CN117820681A - Preparation method of P/benzene/Si flame-retardant system composite powder - Google Patents
Preparation method of P/benzene/Si flame-retardant system composite powder Download PDFInfo
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- CN117820681A CN117820681A CN202311846936.1A CN202311846936A CN117820681A CN 117820681 A CN117820681 A CN 117820681A CN 202311846936 A CN202311846936 A CN 202311846936A CN 117820681 A CN117820681 A CN 117820681A
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 291
- 239000000843 powder Substances 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 113
- 239000003063 flame retardant Substances 0.000 title claims abstract description 112
- 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 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 225
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 219
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims abstract description 154
- JDTMNMAQWVSSOO-MRVPVSSYSA-N (r)-2-(formyloxy)-3-(phosphonooxy)propyl pentanoate Chemical compound CCCCC(=O)OC[C@@H](OC=O)COP(O)(O)=O JDTMNMAQWVSSOO-MRVPVSSYSA-N 0.000 claims abstract description 116
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 100
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- 238000000034 method Methods 0.000 claims abstract description 69
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims abstract description 62
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 description 2
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- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- SHLNAWZFVPZYAG-UHFFFAOYSA-N OP(O)(O)=O.C1=CC=CC=C1.Cl.Cl Chemical compound OP(O)(O)=O.C1=CC=CC=C1.Cl.Cl SHLNAWZFVPZYAG-UHFFFAOYSA-N 0.000 description 1
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- SWRNIYAQKATHDJ-UHFFFAOYSA-N dichloro(dichlorophosphanyl)phosphane Chemical compound ClP(Cl)P(Cl)Cl SWRNIYAQKATHDJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of waste textile recovery, and relates to a preparation method of P/benzene/Si flame-retardant system composite powder, which utilizes phenyl dichlorophosphate to prepare nano SiO 2 Covalent connection with phenylbutanol to obtain modified nano SiO 2 Modified nano SiO 2 Mixing PA6, methanol, ethanol, methyl benzoate and benzamide, and preparing P/benzene/Si flame-retardant system composite powder by a dissolution precipitation method; wherein, PA6 and modified nano SiO 2 The mass of (2) is 12-1The volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, the addition amount of the benzamide is 2-3wt% of the total addition amount of the methanol to the ethanol to the methyl benzoate, and the mass ratio of the total mass of the methanol to the ethanol to the methyl benzoate to the PA6 is 7-8:1. The preparation method is simple, and the prepared composite powder has excellent dimensional stability and flame retardance.
Description
Technical Field
The invention belongs to the technical field of waste textile recovery, and relates to a preparation method of P/benzene/Si flame-retardant system composite powder.
Background
In the past process of global economy development, people can meet the material demands and simultaneously correspondingly increase various types of domestic waste, textiles are an indispensable part of material life, a large amount of waste is generated each year, the number of textiles of synthetic fibers is far higher than that of natural fibers, the synthetic fibers have strong chemical inertness, and the synthetic fibers are difficult to degrade in nature after being abandoned, so that the method has positive significance in recycling the synthetic fibers. Nylon materials are varieties with more usage amount in synthetic fibers, and PA6 (nylon 6) is used as an important member of nylon families, so that the nylon materials are widely used in the textile industry, and are one of widely used nylon fibers, thereby having positive social significance for recycling PA6 textiles and conforming to sustainable social development.
The recovery mode of the synthetic fiber mainly comprises two modes of physical recovery and chemical recovery, the chemical recovery can be used for depolymerizing the synthetic fiber into a monomer for recovery, the conventional method for chemical depolymerization is a hydrolysis method and a pyrolysis method, the requirements on equipment are high, the process parameters are strict, the actual production cost is high, the physical recovery process is simple, the cost is low, but the physical performance of the obtained regenerated product is reduced, and the regenerated product can only be degraded for use generally, so that the recovery and development of the regenerated PA6 product with high added value have positive significance.
Nylon powder is a thermoplastic powder having many excellent properties such as electrical insulation, lubricity, abrasion resistance, impact resistance, etc., and can be used alone or in admixture with other additives. At present, the preparation method of the polymer powder material mainly comprises a dissolution precipitation method, a spray drying method, a direct polymerization method, a cryogenic grinding method and the like, and has different problems at the same time when each method has advantages, and the dissolution precipitation method has the advantages of uniform particle size and higher sphericity of the prepared powder particles and has better application prospect. The common PA6 powder still maintains the inflammable characteristic of the nylon material, can burn to form molten drops and release harmful smog in the use environment, and also faces the characteristic of poor dimensional stability if applied to the laser sintering process of 3D printing, so the PA6 powder with good dimensional stability and flame retardance prepared by using a dissolution precipitation method has positive significance, and can also provide a method with higher added value for recycling waste PA6.
