110499435.5A CN202110499435A CN113214116B CN 113214116 B CN113214116 B CN 113214116B CN 202110499435 A CN202110499435 A CN 202110499435A CN 113214116 B CN113214116 B CN 113214116B
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Abstract
The invention discloses a preparation method of a phosphorus-nitrogen flame retardant and application of the phosphorus-nitrogen flame retardant in an anti-aging flame-retardant composite material. Mixing creatine monohydrate, urea and phosphoric acid solution, stirring in an oil bath for reaction, and naturally cooling to room temperature to obtain a solution after reaction; and pouring the solution after the reaction into absolute ethyl alcohol to generate a flocculent product, centrifuging and washing for multiple times, and drying to obtain the phosphorus-nitrogen flame retardant. Dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol solution; mixing the fluorescent powder, creatine monohydrate and polyvinyl alcohol solution, and uniformly stirring to obtain a dispersion system; drying at room temperature to obtain the anti-aging flame-retardant polyvinyl alcohol composite material. The preparation method has the advantages of cheap raw materials and simple process, and is suitable for large-scale industrial production. The prepared anti-aging flame-retardant polyvinyl alcohol composite material does not change the transparency of the original polyvinyl alcohol, and can be widely applied to the field of decoration.
Description
Technical Field
The invention belongs to the technical field of flame retardance, and relates to a preparation method of a novel phosphorus-nitrogen flame retardant; the invention also relates to the application of the flame retardant prepared by the preparation method and the fluorescent powder which can be effectively excited by ultraviolet and near ultraviolet in the anti-aging flame-retardant polyvinyl alcohol composite material.
Background
The organic polymer material which is easy to process and low in cost is widely applied to various fields, but the organic polymer material is extremely easy to burn, and greatly threatens the life and property safety of human beings. Meanwhile, organic polymers are easy to age under the action of ultraviolet light, often causing adverse effects such as premature failure of instruments and equipment, large loss of materials and the like, so that economic loss and resource waste are caused, and the environment is polluted by the failure decomposition of the materials. To solve these problems, flame retardants and ultraviolet absorbers are generally added to organic polymer materials.
At present, the most common method for improving the flame retardant property and the aging resistance of the organic polymer material is to add a flame retardant and an ultraviolet absorbent into a polymer matrix. Common flame retardants include halogen flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, metal hydroxide flame retardants, and the like. Among various flame retardants, the halogen flame retardant has a good effect, but generates toxic carcinogenic substances when burned, generates a large amount of smoke and corrosive gases, and is liable to cause environmental damage. Most countries have therefore gradually banned the use of halogen-containing flame retardants.
The common absorbent is TiO 2 ZnS, etc., TiO 2 And ZnS has better ultraviolet absorption performance, but generates holes with strong oxidizing property and photo-generated electrons with strong reducing property after absorbing ultraviolet rays, and the holes and the electrons can react with O 2 、H 2 And O and other substances react to generate free radicals with high chemical activity, and the free radicals can react with the high polymer material to break chemical bonds among molecules, reduce the performance of the high polymer material and finally cause the decomposition of the high polymer material. Therefore, the design and development of environment-friendly halogen-free flame retardant and aging-resistant flame retardant polymer are urgent.
Creatine monohydrate (creatine monohydrate) is a nitrogen-rich organic acid naturally existing in vertebrate bodies, has wide sources and low price, can be produced on a large scale in industry, but is never applied to the field of flame retardance.
The fluorescent powder can effectively absorb ultraviolet light and near ultraviolet light and convert the ultraviolet light and the near ultraviolet light into other visible light, so that the aging resistance of the material is improved. The aging-resistant polyvinyl alcohol composite material can be prepared by adding the fluorescent powder into polyvinyl alcohol.
Disclosure of Invention
The invention aims to provide a preparation method of a phosphorus-nitrogen flame retardant which does not contain halogen, is environment-friendly and has excellent flame retardant performance.
