CN111621021A - Polyphosphoric acid piperazine composite flame retardant and preparation method thereof - Google Patents
Polyphosphoric acid piperazine composite flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyphosphoric acid piperazine composite flame retardant which comprises the following components in percentage by mass: 87.1 to 99.4 percent of polyphosphoric acid piperazine, 0.5 to 7.1 percent of silane coupling agent and 0.1 to 5.8 percent of antioxidant; the silane coupling agent is coated on the outer layer of polyphosphoric acid piperazine; the invention also discloses a preparation method of the polyphosphoric acid piperazine compound flame retardant, wherein phosphoric acid aqueous solution and piperazine are added into a reaction device and stirred; introducing protective gas, adding an antioxidant, raising the temperature, and performing dehydration condensation reaction to prepare polyphosphoric acid piperazine; cooling, adding a silane coupling agent, mixing and coating, and discharging; the method has the advantages of high yield, low cost and easy operation, and the polyphosphoric acid piperazine composite flame retardant prepared by the method has high whiteness, good water resistance, high flame retardant efficiency and good material compatibility.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a polyphosphoric acid piperazine composite flame retardant and a preparation method thereof.
Background
With the rapid development of Chinese economy, the consumption of the flame retardant is greatly increased, the attention degree of the Chinese government on the health and safety conditions of fire fighting and consumers is improved, the development of the flame retardant industry is facilitated, the Chinese flame retardant demand keeps 8 percent of the increase rate every year, and the market value reaches 22.45 billion dollars. Because domestic environmental protection standards and regulations are not perfect, domestic flame retardants are still mainly halogen, but with the enhancement of domestic environmental protection consciousness, the development potential of halogen-free flame retardants is huge. The halogen-free flame retardant may be phosphorus flame retardant, nitrogen flame retardant, boron flame retardant, silicon flame retardant, metal hydroxide flame retardant, intumescent flame retardant, etc. depending on the main elements contained in the flame retardant.
The phosphorus-nitrogen synergistic flame retardant is also called an Intumescent Flame Retardant (IFR), contains C, N, P as the main element, has the advantages of low smoke, low toxicity, high efficiency, environmental protection, small addition amount, good flame retardance and the like, and is widely applied in the fields of paint, rubber, wood and particularly plastics; the carbon residue layer is covered with glassy thin-layer polymetaphosphoric acid to inhibit further oxidation of the carbon layer, and the nitrogen-containing component is decomposed into ammonia gas, nitrogen gas and other nonflammable gases to dilute the flammable gases, slow down the spread of combustion and promote the formation of an expanded carbon layer.
Intumescent flame retardants can be divided into mixed intumescent flame retardants and single component intumescent flame retardants. The IFR used in the current market mainly adopts a multi-component formula taking ammonium polyphosphate (APP) with large molecular weight as an acid source, and the mixed IFR has the characteristics of wide sources of three-source components, simple composite processing technology, low cost and the like, but the proportion among the acid source, the carbon source and the gas source is extremely complex, the proportion relation among the three is difficult to control, and the systems are easy to have the phenomenon of uneven dispersion of a flame retardant in a polymer due to uneven mixing, so that the synergistic effect is not ideal, and the flame retardant efficiency is reduced or the flame retardant result is unstable, and the defects of easy moisture absorption, precipitation and the like are caused; the single-component intumescent flame retardant contains a part which can play the roles of an acid source, a carbon source and a gas source in the same molecule, has excellent moisture absorption resistance, thermal stability and compatibility, and can well overcome the problems of the multi-component flame retardant. The polyphosphoric piperazine (PPAP) is a P-N type monomolecular intumescent flame retardant obtained by reacting piperazine with other phosphorus-containing bifunctional compounds based on a phosphorus/nitrogen synergistic flame retardant principle, and is a hotspot and a key point for developing novel intumescent flame retardants at present; structurally, the polyphosphate piperazine belongs to phosphate polymers like APP, but is different from APP in that the polyphosphate piperazine is not only a good acid source but also an excellent char-forming agent and also has the function of a foaming agent; in addition, the piperazine ring structure is similar to a benzene ring, so that the piperazine ring structure has outstanding thermal stability, the piperazine chain segment is also possible to improve the interaction between the inorganic flame retardant and a polymer matrix, and the flame retardant prospect is good.