Document 1A nanosilica/nylon-12composite powder for selective laser sintering[J]Journal of Reinforced Plastics and Composites,2009,28 (23): 2889-2902. SiO was modified by using a silane coupling agent 2 With modified SiO 2 As a core, a mixed solvent of ethanol/butanone/water was used as a mixed solvent, and after the PA12 (nylon 12) was completely dissolved, the PA12 was cooled to make SiO a solution of PA12 2 Surface precipitation, siO modified with silane coupling agent 2 Has amino group, and can generate amidation reaction with carboxyl of PA12 macromolecular chain in the precipitation process to promote PA12 in SiO 2 Upper precipitation and enhancement of PA12 macromolecular chain and SiO 2 The composite powder finally obtained in the document 1 has no flame retardant property and still faces the problem of flammability of the high molecular polymer.
Literature 2 organic phosphorus modified nano SiO 2 And its use in PP [ J]Chinese plastics, 2016,30 (2): 59-63 et al describe a modified SiO 2 Thermal stability for improved polypropylene materials (PP)Qualitative and flame retardant Properties, literature 2 modification of SiO by organophosphorus 2 Imparting heat stability and flame retarding effect, isopropanol imparts SiO 2 Hydrophobicity, avoiding SiO originally having hydroxyl groups 2 Aggregation in PP melt affects the dispersibility of inorganic particles, and a composite material with improved flame retardance and thermal stability is obtained by melt blending, but in document 2, powder material cannot be prepared by melt blending functional inorganic particles with a polymer matrix, and irregular-shaped composite powder can be obtained only by granulating and then grinding.
Theoretically, if document 2 and document 1 are combined, the organic phosphorus is used for SiO first 2 The modification is performed, and then the composite powder with good dimensional stability and flame retardance can be prepared by using a dissolution precipitation method, however, in the actual experimental process, the finally prepared composite powder is found to have poor flame retardance, because the flame retardance elements in the composite powder are only P and Si, and a better synergistic effect cannot be achieved, and in addition, the reaction mode is too complex because the interaction force among molecules is increased by using a chemical reaction mode in the literature 1.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of P/benzene/Si flame-retardant system composite powder.
In order to achieve the above purpose, the invention adopts the following technical scheme:
preparation method of P/benzene/Si flame-retardant system composite powder, wherein nano SiO is prepared by using phenyl dichlorophosphate 2 Covalent connection with phenylbutanol to obtain modified nano SiO 2 Modified nano SiO 2 Mixing PA6, methanol, ethanol, methyl benzoate and benzamide, and preparing P/benzene/Si flame-retardant system composite powder by a dissolution precipitation method; wherein, PA6 and modified nano SiO 2 The mass ratio of the methanol to the ethanol to the methyl benzoate is 10-12:1, the volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, the addition amount of the benzamide is 2-3 wt% of the total addition amount of the methanol to the ethanol to the methyl benzoate, and the mass ratio of the total mass of the methanol to the ethanol to the methyl benzoate to the PA6 is 7-8:1.
The invention prepares the P/benzene/Si flame-retardant system composite powderDuring the process of (1) utilizing phenyl dichlorophosphate and phenylbutanol to SiO 2 The purpose of the modification is to endow the P/benzene/Si flame-retardant system composite powder with good flame-retardant performance, and the specific principle is as follows: the flame-retardant elements comprise P, si, the benzene ring also has the capability of improving the thermal stability, and different structural combinations can exert better flame-retardant effect, while the nano SiO 2 As inorganic particles, the inorganic particles have good thermal stability and dimensional stability, the Si has smoke suppression effect, the phenylbutanol has benzene ring structure, the phenylbutanol has the potential of becoming a flame retardant, the dichlorophosphate has P, the phenyldichlorophosphate is a common synthetic raw material of the flame retardant, the P-Cl bond on the dichlorophosphate can react with-OH, and the nano SiO can be prepared 2 Is connected with phenylbutanol and simultaneously provides a benzene ring structure to ensure that the modified nano SiO 2 Becomes a P/benzene/Si flame-retardant system with good flame-retardant performance, and modified nano SiO 2 After the P/benzene/Si flame-retardant system composite powder is prepared by a dissolution precipitation method as a nucleating agent, the P/benzene/Si flame-retardant system composite powder has good flame-retardant performance.