The invention also aims to provide application of the phosphorus-nitrogen flame retardant prepared by the preparation method in an anti-aging flame-retardant polyvinyl alcohol composite material.
The technical scheme adopted by the invention is as follows: a preparation method of a phosphorus-nitrogen flame retardant specifically comprises the following steps:
1) taking creatine monohydrate and urea respectively according to the mass ratio of 1: 2-5, and taking a phosphoric acid solution according to the proportion that 1g of creatine monohydrate needs to be 30-50 mL of a phosphoric acid solution with the mass fraction of 80-90%; mixing creatine monohydrate, urea and phosphoric acid solution, stirring and reacting for 2-10 h at the oil bath temperature of 110-150 ℃ at the rotating speed of 400-500 rpm, and naturally cooling to room temperature to obtain reacted solution;
2) and (2) respectively taking the reacted solution and absolute ethyl alcohol according to the volume ratio of 2-3: 5, pouring the reacted solution into the absolute ethyl alcohol to generate a white flocculent product, carrying out multiple centrifugal washing by using ethanol or acetone, and drying for 10 hours in an environment at the temperature of 60 ℃ to obtain the phosphorus-nitrogen flame retardant (phosphocreatine monohydrate).
The other technical scheme adopted by the invention is as follows: an application method of the phosphorus-nitrogen flame retardant prepared by the preparation method in anti-aging flame-retardant polyethylene. The method specifically comprises the following steps:
1) respectively taking polyvinyl alcohol and deionized water according to the mass ratio of 1: 20-25, dissolving the polyvinyl alcohol in the deionized water, heating to 90-95 ℃, and stirring for 3-4 hours to obtain a polyvinyl alcohol solution;
2) respectively taking fluorescent powder Sr according to the mass ratio of 1: 2-4: 515-517 8 CaBi(PO 4 ) 7 ：Eu 2+ (ii) a (Zhang Qiang, Wang Xicheng, Ding Xin, etc.. A bouad band yellow-emitting Sr 8 CaBi(PO 4 ) 7 :Eu 2+ phosphor for n-UV pumped white light emitting devices[J]DYES AND PIGMENTS, 2017, 149(2): 268-275), the phosphorus-nitrogen flame retardant and the polyvinyl alcohol solution are mixed and stirred evenly to obtain a dispersion system;
3) and drying the dispersion system at room temperature to obtain the anti-aging flame-retardant polyvinyl alcohol composite material.
The creatine monohydrate is used as a biological base material rich in nitrogen elements, is green and environment-friendly, avoids the high pollution problem caused by a halogen flame retardant, and has wide application prospect in the flame retardant field. The preparation method of the invention performs phosphorylation reaction on creatine monohydrate to synthesize a novel phosphorus-nitrogen type flame retardant, and the flame retardant and fluorescent powder are added into polyvinyl alcohol together to prepare the anti-aging flame-retardant polyvinyl alcohol composite material. The compounding of the inorganic fluorescent powder and the organic flame retardant has more excellent flame retardant effect.
The combustion of the phosphorylated creatine monohydrate produces phosphorus-containing compounds that accelerate coke formation, thereby forming a char layer that effectively blocks the exchange of energy and materials between the polymer and the flame, acting as a physical barrier. Secondly, a large amount of nitrogen-containing non-combustible gas can be generated by the combustion of the phosphorylated creatine monohydrate, and the concentration of the combustible gas and the concentration of oxygen can be diluted by a large amount of the non-combustible gas, so that the flame retardant effect is achieved. The phosphocreatine monohydrate has good flame retardant effect, simple synthesis and low cost, and does not generate corrosive gas; provides more choices for selecting flame retardant raw materials in the future.
On the other hand, the flame retardant and the fluorescent powder prepared by the preparation method are added into a polyvinyl alcohol solution to prepare the anti-aging flame-retardant polyvinyl alcohol composite material, and the fluorescent powder can effectively absorb ultraviolet rays with the wavelength of 200-400 nm and convert the ultraviolet rays into visible light, so that the anti-aging performance of polyvinyl alcohol is enhanced; prevent the polymer from degrading and achieve the effect of aging resistance.