The existing preparation method of the piperazine polyphosphate flame retardant roughly comprises the following steps: 1) the double decomposition method is characterized in that sodium pyrophosphate and piperazine are used for generating a water-insoluble piperazine polyphosphate precipitate product in a hydrochloric acid solution, and the method has the problems that by-product sodium chloride or piperazine sodium pyrophosphate is generated, the yield of a target product is reduced, and the flame retardant property of the product is influenced; 2) the phosphorus pentoxide method, utilize phosphorus pentoxide, piperazine in the presence of oxalic acid through the water that oxalic acid decomposes and produces make phosphorus pentoxide produce pyrophosphoric acid, and then form salt with piperazine, this method has long reaction implementation step, and in the actual application because of the volatilization of piperazine, phosphorus pentoxide depolymerization degree is difficult to control, the temperature is slightly high causes piperazine carbonization, cause the lower problem of actual efficiency; 3) ammonium dihydrogen phosphate method, this method uses ammonium dihydrogen phosphate to replace phosphoric acid solution as the acid source to react with piperazine, ammonium dihydrogen phosphate and piperazine remove ammonia and produce the midbody first, through dehydrating the condensation reaction, thus get PPAP powder, this method has overcome the corrosion to apparatus while using liquid phosphoric acid usually with solid phosphorus source, the ammonia released in the reaction can be regarded as the protective atmosphere of the reaction system, but there is the question of exhaust emission too; 4) the method comprises the steps of firstly, reacting phosphoric acid and piperazine in solvents such as water and acetic acid to prepare intermediate piperazine diphosphate, precipitating crystals of the intermediate piperazine diphosphate, and then carrying out high-temperature dehydration condensation on the piperazine diphosphate to prepare polyphosphoric acid piperazine.
Piperazine polyphosphate has many advantages, but the current industrial production process has certain defects, and the compatibility of piperazine polyphosphate and a high polymer material system is poor, when piperazine polyphosphate is used, the piperazine polyphosphate is a powder material and is simply and physically mixed with the high polymer material, the uniformity is poor, the actual effect of a flame retardant in a formula is not fully exerted, and a migration phenomenon also exists in the use process of the material, and meanwhile, a large number of fine cracks exist in piperazine polyphosphate crystals in the synthesis process, so that the piperazine polyphosphate has the problems of moisture absorption, poor water resistance and influence on the appearance size stability of a product.
Disclosure of Invention
In view of the above problems, a first object of the present invention is to provide a piperazine polyphosphate composite flame retardant; the silane coupling agent is coated on the outer layers of the piperazine polyphosphate and the antioxidant, so that the prepared piperazine polyphosphate composite flame retardant has high whiteness, good water resistance, good flame retardant property and good material compatibility.
The second purpose of the invention is to provide the preparation method of the piperazine polyphosphate composite flame retardant, the piperazine polyphosphate is directly synthesized by adopting a one-step method, the preparation process of the piperazine polyphosphate is simplified, the yield is improved, the antioxidant is added in the step of high-temperature dehydration condensation, the problems of yellowing and low whiteness of the piperazine polyphosphate caused by high temperature are solved, and the whiteness of the product piperazine polyphosphate composite flame retardant is improved; in the method, piperazine is added to react with phosphoric acid aqueous solution, then a silane coupling agent is added to carry out coating, and the final polyphosphoric acid piperazine composite flame retardant is directly prepared from the raw material piperazine through one-time process operation; compared with the method that the raw material piperazine polyphosphate is added and the silane coupling agent is added for coating, the method directly prepares the piperazine polyphosphate composite flame retardant through the raw material piperazine by one-step process, thereby greatly reducing the production cost; moreover, the method is suitable for batch production, high in yield and easy to operate.
The first technical scheme adopted by the invention is as follows: the polyphosphoric acid piperazine composite flame retardant comprises the following components in percentage by mass: 87.1 to 99.4 percent of polyphosphoric acid piperazine, 0.5 to 7.1 percent of silane coupling agent and 0.1 to 5.8 percent of antioxidant; the silane coupling agent is coated on the outer layer of polyphosphoric acid piperazine.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP and antioxidant TNP.
Preferably, the silane coupling agent is one of vinyl silane, amino silane, epoxy silane and methacryloxy silane.