The invention adds benzamide and methyl benzoate in the process of preparing P/benzene/Si flame-retardant system composite powder by a dissolution precipitation method, and aims to strengthen PA6 macromolecular chains and modified nano SiO 2 The specific principle is as follows: in the process of dissolving and precipitating PA6, the macromolecular chains of PA6 after dissolution are in a free state in a solvent, at the moment, in the process of precipitating, the macromolecular chains of PA6 can be entangled with each other to form crystal nucleus, then continuously grow around the crystal nucleus, and finally precipitate and form, if nano particles are added in a mixed solvent, the macromolecular chains of PA6 can be gradually aggregated on the nano particles in a heterogeneous nucleation mode in the process of precipitating, so in order to enable the macromolecular chains of PA6 to be better aggregated, the invention uses benzamide and methyl benzoate to strengthen the macromolecular chains of PA6 and modified nano SiO 2 The benzamide is dissolved in a mixed solvent, the amide bond energy of the benzamide and the amide bond of the PA6 form a strong hydrogen bond effect, the benzene ring of the methyl benzoate is easy to aggregate with the benzamide, and the benzene ring and the benzamide form a stronger pi stacking effect in an auxiliary way, so that the nano SiO is modified 2 The benzene ring on can be replaced byStrong pi stacking attraction, once benzamide is modified to nano SiO 2 The benzamide forming hydrogen bond with the PA6 can drag the PA6 molecular chain to modify nano SiO after aggregation 2 Aggregation to make PA6 macromolecular chain capable of modifying nano SiO 2 Is formed by aggregation of the surfaces of the glass substrates.
The invention selects the mixed solvent of methanol, ethanol and methyl benzoate as the dissolution solvent when preparing the P/benzene/Si flame-retardant system composite powder by a dissolution precipitation method, because: while PA6 is soluble in organic solvents of high polarity such as formic acid, m-cresol, trifluoroacetic acid, etc. at normal temperature and insoluble in organic reagents such as DMF (N, N-dimethylformamide), ethanol, methanol, acetone, etc., the dissolution precipitation method is a method requiring that PA6 can be precipitated by temperature change in the dissolution solvent, so that good solvents such as formic acid dissolve PA6 at room temperature to precipitate PA6 with difficulty in temperature change, whereas mixed solvents of methanol/ethanol are used, PA6 has property of being insoluble at room temperature and soluble at high temperature, and further precipitation of PA6 can be achieved by temperature change, so that methanol/ethanol is good solvent of PA6 at high temperature, and proper addition of poor solvent can increase solubility, so that addition of poor solvent methyl benzoate can increase solubility of PA6 in solvent to increase degree of freedom of PA6, make it better contact with added benzamide, and also can enhance modification of nano SiO 2 The dispersion degree in the solvent can also form stronger pi stacking effect with the benzamide, thereby reinforcing the benzamide and the modified nano SiO 2 Is described in (a) and (b) interact with each other.
The invention controls PA6 and modified nano SiO in the process of preparing the P/benzene/Si flame-retardant system composite powder by a dissolution precipitation method 2 The mass of the modified nano SiO is 12-10:1 2 As a core, thereby controlling the particle size of the composite powder to a proper size;
the volume ratio of methanol, ethanol and methyl benzoate is controlled to be 70:25:5 on one hand to control the dissolving capacity of the mixed solvent to PA6 and on the other hand to control the benzamide to the modified nano SiO 2 Effective aggregation, concrete principleThe method comprises the following steps: methanol/ethanol is a good solvent of PA6 at normal temperature, and proper addition of poor solvent methyl benzoate can increase the contact site of PA6 and good solvent, so as to strengthen the dissolution process, and in the dissolution and precipitation process, benzamide and methyl benzoate can act on the modified nano SiO due to strong pi accumulation effect 2 The surfaces are close, and the benzamide is modified by nano SiO 2 After the benzene ring on the surface attracts, benzamide and modified nano SiO 2 A linkage, methyl benzoate detachment; too much methyl benzoate can cause excessive reduction of the dissolution capacity of the mixed solvent, so that PA6 cannot be completely dissolved, and too little methyl benzoate can cause insignificant increase of contact sites, so that the influence on the dissolution capacity of methanol/ethanol is limited, and the benzamide cannot be made to enter into modified nano SiO 2 Efficient aggregation;
the addition amount of the benzamide is controlled to be 2-3 wt% of the total addition amount of the methanol, the ethanol and the methyl benzoate because the benzamide needs to form proper aggregate with the methyl benzoate after forming hydrogen bonds with the amide bond of the PA6 macromolecular chain and then form proper aggregate with the modified SiO 2 When the attraction and the addition amount are too high, the benzamide can cause solid state transition after being dissolved, and the benzamide in the state can occupy most of the space of the PA6 macromolecular chain, so that the precipitation process is influenced, the distribution of the PA6 macromolecular chain in the mixed solvent is not free, and severe entanglement easily occurs in the precipitation process, so that the PA6 macromolecular chain is influenced in the modified nano SiO 2 Aggregation to the final different modified nano SiO 2 When the addition amount is too low, the benzamide can not form an aggregate with strong pi stacking effect with the methyl benzoate, so that the modified nano SiO is influenced 2 Leading to self-aggregation nucleation of part of PA6 macromolecular chains, resulting in failure to modify nano SiO 2 Upper aggregation;
the aim of controlling the mass ratio of the total mass of the methanol, the ethanol and the methyl benzoate to the mass of the PA6 to be 7-8:1 is to ensure that the macromolecular chains of the PA6 after dissolution are freely distributed in the mixed solvent, and the precipitation process can be more uniform.