The prepared anti-aging flame-retardant polyvinyl alcohol composite material does not change the transparency of the original polyvinyl alcohol, and can be widely applied to the field of decoration.
The preparation method has the advantages of cheap raw materials and simple process, and is suitable for large-scale industrial production.
Drawings
Fig. 1a is an SEM image of creatine monohydrate; FIG. 1b is an SEM image of phosphocreatine monohydrate prepared by the preparation method of the present invention.
FIG. 2 is a FTIR plot of creatine monohydrate and phosphorus-nitrogen flame retardant prepared by the preparation method of the present invention in the prior art.
FIG. 3 shows a phosphor Sr in the prior art 8 CaBi(PO 4 ) 7 ：Eu 2+ The excitation spectrum of (1).
FIG. 4 is a DRS graph of a polyvinyl alcohol solid material prepared in comparative example 1 and an aging-resistant flame-retardant polyvinyl alcohol composite prepared in example 1.
FIG. 5 is a graph showing the vertical burning results of the aging-resistant and flame-retardant polyvinyl alcohol composite materials prepared in examples 1 to 3.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1
Pouring 1g of creatine monohydrate, 5g of urea and 30mL of phosphoric acid solution with the mass fraction of 80% into a container, stirring at the oil bath temperature of 110 ℃ and the rotating speed of 400rpm for 2 hours, and naturally cooling to room temperature to obtain a solution after reaction; respectively taking the reacted solution and absolute ethyl alcohol according to the volume ratio of 2: 3, pouring the reacted solution into the absolute ethyl alcohol to generate a white flocculent product, centrifuging and washing the white flocculent product by using the ethyl alcohol for multiple times, and drying the white flocculent product for 10 hours in an environment with the temperature of 60 ℃ to obtain the phosphorus-nitrogen flame retardant (phosphocreatine monohydrate).
Respectively taking polyvinyl alcohol and deionized water according to the mass ratio of 1: 20, dissolving the polyvinyl alcohol in the deionized water, heating to 90 ℃, and stirring for 4 hours to obtain a polyvinyl alcohol solution; respectively collecting fluorescent powder (Sr) at a mass ratio of 1: 2: 515 8 CaBi(PO 4 ) 7 ：Eu 2+ ) The phosphorylated creatine monohydrate and the polyvinyl alcohol solution are uniformly stirred to obtain a dispersion system; and drying the dispersion system at room temperature to obtain the anti-aging flame-retardant polyvinyl alcohol composite material.
Example 2
2g of creatine monohydrate solid, 7g of urea and 40mL of phosphoric acid solution with the mass fraction of 90% are taken and poured into a container, stirred for 6 hours at the rotating speed of 500rpm under the condition of 130 ℃ oil bath, and naturally cooled to room temperature to obtain the solution after reaction. Respectively taking the reacted solution and absolute ethyl alcohol according to the volume ratio of 3: 5, pouring the reacted solution into the absolute ethyl alcohol to generate a white flocculent product, centrifuging and washing the white flocculent product by using acetone for multiple times, and drying the white flocculent product for 10 hours in an environment at the temperature of 60 ℃ to obtain the phosphorus-nitrogen flame retardant (phosphocreatine monohydrate).
Respectively taking polyvinyl alcohol and deionized water according to the mass ratio of 1: 25, dissolving the polyvinyl alcohol in the deionized water, heating to 95 ℃, and stirring for 3 hours to obtain a polyvinyl alcohol solution; respectively collecting fluorescent powder (Sr) at a mass ratio of 1: 4: 517 8 CaBi(PO 4 ) 7 ：Eu 2+ ) The phosphorylated creatine monohydrate and the polyvinyl alcohol solution are uniformly stirred to obtain a dispersion system; and drying the dispersion system at room temperature to obtain the anti-aging flame-retardant polyvinyl alcohol composite material.