The second technical scheme adopted by the invention is as follows: the preparation method of the piperazine polyphosphate composite flame retardant comprises the following steps:
s1: adding phosphoric acid aqueous solution and piperazine into a reaction device, and stirring;
s2: introducing protective gas, adding an antioxidant, raising the temperature, and performing dehydration condensation reaction to prepare polyphosphoric acid piperazine;
s3: and cooling, adding a silane coupling agent, mixing and coating, and discharging to obtain the polyphosphoric acid piperazine composite flame retardant.
Preferably, the molar ratio of the phosphoric acid to the piperazine is 1: 1-4: 1; the mass ratio of the antioxidant to the phosphoric acid is 1: 1000-8: 100; the mass ratio of the silane coupling agent to the phosphoric acid is 1: 100-1: 5.
Preferably, the molar ratio of the phosphoric acid to the piperazine is 1.5: 1-3: 1; the mass ratio of the antioxidant to the phosphoric acid is 1: 100-6: 100; the mass ratio of the silane coupling agent to the phosphoric acid is 3: 100-3: 50.
Preferably, the phosphoric acid content of the phosphoric acid aqueous solution is more than or equal to 50 percent.
Preferably, the reaction temperature in the step S1 is 60-100 ℃, and the stirring time is 1-6 h.
Preferably, the protective gas in the step S2 is inert gas or nitrogen, the temperature is raised to 200-300 ℃, and the heat is preserved for 0.5-3 hours to prepare polyphosphoric acid piperazine.
Preferably, the temperature in step S3 is reduced to 60 ℃ to 90 ℃.
The beneficial effects of the above technical scheme are that:
(1) the piperazine polyphosphate composite flame retardant prepared by the invention can be directly used without other treatment, and is flame retardant powder which can be directly used for modified plastics.
(2) Compared with a piperazine diphosphate condensation method, the method provided by the invention has the advantages that the polyphosphoric acid piperazine is directly synthesized by a one-step method, so that the precipitation of an intermediate piperazine diphosphate is avoided, and the yield is improved; and the phosphoric acid aqueous solution is directly used for reaction, the reaction process is green and environment-friendly, and the production cost is low.
(3) According to the invention, the antioxidant is added in the high-temperature condensation dehydration reaction stage, so that the sensitivity of the intermediate product to oxygen is reduced, the problems of yellowing and low whiteness of the prepared piperazine polyphosphate under a high-temperature condition are solved, the whiteness and the competitiveness of the product piperazine polyphosphate composite flame retardant are improved, and the control difficulty of key quality indexes in the production process of the piperazine polyphosphate composite flame retardant is reduced.
(4) According to the invention, the polyphosphoric acid piperazine is obtained by directly synthesizing raw material piperazine and phosphoric acid aqueous solution, and then the polyphosphoric acid piperazine is coated by taking a silane coupling agent as a coating material, so that the water resistance of the polyphosphoric acid piperazine is improved, the flame retardant efficiency of the polyphosphoric acid piperazine is improved, and the use cost of the flame retardant is reduced.
(5) The polyphosphoric acid piperazine compound flame retardant is directly prepared from raw material piperazine through a one-step process, and the method is suitable for batch production, high in yield and easy to operate.
(6) According to the preparation method of the piperazine polyphosphate composite flame retardant disclosed by the invention, the piperazine polyphosphate composite flame retardant with high whiteness, good water resistance and good material compatibility can be directly obtained through a one-step process by using the raw material piperazine without changing the conventional synthesis production condition, so that the production cost is reduced, and the comprehensive competitiveness of the piperazine polyphosphate composite flame retardant as a composite flame retardant is enhanced.
Drawings
FIG. 1 is a flow chart of a preparation process of a piperazine polyphosphate composite flame retardant;
FIG. 2 is a reaction scheme of the piperazine polyphosphate synthesis route of the present invention;
FIG. 3 is a particle size distribution diagram of a piperazine polyphosphate composite flame retardant prepared in example 1 of the present invention;
FIG. 4 is a particle size distribution diagram of a piperazine polyphosphate composite flame retardant prepared in example 2 of the present invention;
FIG. 5 is a particle size distribution diagram of a piperazine polyphosphate composite flame retardant prepared in example 3 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, it should be noted that, for those skilled in the art, variations and modifications can be made without departing from the principle of the present invention, and these should also be construed as falling within the scope of the present invention.