As a preferable technical scheme:
according to the preparation method of the P/benzene/Si flame-retardant system composite powder, the molar ratio of the phenylbutanol to the phenyl dichlorophosphate is 8-9:10, and the nano SiO is prepared by the following steps 2 The molar ratio of the catalyst to the phenyl dichlorophosphate is 1:3.5-4.
The preparation method of the P/benzene/Si flame-retardant system composite powder modifies nano SiO 2 The preparation process of (2) is as follows: dripping the solution containing phenyl dichlorophosphate into the solution simultaneously containing nano SiO within 20 to 35 minutes 2 And phenylbutanol, and reacting at 60-85 deg.C for 6-12 hr, during which the phenyl dichlorophosphate is combined with phenylbutanol by P-Cl bond and-OH reaction of phenylbutanol, and the P-Cl bond of phenyl dichlorophosphate is also combined with SiO 2 Is connected with-OH to obtain the modified nano SiO 2 。
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the steps that the mass fraction of the phenyl dichlorophosphate in the solution containing the phenyl dichlorophosphate is 20-25 wt%; containing SiO 2 And SiO in solution with phenylbutanol 2 The mass fraction of the benzene butanol is 0.9 to 1 weight percent, and the mass fraction of the benzene butanol is 15 to 17 weight percent; solution containing phenyl dichlorophosphate and SiO containing 2 And phenylbutanol in a mass ratio of 7-8:10.
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the steps of solution containing phenyl dichlorophosphate and SiO 2 And benzene butanol are each independently selected from toluene and xylene.
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the following specific processes of: modified nano SiO 2 And heating the mixture of PA6, methanol, ethanol, methyl benzoate and benzamide to 145-160 ℃ and keeping the temperature for 1-2 h, cooling the mixture to below 40 ℃ at a cooling rate of 0.2-1 ℃/min to obtain precipitated particles, and washing and drying the particles to obtain the P/benzene/Si flame-retardant system composite powder.
The methanol/ethanol is a poor solvent for the PA6 at room temperature, the PA6 can be dissolved only at a higher temperature, when the temperature is lower, the PA6 can not be completely dissolved, and the too high temperature can cause the breakage of the PA6 macromolecular chain due to the extension of the dissolution time, so that the invention adopts 145-160 ℃ as the dissolution temperature, and the PA6 can be ensured to be completely dissolved after the temperature is raised for 1-2 hours.
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the following steps of washing and drying the PA6 before dissolving: immersing PA6 in the soap lotion, controlling the bath ratio to be 1:30-50, immersing and washing the soap lotion for 1h at 25-35 ℃ and drying the soap lotion for 12-24 h at 25-35 ℃.
The preparation method of the P/benzene/Si flame-retardant system composite powder has the yield of 78-83%, and the yield=the mass/(the mass addition of PA 6+the modified nano SiO) of the dried P/benzene/Si flame-retardant system composite powder 2 The mass addition amount of the (B) is multiplied by 100 percent, the average particle size of the P/benzene/Si flame-retardant system composite powder is 40-60 mu m, the PDI is 0.1-0.15, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder is 30-32 percent.
The principle of the invention:
the invention adopts SiO 2 The benzene dichloride phosphate and the phenylbutanol form a P/benzene/Si flame-retardant system, and the flame-retardant performance is endowed to the original SiO 2 Then modified SiO 2 Dispersing in methanol/ethanol mixed solution, adding PA6, dissolving PA6 in the mixed solvent at high temperature, cooling to precipitate PA6, and collecting macromolecular chain of PA6 in the process of precipitation 2 On the surface, modified SiO is wrapped in a heterogeneous nucleation mode 2 To prevent the PA6 from precipitating as uniformly as possible during the precipitation process and promote the PA macromolecular chains to form a composite powder in the modified SiO 2 Adding benzamide to make it and macromolecular interchain of PA6 and modified SiO 2 Pi-pi stacking is formed, and the high viscosity characteristic of the PA-6 macromolecular chain enables intermolecular forces to be formed between adjacent macromolecular chains so as to stabilize the macromolecular chains, so that the PA-6 macromolecular chains can be uniformly precipitated in the precipitation process.