Example 3
Pouring 1.5g of creatine monohydrate solid, 7.5g of urea and 50mL of phosphoric acid into a container, stirring at the rotating speed of 450rpm for 10 hours under the condition of 150 ℃ oil bath, and naturally cooling to room temperature to obtain a solution after reaction; respectively taking the reacted solution and absolute ethyl alcohol according to the volume ratio of 2.5: 5, pouring the reacted solution into the absolute ethyl alcohol to generate a white flocculent product, carrying out multiple centrifugal washing by using ethanol or acetone, and drying for 10 hours in an environment at the temperature of 60 ℃ to obtain the phosphorus-nitrogen flame retardant (phosphocreatine monohydrate).
Respectively taking polyvinyl alcohol and deionized water according to the mass ratio of 1: 22.5, dissolving the polyvinyl alcohol in the deionized water, heating to 92.5 ℃, and stirring for 3.5 hours to obtain a polyvinyl alcohol solution; respectively collecting fluorescent powder (Sr) at a mass ratio of 1: 3: 516 8 CaBi(PO 4 ) 7 ：Eu 2 + ) The phosphorylated creatine monohydrate and the polyvinyl alcohol solution are uniformly stirred to obtain a dispersion system; and drying the dispersion system at room temperature to obtain the anti-aging flame-retardant polyvinyl alcohol composite material.
Comparative example 1
Weighing 4g of polyvinyl alcohol, pouring the polyvinyl alcohol into 100mL of deionized water, heating to 90 ℃, reacting for 2h, uniformly stirring, pouring the solution into a fixed mold, and drying at room temperature to obtain the polyvinyl alcohol solid material.
The results of the flame retardant property test of the polyvinyl alcohol solid material prepared in comparative example 1, and the polyvinyl alcohol composite materials prepared in example 1, example 2 and example 3 are shown in tables 1 and 2.
Table 1 UL-94 and limiting oxygen index measurements for materials
TABLE 2 Heat Release Rate and Total Release of materials
From the results of the UL-94 and limiting oxygen index measurements in Table 1, the UL-94 rating of the pure polyvinyl alcohol prepared in comparative example 1 is NR, and there is no flame retardant effect. The UL-94 grade of the flame-retardant polyvinyl alcohol composite material prepared in the embodiments 1-3 reaches the V-0 grade, which shows that the flame-retardant polyvinyl alcohol composite material prepared by adding the phosphorus-nitrogen flame retardant prepared by the preparation method of the invention into polyvinyl alcohol has good flame-retardant performance.
As can be observed from Table 2, the maximum heat release rate of the polyvinyl alcohol solid material prepared in comparative example 1 is 813 (W/g), while the maximum heat release rates of the aging-resistant and flame-retardant polyvinyl alcohol composite materials prepared in examples 1-3 after adding flame retardants with different addition amounts are greatly reduced, and the maximum heat release rate is reduced by 77%; the maximum reduction of the total heat release is 35 percent, which shows that the anti-aging flame-retardant polyvinyl alcohol prepared by the invention has good flame-retardant property.
Creatine monohydrate (fig. 1 a) and phosphocreatine monohydrate (fig. 1 b) in the prior art have different morphologies. As can be seen in FIG. 2, synthetic phosphocreatine monohydrate is found at 2362cm -1 、1403cm -1 、987cm -1 、496cm -1 Produce a new peak at 2362cm -1 Is caused by vibration of P-H, 1403cm -1 And 987cm -1 Peak at 1255cm due to vibration of P-N -1 Is due to vibration of P = O, 496cm -1 The peak is caused by P-O vibration, and the results can show that the preparation method successfully synthesizes the phosphocreatine monohydrate.