The invention discloses a polyphosphoric acid piperazine composite flame retardant which comprises the following components in percentage by mass: 87.1 to 99.4 percent of polyphosphoric acid piperazine, 0.5 to 7.1 percent of silane coupling agent and 0.1 to 5.8 percent of antioxidant; the silane coupling agent is coated on the outer layer of the polyphosphoric acid piperazine.
The antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP and antioxidant TNP. The silane coupling agent is one of vinyl silane, amino silane, epoxy silane and methacryloxy silane, and the specific trade mark includes but is not limited to KH-540, KH-550, KH-560, KH-570, KH-590, A-151, A-171, A-172, Si-563 and YDH-201.
As shown in fig. 1, the piperazine polyphosphate composite flame retardant is prepared by the following steps:
s1: adding phosphoric acid aqueous solution and piperazine into a reaction device, stirring and reacting for 1-6 h at the temperature of 60-100 ℃, wherein the phosphoric acid content of the phosphoric acid aqueous solution is more than or equal to 50%; the reaction apparatus is an apparatus capable of heating and dehydrating, such as an extruder, a kneader, a mixer, etc.
S2: introducing inert gas or nitrogen, adding an antioxidant, raising the temperature to 200-300 ℃ for dehydration condensation reaction, and keeping the temperature for 0.5-3 h to prepare polyphosphoric acid piperazine; the reaction formula of the piperazine polyphosphate synthetic route is shown in figure 2.
S3: cooling to 60-90 ℃, adding a silane coupling agent, mixing and coating uniformly, cooling to room temperature, and discharging; and continuously carrying out three steps of reactions to obtain the polyphosphoric acid piperazine composite flame retardant.
The molar ratio of the phosphoric acid to the piperazine is 1: 1-4: 1, preferably 1.5: 1-3: 1; the mass ratio of the antioxidant to the phosphoric acid is 1: 1000-8: 100, preferably 1: 100-6: 100; the mass ratio of the silane coupling agent to the phosphoric acid is 1: 100-1: 5, preferably 3: 100-3: 50.
The prepared piperazine polyphosphate composite flame retardant is characterized by comprising the following components in parts by weight:
1) particle size
And detecting the particle size of the prepared piperazine polyphosphate composite flame retardant by using a laser particle sizer.
2) Whiteness degree
And (3) performing whiteness detection on the prepared piperazine polyphosphate composite flame retardant by adopting a whiteness measuring instrument.
3) Water resistance
The water resistance detection is carried out according to the solubility of the product in water, specifically, products to be detected with different masses are added into 100mL of water, and the greater the mass of each product to be detected dissolved in 100mL of water is, namely the greater the solubility is, the poorer the water resistance is.
Example 1
860g of piperazine and 1960g of 50% phosphoric acid aqueous solution are added into a 5L kneader, after the reaction is carried out for 1 hour at the temperature of 60 ℃, nitrogen is introduced for protection, 1.9g of antioxidant 1010 is added, the temperature is raised to 200 ℃ for dehydration condensation reaction for 0.5 hour, then the temperature is reduced to 90 ℃, 9.8g of silane coupling agent KH-550 is added, the stirring and mixing are continued for 1 hour, the temperature is reduced to room temperature, and then the material is discharged, so that 1.58kg of piperazine polyphosphate composite flame retardant is obtained, wherein the yield is 95%.
The polyphosphoric acid piperazine composite flame retardant prepared by the embodiment comprises the following components in percentage by mass: 99.4% of polyphosphoric acid piperazine, 0.5% of silane coupling agent and 0.1% of antioxidant.
The water resistance is 0.02g/(100mL of water); the whiteness was 97.
The particle size of the prepared piperazine polyphosphate composite flame retardant was measured by a laser particle sizer, the measurement results are shown in table 1, and the particle size of the product D509.432 μm, D90The particle size distribution of the piperazine polyphosphate composite flame retardant is 34.317 mu m, and is shown in figure 3.