The main difference between the present invention and document 1 is that: literature 1 is passed throughSilane coupling agent modified SiO 2 As a nucleus, then dispersed in a mixed solvent of ethanol/butanone/water, modified SiO during the cooling and precipitation process 2 Amidation reaction with PA12 macromolecular chain to strengthen acting force of the two and make PA12 macromolecular chain in SiO better 2 Surface precipitation; however, the composite powder finally obtained in document 1 still has no flame retardant property and still faces the problem of flammability of the high molecular polymer. While the invention is realized by modifying SiO 2 The flame retardant system of P/benzene/Si is constructed to endow the powder with flame retardant property, and benzamide is used for enhancing macromolecule chains and modified SiO in the process of dissolving and precipitating 2 Interactions between the modified SiO and the PA6 macromolecular chain are promoted 2 The upper precipitation makes the precipitation uniform and is beneficial to the follow-up processing application.
The main difference between the present invention and document 2 is that: document 2 p-SiO using phosphorus oxychloride and isopropanol 2 Modified to obtain modified SiO with flame retardant property 2 Modified SiO by means of conical twin-screw 2 Melt blending with PP, extrusion granulating to obtain modified composite material, wherein the melt blending is used in literature 2 to prepare dispersed powder material, and the dispersed powder material can only be subjected to granulating and then grinding to obtain irregularly-shaped composite powder.
The beneficial effects are that:
(1) According to the preparation method of the P/benzene/Si flame-retardant system composite powder, disclosed by the invention, the composite powder with good dimensional stability and regular shape can be prepared by a dissolution precipitation method, and the prepared P/benzene/Si flame-retardant system composite powder is a P/benzene/Si flame-retardant system, so that the flame-retardant effect is better.
(2) The preparation method of the P/benzene/Si flame-retardant system composite powder can prepare the flame-retardant composite powder by taking the PA6 as the raw material, effectively solves the problems of accumulation and pollution of solid waste caused by waste of the PA6, and is beneficial to environmental protection and resource utilization.
(3) The invention uses methyl benzoate/benzamide to lead PA6 and modified SiO 2 Is enhanced by intermolecular forcesComplex chemical reactions are avoided.
Drawings
FIG. 1 is a modified nano SiO according to example 1 of the present invention 2 And nano SiO 2 Is an infrared spectrum of (2);
FIG. 2 is a scanning electron microscope image of the P/benzene/Si flame retardant system composite powder prepared in example 1 of the present invention.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following are test methods for each performance in the examples:
yield: yield = mass of P/benzene/Si flame retardant system composite powder after drying/(mass addition of PA6 + modified SiO) 2 Mass) x 100%.
Average particle diameter: 200 particles were selected to obtain the average particle size by scanning electron microscopy with scale using Nano measure1.2 software.
PDI: after 0.5g of composite powder is manually ground by a mortar, 0.1g of composite powder of the P/benzene/Si flame-retardant system to be measured is accurately weighed, the composite powder is dispersed in 50mL of deionized water, diluted to be transparent, balanced for 10s on a Nano-particle sizer of Nano-ZS90 at 25 ℃, and tested to obtain the PDI of the composite powder.
Limiting oxygen index: the P/benzene/Si flame-retardant system composite powder is poured into a polytetrafluoroethylene mould with the thickness of 10mm and the size of 200 multiplied by 20 multiplied by 10mm in a molten state, cooled and cut into test samples with the thickness of 4mm and the size of 120 multiplied by 10 multiplied by 4mm, and the test is carried out according to the limit oxygen index national standard GB/T2406-2009-plastics combustion behavior is measured by an oxygen index method.