FIG. 3 shows phosphor Sr in the prior art 8 CaBi(PO 4 ) 7 ：Eu 2+ The excitation spectrogram can observe that the fluorescent powder shows 240-500 nm broadband excitation under the monitoring of 606nm, which shows that the fluorescent powder has obvious absorption in the 240-500 nm region. FIG. 4 is a DRS diagram of the polyvinyl alcohol solid material prepared in comparative example 1 and the aging-resistant and flame-retardant polyvinyl alcohol composite material prepared in example 1, and it can be observed that the light transmitted by the aging-resistant and flame-retardant polyvinyl alcohol composite material is less in the range of 200-400 nm, especially in the vicinity of 250nm, which indicates that the ultraviolet ray in the region is absorbed by the fluorescent powder in the aging-resistant and flame-retardant polyvinyl alcohol composite material, so that the damage of the ultraviolet ray on the service life of the polyvinyl alcohol can be reduced, and the aging resistance can be improved. The results of the vertical burning test of the aging resistant flame retardant polyvinyl alcohol composites prepared in example 1, example 2 and example 3 are shown in fig. 5. The figure shows that the aging-resistant flame-retardant polyvinyl alcohol composite material after combustion has a compact carbon layer, and can effectively prevent further combustion of the matrix. The phosphorylation creatine monohydrate prepared by the preparation method has good flame retardant effect, and the prepared aging-resistant flame-retardant polyvinyl alcohol has good flame retardant and aging resistance.
Claims (4)
1. The preparation method of the phosphorus-nitrogen flame retardant is characterized by comprising the following steps:
1) taking creatine monohydrate and urea respectively according to the mass ratio of 1: 2-5, and taking a phosphoric acid solution according to the proportion that 1g of creatine monohydrate needs 30-50 mL of phosphoric acid solution; mixing creatine monohydrate, urea and phosphoric acid solution, stirring and reacting for 2-10 hours at the oil bath temperature of 110-150 ℃, and naturally cooling to room temperature to obtain a reacted solution;
2) and (3) respectively taking the reacted solution and absolute ethyl alcohol according to the volume ratio of 2-3: 5, pouring the reacted solution into the absolute ethyl alcohol to generate a flocculent product, centrifuging and washing for multiple times, and drying to obtain the phosphorus-nitrogen flame retardant.
2. The method for preparing a phosphorus-nitrogen type flame retardant according to claim 1, wherein the phosphoric acid solution is 80 to 90 mass%.
3. The method of claim 1, wherein in the step 2), after the flocculent product is generated, the flocculent product is washed by centrifugation with ethanol or acetone for a plurality of times.
4. The application of the phosphorus-nitrogen flame retardant prepared by the preparation method of the phosphorus-nitrogen flame retardant disclosed by claim 1 in an aging-resistant flame-retardant composite material is characterized in that the preparation of the phosphorus-nitrogen flame retardant comprises the following steps:
1) taking creatine monohydrate and urea respectively according to the mass ratio of 1: 2-5, and taking a phosphoric acid solution according to the proportion that 1g of creatine monohydrate needs 30-50 mL of phosphoric acid solution; mixing creatine monohydrate, urea and phosphoric acid solution, stirring and reacting for 2-10 hours at the oil bath temperature of 110-150 ℃, and naturally cooling to room temperature to obtain a reacted solution;
2) respectively taking the reacted solution and absolute ethyl alcohol according to the volume ratio of 2-3: 5, pouring the reacted solution into the absolute ethyl alcohol to generate a flocculent product, centrifuging and washing for multiple times, and drying to obtain the phosphorus-nitrogen flame retardant;
the application of the phosphorus-nitrogen flame retardant in the anti-aging flame-retardant composite material specifically comprises the following steps:
1) respectively taking polyvinyl alcohol and deionized water according to the mass ratio of 1: 20-25, dissolving the polyvinyl alcohol in the deionized water, heating to 90-95 ℃, and stirring for 3-4 hours to obtain a polyvinyl alcohol solution;
2) respectively taking the phosphor powder Sr according to the mass ratio of 1: 2-4: 515-517 8 CaBi(PO 4 ) 7 ：Eu 2+ Uniformly stirring the phosphorus-nitrogen flame retardant and the polyvinyl alcohol solution to obtain a dispersion system; drying at room temperature to obtain the aging-resistant flame-retardant composite material.
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