TABLE 1 particle size of piperazine polyphosphate composite flame retardants
| Particle size distribution | D10 | D25 | D50 | D75 | D90 |
| Particle size | 2.706μm | 5.024μm | 9.432μm | 19.967μm | 34.317μm |
Example 2
Adding 8.6kg of piperazine and 26.1kg of 75% phosphoric acid aqueous solution into a 50L kneader, reacting for 3 hours at the temperature of 80 ℃, introducing nitrogen for protection, adding 320g of antioxidant 1076 and 200g of antioxidant 168, raising the temperature to 260 ℃ for dehydration condensation reaction for 2 hours, then reducing the temperature to 80 ℃, adding 1305g of silane coupling agent KH-590, continuously stirring and mixing for 1 hour, reducing the temperature to room temperature, and discharging to obtain 27.6kg of polyphosphoric acid piperazine composite flame retardant with the yield of 97%.
The polyphosphoric acid piperazine composite flame retardant prepared by the embodiment comprises the following components in percentage by mass: 94% of polyphosphoric acid piperazine, 4.3% of silane coupling agent and 1.7% of antioxidant.
The water resistance is 0.01g/(100mL of water); the whiteness was 98.
The particle size of the prepared piperazine polyphosphate composite flame retardant was measured by a laser particle sizer, the measurement results are shown in table 2, and the particle size of the product D5010.435 μm, D90The particle size distribution of the piperazine polyphosphate composite flame retardant is 20.812 mu m, and is shown in figure 4.
TABLE 2 particle size of piperazine polyphosphate composite flame retardants
| Particle size distribution | D10 | D25 | D50 | D75 | D90 |
| Particle size | 4.164μm | 6.847μm | 10.435μm | 15.264μm | 20.812μm |
Example 3
Adding 86kg of piperazine and 522kg of 75% phosphoric acid aqueous solution into a 1000L kneader, reacting for 6 hours at the temperature of 100 ℃, introducing nitrogen for protection, adding 25kg of antioxidant 1010 and 7kg of antioxidant DLTDP, raising the temperature to 300 ℃ for dehydration condensation reaction for 3 hours, then reducing the temperature to 60 ℃, adding 39kg of silane coupling agent A-172, continuously stirring and mixing for 1 hour, cooling to room temperature, and discharging to obtain 521kg of polyphosphoric acid piperazine composite flame retardant, wherein the yield is 98%.
The polyphosphoric acid piperazine composite flame retardant prepared by the embodiment comprises the following components in percentage by mass: 87.1% of polyphosphoric acid piperazine, 7.1% of silane coupling agent and 5.8% of antioxidant.
The water resistance is 0.01g/(100mL of water); the whiteness was 98.
The particle size of the prepared piperazine polyphosphate composite flame retardant was measured by a laser particle sizer, the measurement results are shown in table 3, and the particle size of the product D5011.643 μm, D90The particle size distribution of the piperazine polyphosphate composite flame retardant is 34.285 μm, and is shown in FIG. 5.
TABLE 3 particle size of piperazine polyphosphate composite flame retardants
| Particle size distribution | D10 | D25 | D50 | D75 | D90 |
| Particle size | 3.506μm | 6.369μm | 11.643μm | 21.200μm | 34.285μm |
Comparative example 1
Adding 8.6kg of piperazine and 26.1kg of 75% phosphoric acid aqueous solution into a 50L kneader, reacting for 3 hours at the temperature of 80 ℃, introducing nitrogen for protection, adding 320g of antioxidant 1076 and 200g of antioxidant 168, raising the temperature to 260 ℃ for dehydration condensation reaction for 2 hours, and then reducing the temperature to 80 ℃ to obtain 28.1 kg of polyphosphoric acid piperazine; the yield is 98%, and the whiteness is 98; the water resistance was 0.5g/(100mL of water).
Comparative example 2
Adding 8.6kg of piperazine and 26.1kg of 75% phosphoric acid aqueous solution into a 50L kneader, reacting for 3 hours at the temperature of 80 ℃, introducing nitrogen for protection, raising the temperature to 260 ℃ for dehydration condensation reaction for 2 hours, and then reducing the temperature to 80 ℃ to obtain polyphosphoric acid piperazine; the whiteness is 81; the water resistance was 0.5g/(100mL of water).