Example 1
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the following steps:
(1) Preparing raw materials;
solution of phenyl dichlorophosphate: the solvent is dimethylbenzene;
nano SiO 2 And phenylbutanol: the solvent is dimethylbenzene;
methanol;
PA6: CAS number 25038-54-4;
ethanol;
methyl benzoate;
benzamide;
(2) Dropwise adding the solution of phenyl dichlorophosphate to the nano SiO within 20min 2 And benzene butanol, reacting at 85deg.C for 12 hr to obtain modified nanometer SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the mass fraction of the phenyl dichlorophosphate in the phenyl dichlorophosphate solution is 25wt%, and the phenyl dichlorophosphate solution and SiO 2 The mass ratio of the solution to the phenylbutanol is 8:10, the molar ratio of the phenylbutanol to the phenyl dichlorophosphate is 13:10, and the nano SiO is prepared by the following steps 2 The molar ratio of the catalyst to the phenyl dichlorophosphate is 1:3.5;
the obtained modified nano SiO 2 And nano SiO 2 An infrared spectrum test was performed, as shown in FIG. 1, from which it can be seen that 2946cm -1 at-CH 2 Asymmetric telescopic vibration 2869cm -1 at-CH 2 -symmetrical stretching vibration of asymmetric stretching vibration 1455cm -1 is-CH 2 Bending vibration peak, 750cm -1 The characteristic peak of P-O-C is shown, and according to the patent document Peng Zhongli, duan Xianjian, yellow national book, organophosphorus modified nano SiO 2 And its use in PP [ J]Chinese plastics, 2016,30 (2): 59-63., it is known that benzyl alcohol and phenyl dichlorophosphate were successfully grafted onto SiO 2 Applying;
(3) Modified nano SiO 2 Heating the mixture of PA6, methanol, ethanol, methyl benzoate and benzamide to 160 ℃ and keeping the temperature for 2 hours, and cooling to 35 ℃ at a cooling rate of 0.5 ℃/min to obtain the P/benzene/Si flame-retardant system composite powder; wherein, PA6 and modified nano SiO 2 The mass ratio of the methanol to the ethanol to the methyl benzoate is 10:1, the volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, and the addition amount of the benzamide is methanol, ethanol and benzylThe mass ratio of the total mass of methyl benzoate to PA6 to the total addition of methyl acrylate of 3wt% is 8:1.
The final P/benzene/Si flame retardant system composite powder (as shown in FIG. 2) had a yield of 78%, an average particle diameter of 60 μm, a PDI of 0.1 and a limiting oxygen index of 32%.
Comparative example 1
A method for preparing a P/benzene/Si flame retardant system composite powder, which is basically the same as in example 1, except that: in the step (3), PA6 and modified nano SiO 2 The mass ratio of (2) is 9:1.
The final yield of the P/benzene/Si flame-retardant system composite powder was 78%, the average particle diameter was 53 μm, the PDI was 0.26, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 31.8%.
As can be seen from comparing comparative example 1 with example 1, since nano SiO was modified in comparative example 1 2 The content of the (B) is increased, so that the particle size of the prepared P/benzene/Si flame-retardant system composite powder is reduced, and the PDI is increased, because PA6 macromolecular chains need to be gathered on modified nano SiO in the process of dissolution and precipitation 2 Surface, proper mass ratio can lead the modified nano SiO to be gathered 2 Is to modify nano SiO on the surface of (a) 2 Is entirely covered with SiO 2 If too much, the nuclei in the solvent during precipitation of PA6 macromolecular chains are increased, so that the modified nano SiO can be covered better originally 2 The PA6 macromolecular chain on the modified nano SiO has a vacancy 2 The PA6 macromolecular chains on the surface are unevenly distributed, the particle size of composite powder formed by final precipitation is reduced, but the morphology is more uneven, and the PDI is increased.
Comparative example 2
A method for preparing a P/benzene/Si flame retardant system composite powder, which is basically the same as in example 1, except that: in the step (3), PA6 and modified nano SiO 2 The mass ratio of (2) is 13:1.
The final yield of the P/benzene/Si flame-retardant system composite powder was 78%, the average particle diameter was 70 μm, the PDI was 0.28, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 32.1%.
As can be seen from comparison of comparative example 2 and example 1, since nano SiO was modified in comparative example 2 2 The content of the (B) is reduced, so that the particle size and PDI of the prepared P/benzene/Si flame-retardant system composite powder are increased, and the PA6 macromolecular chain is required to be aggregated on the modified nano SiO in the dissolving and precipitating process 2 Surface, proper proportion can lead the modified nano SiO to be 2 The surface of (C) is totally covered by PA6 macromolecular chains, and modified nano SiO 2 When the content of (C) is too small, the particles are accumulated in the modified nano SiO 2 The PA6 macromolecular chains on the surface are increased, and the PA6 macromolecular chains on the outer surface layer are easy to be combined with nearby modified nano SiO 2 The PA6 macromolecular chains on the surface are entangled to cause aggregation of particles, so that the particle size is increased, and the PDI is increased.
Comparative example 3
A method for preparing a P/benzene/Si flame retardant system composite powder, which is basically the same as in example 1, except that: the addition amount of the benzamide in the step (3) is 1 weight percent of the total addition amount of the methanol, the ethanol and the methyl benzoate.
The final yield of the P/benzene/Si flame-retardant system composite powder was 78%, the average particle diameter was 52 μm, the PDI was 0.3, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 31.8%.
As can be seen from comparison of comparative example 3 and example 1, the too low addition of benzamide in comparative example 3 results in reduced particle size and increased PDI of the prepared P/benzene/Si flame retardant system composite powder, because too small addition of benzamide can not form aggregates with strong pi stacking effect with methyl benzoate, thereby affecting the modification of nano SiO 2 Leading to self-aggregation nucleation of partial PA6 macromolecular chain, so that the nano SiO can not be modified 2 And (5) aggregating.
Comparative example 4
A method for preparing a P/benzene/Si flame retardant system composite powder, which is basically the same as in example 1, except that: the addition amount of the benzamide in the step (3) is 4wt% of the total addition amount of the methanol, the ethanol and the methyl benzoate.
The final yield of the P/benzene/Si flame-retardant system composite powder was 78%, the average particle diameter was 71 μm, the PDI was 0.32, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 32%.
As can be seen from comparison of comparative example 4 and example 1, the too low amount of benzamide in comparative example 4 increases the particle size and PDI of the prepared P/benzene/Si flame retardant system composite powder, because the too much amount of benzamide is added, after the benzamide is dissolved in methanol/ethanol, the solid state is changed, and the benzamide in this state occupies part of the space of the PA6 macromolecular chain, thereby influencing the precipitation process, so that the distribution of the PA6 macromolecular chain in the mixed solvent becomes not free, and severe entanglement easily occurs in the precipitation process, thereby influencing the modification of nano SiO 2 Aggregation thereon, resulting in different modified nano SiO 2 Are connected together.
Comparative example 5
A method for preparing a P/benzene/Si flame retardant system composite powder, which is basically the same as in example 1, except that: in the step (3), the mass ratio of the total mass of the methanol, the ethanol and the methyl benzoate to the PA6 is 6:1.
The final yield of the P/benzene/Si flame-retardant system composite powder was 78%, the average particle diameter was 78 μm, the PDI was 0.34, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 31.9%.
As can be seen from comparison of comparative example 5 and example 1, since the ratio of the total mass of methanol, ethanol and methyl benzoate to PA6 in comparative example 5 is small, the particle size of the prepared P/benzene/Si flame retardant system composite powder is reduced, PDI is increased, since the degree of freedom of PA6 in the dissolution solvent is reduced and entanglement is easy in precipitation when the content of PA6 is increased, severe entanglement of PA6 macromolecular chains occurs in precipitation to coat different numbers of modified nano SiO 2 Irregular aggregates are formed.
Comparative example 6
A method for preparing a P/benzene/Si flame retardant system composite powder, which is basically the same as in example 1, except that: in the step (3), the mass ratio of the total mass of the methanol, the ethanol and the methyl benzoate to the PA6 is 9:1.
The final P/benzene/Si flame-retardant system composite powder was 55% in yield, 58 μm in average particle diameter, 0.1 in PDI, and 32% in limiting oxygen index.
As can be seen from comparison of comparative example 6 and example 1, the ratio of the total mass of methanol, ethanol and methyl benzoate to PA6 in comparative example 6 is large, resulting in a decrease in the yield of the prepared P/benzene/Si flame retardant system composite powder, because the PA6 content is small, degradation occurs to some extent, and the yield is decreased.
Comparative example 7
A method for preparing a P/benzene/Si flame retardant system composite powder, which is basically the same as in example 1, except that: in the step (3), the volume ratio of the methanol to the ethanol to the methyl benzoate is 20:20:60.
The solubility of methanol/ethanol is drastically reduced due to the excessive content of methyl benzoate, and PA6 cannot be completely dissolved.
As can be seen from comparison of comparative example 7 and example 1, the volume ratio of methanol, ethanol and methyl benzoate in comparative example 7 is 20:20:60, wherein the content of methyl benzoate is too high, and the content of the introduced poor solvent is too high, so that the solubility of methanol/ethanol is severely reduced, and PA6 cannot be completely dissolved, thereby preparing composite powder.
Example 2
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the following steps:
(1) Preparing raw materials;
solution of phenyl dichlorophosphate: the solvent is toluene;
nano SiO 2 And phenylbutanol: the solvent is toluene;
methanol;
PA6: CAS number 25038-54-4;
ethanol;
methyl benzoate;
benzamide;
(2) Dropwise adding the solution of phenyl dichlorophosphate to the nano SiO in 35min 2 And benzene butanol, and reacting at 60deg.C for 6 hr to obtain modified nanometer SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, phosphorus dichloride in the solution of phenyl dichlorophosphateThe mass fraction of the phenyl acid ester is 20wt%, and the solution of the phenyl dichlorophosphate and SiO 2 And the mass ratio of the solution of the phenylbutanol to the solution of the phenylbutanol is 7:10, the molar ratio of the phenylbutanol to the phenyl dichlorophosphate is 21:10, and the nano SiO is prepared by the following steps 2 The molar ratio of the catalyst to the phenyl dichlorophosphate is 1:3.75;
(3) Modified nano SiO 2 Heating the mixture of PA6, methanol, ethanol, methyl benzoate and benzamide to 145 ℃ and keeping the temperature for 1h, and cooling to 30 ℃ at a cooling rate of 1 ℃/min to obtain P/benzene/Si flame-retardant system composite powder; wherein, PA6 and modified nano SiO 2 The mass ratio of the methanol to the ethanol to the methyl benzoate is 12:1, the volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, the addition amount of the benzamide is 2wt% of the total addition amount of the methanol to the ethanol to the methyl benzoate, and the mass ratio of the total mass of the methanol to the ethanol to the methyl benzoate to the PA6 is 7:1.