Comparative example 3
According to the comparative example, piperazine diphosphate is prepared by a piperazine diphosphate condensation method, nitrogen is introduced into a 500mL five-necked bottle for protection, 115.3g of phosphoric acid solution is added, 43.1g of anhydrous piperazine is added into a 250mL beaker, water is added for complete dissolution, the anhydrous piperazine is slowly dropped into a reaction vessel for reaction at 85 ℃ for 2 hours, after the reaction is finished, the reaction solution is cooled to room temperature, products are filtered, then the product is washed by deionized water and dried, 133.24g of intermediate piperazine diphosphate is obtained, and the yield is 94.5%. Then the obtained intermediate is put into a kneader to be kneaded and dehydrated at high temperature, dehydration polycondensation reaction is carried out for 1h at 230 ℃, cooling is carried out to room temperature, 121.51g of polyphosphoric acid piperazine is obtained, and wastewater is treated. The yield of piperazine polyphosphate was 92.1%. The comprehensive yield of the two-step method is 87.03 percent, and the whiteness is 92; the water resistance was 0.5g/(100mL of water).
Comparative test of flame retardancy
Selecting 100g of a flame retardant basic formula (80g of polypropylene and 20g of an auxiliary flame retardant), and setting an experimental group and a control group, wherein the experimental group is that 20g of the polyphosphoric acid piperazine composite flame retardant prepared in the embodiment 1-3 is added into 100g of the flame retardant basic formula (coated by a silane coupling agent) respectively, and an experimental group test sample strip 1, an experimental group test sample strip 2 and an experimental group test sample strip 3 are correspondingly prepared; in the control group, 20g of polyphosphoric acid piperazine (without silane coupling agent coating) prepared in comparative examples 1-3 is added into 100g of flame retardant basic formula respectively, and a control group test sample strip 1, a control group test sample strip 2 and a control group test sample strip 3 are correspondingly prepared; and (4) carrying out flame retardant property test on the prepared experimental group test sample strips and the prepared comparison group test sample strips. The test results are shown in Table 4.
TABLE 4 test results of flame retardancy of test sample strips of experimental group and test sample strips of control group
| Numbering | Limiting oxygen index |
| Experimental group test specimen 1 (coated with silane coupling agent) | 28.0％ |
| Experimental group test specimen bar 2 (coated with silane coupling agent) | 29.0％ |
| Experimental group test specimen No. 3 (coated with silane coupling agent) | 29.0％ |
| Control test specimen 1 (not coated with silane coupling agent) | 27.0％ |
| Control test specimen 2 (not coated with silane coupling agent) | 27.0％ |
| Control test specimen 3 (uncoated with silane coupling agent) | 26.0％ |
In comparative example 1, the antioxidant is added in the high-temperature condensation dehydration reaction stage, and in comparative example 2, the antioxidant is not added in the high-temperature condensation dehydration reaction stage, and as can be seen from the comparison between comparative example 1 and comparative example 2, the whiteness (98) of the piperazine polyphosphate prepared by comparative example 1 is greater than the whiteness (81) of the piperazine polyphosphate prepared by comparative example 2; therefore, the whiteness of the polyphosphoric acid piperazine is improved by adding the antioxidant in the high-temperature condensation dehydration reaction stage.
In the example 2, the prepared polyphosphoric acid piperazine is coated by a silane coupling agent, and in the comparative example 1, the step of coating by the silane coupling agent is not added; as is clear from comparison between example 2 and comparative example 1, the water resistance (0.01g/100mL) of the piperazine polyphosphate composite flame retardant prepared in example 2 is better than that (0.5g/100mL) of the piperazine polyphosphate prepared in comparative example 1 (the larger the value of the water resistance, the worse the water resistance is shown), and thus it can be seen that the water resistance of the piperazine polyphosphate is improved after being coated with the silane coupling agent.
Compared with the piperazine diphosphate condensation method, the method disclosed by the invention has the advantages that the polyphosphoric acid piperazine is directly synthesized by adopting a one-step method, so that the precipitation of intermediate piperazine diphosphate is avoided, and the yield is improved.
As can be seen from Table 4, the flame retardant property of the polyphosphoric acid piperazine is improved after the coating of the silane coupling agent.
Compared with a piperazine diphosphate condensation method, the method provided by the invention has the advantages that the polyphosphoric acid piperazine is directly synthesized by a one-step method, so that the precipitation of an intermediate piperazine diphosphate is avoided, and the yield is improved; and the phosphoric acid aqueous solution is directly used for reaction, the reaction process is green and environment-friendly, and the production cost is low. According to the invention, the antioxidant is added in the high-temperature condensation dehydration reaction stage, so that the sensitivity of the intermediate product to oxygen is reduced, the problems of yellowing and low whiteness of the prepared piperazine polyphosphate under a high-temperature condition are solved, the whiteness and the competitiveness of the product piperazine polyphosphate composite flame retardant are improved, and the control difficulty of key quality indexes in the production process of the piperazine polyphosphate composite flame retardant is reduced.
According to the invention, the polyphosphoric acid piperazine is obtained by directly synthesizing raw material piperazine and phosphoric acid aqueous solution, and then the polyphosphoric acid piperazine is coated by taking a silane coupling agent as a coating material, so that the water resistance of the polyphosphoric acid piperazine is improved, the flame retardant efficiency of the polyphosphoric acid piperazine is improved, and the use cost of the flame retardant is reduced. The polyphosphoric acid piperazine composite flame retardant is directly prepared from raw material piperazine through a one-step process, so that the production cost is greatly reduced; moreover, the method is suitable for batch production, high in yield and easy to operate.
According to the preparation method of the piperazine polyphosphate composite flame retardant disclosed by the invention, the piperazine polyphosphate composite flame retardant with high whiteness, good water resistance and good material compatibility can be directly obtained through a one-step process by using the raw material piperazine without changing the conventional synthesis production condition, so that the production cost is reduced, and the comprehensive competitiveness of the piperazine polyphosphate composite flame retardant as a composite flame retardant is enhanced. The piperazine polyphosphate composite flame retardant prepared by the invention can be directly used without other treatment, and is flame retardant powder which can be directly used for modified plastics.
Claims (10)
1. The piperazine polyphosphate composite flame retardant is characterized by comprising the following components in percentage by mass: 87.1 to 99.4 percent of polyphosphoric acid piperazine, 0.5 to 7.1 percent of silane coupling agent and 0.1 to 5.8 percent of antioxidant; the silane coupling agent is coated on the outer layer of polyphosphoric acid piperazine.
2. The piperazine polyphosphate composite flame retardant according to claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP and antioxidant TNP.
3. The piperazine polyphosphate composite flame retardant according to claim 1, wherein the silane coupling agent is one of vinyl silane, amino silane, epoxy silane and methacryloxy silane.
4. The preparation method of the piperazine polyphosphate composite flame retardant is characterized by comprising the following steps:
s1: adding phosphoric acid aqueous solution and piperazine into a reaction device, and stirring;
s2: introducing protective gas, adding an antioxidant, raising the temperature, and performing dehydration condensation reaction to prepare polyphosphoric acid piperazine;
s3: and cooling, adding a silane coupling agent, mixing and coating, and discharging to obtain the polyphosphoric acid piperazine composite flame retardant.
5. The preparation method of the piperazine polyphosphate composite flame retardant according to claim 4, wherein the molar ratio of phosphoric acid to piperazine is 1: 1-4: 1; the mass ratio of the antioxidant to the phosphoric acid is 1: 1000-8: 100; the mass ratio of the silane coupling agent to the phosphoric acid is 1: 100-1: 5.
6. The preparation method of the piperazine polyphosphate composite flame retardant according to claim 5, wherein the molar ratio of phosphoric acid to piperazine is 1.5: 1-3: 1; the mass ratio of the antioxidant to the phosphoric acid is 1: 100-6: 100; the mass ratio of the silane coupling agent to the phosphoric acid is 3: 100-3: 50.
7. The preparation method of the piperazine polyphosphate composite flame retardant according to claim 4, wherein the phosphoric acid content of the phosphoric acid aqueous solution is not less than 50%.
8. The preparation method of the piperazine polyphosphate composite flame retardant according to claim 4, wherein the reaction temperature in the step S1 is 60-100 ℃, and the stirring time is 1-6 hours.
9. The preparation method of the piperazine polyphosphate composite flame retardant according to claim 4, wherein the protective gas in the step S2 is inert gas or nitrogen, the temperature is raised to 200-300 ℃, and the heat is preserved for 0.5-3 h to prepare the piperazine polyphosphate.
10. The preparation method of the piperazine polyphosphate composite flame retardant according to claim 4, wherein the temperature is reduced to 60-90 ℃ in the step S3.
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