The final yield of the P/benzene/Si flame-retardant system composite powder was 83%, the average particle diameter was 50 μm, the PDI was 0.15, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 31%.
Example 3
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the following steps:
(1) Preparing raw materials;
solution of phenyl dichlorophosphate: the solvent is dimethylbenzene;
nano SiO 2 And phenylbutanol: the solvent is toluene;
methanol;
PA6: CAS number 25038-54-4;
ethanol;
methyl benzoate;
benzamide;
(2) Dropwise adding the solution of phenyl dichlorophosphate to the nano SiO within 28min 2 And phenylbutanol, and reacting at 73 ℃ for 9 hours to obtain the modified nano SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the mass fraction of the phenyl dichlorophosphate in the phenyl dichlorophosphate solution is 22wt%, and the phenyl dichlorophosphate solution and SiO 2 And phenylbutanol at a mass ratio of 7.5:10, the molar ratio of phenylbutanol to phenyl dichlorophosphate being 1710, nano SiO 2 The molar ratio of the catalyst to the phenyl dichlorophosphate is 1:4.4;
(3) Modified nano SiO 2 Heating the mixture of PA6, methanol, ethanol, methyl benzoate and benzamide to 153 ℃ and keeping the temperature for 1.5 hours, and cooling to 35 ℃ at a cooling rate of 0.2 ℃/min to obtain the P/benzene/Si flame-retardant system composite powder; wherein, PA6 and modified nano SiO 2 The mass ratio of the methanol, the ethanol and the methyl benzoate is 11:1, the volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, the addition amount of the benzamide is 2.5 weight percent of the total addition amount of the methanol to the ethanol to the methyl benzoate, and the mass ratio of the total mass of the methanol to the ethanol to the methyl benzoate to the PA6 is 7.5:1.
The final P/benzene/Si flame-retardant system composite powder had a yield of 81%, an average particle diameter of 40 μm, a PDI of 0.125 and a limiting oxygen index of 30%.
Example 4
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the following steps:
(1) Preparing raw materials;
solution of phenyl dichlorophosphate: the solvent is toluene;
nano SiO 2 And phenylbutanol: the solvent is dimethylbenzene;
methanol;
PA6: CAS number 25038-54-4;
ethanol;
methyl benzoate;
benzamide;
(2) Dropwise adding the solution of phenyl dichlorophosphate to the nano SiO within 30min 2 And benzene butanol, and reacting at 80deg.C for 12 hr to obtain modified nanometer SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the mass fraction of the phenyl dichlorophosphate in the phenyl dichlorophosphate solution is 25wt%, and the phenyl dichlorophosphate solution and SiO 2 The mass ratio of the solution to the phenylbutanol is 8:10, the molar ratio of the phenylbutanol to the phenyl dichlorophosphate is 13:10, and the nano SiO is prepared by the following steps 2 The molar ratio of the catalyst to the phenyl dichlorophosphate is 1:3.5;
(3) Modified nano SiO 2 PA6, methanol, ethanol,After the mixture of methyl benzoate and benzamide is heated to 145 ℃ and kept for 1.5 hours, cooling to 30 ℃ at a cooling rate of 0.5 ℃/min to obtain P/benzene/Si flame-retardant system composite powder; wherein, PA6 and modified nano SiO 2 The mass ratio of the methanol, the ethanol and the methyl benzoate is 10:1, the volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, the addition amount of the benzamide is 3 weight percent of the total addition amount of the methanol, the ethanol and the methyl benzoate, and the mass ratio of the total mass of the methanol, the ethanol and the methyl benzoate to the PA6 is 8:1.
The final yield of the P/benzene/Si flame-retardant system composite powder was 83%, the average particle diameter was 57 μm, the PDI was 0.1, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 32%.
Example 5
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the following steps:
(1) Preparing raw materials;
solution of phenyl dichlorophosphate: the solvent is dimethylbenzene;
nano SiO 2 And phenylbutanol: the solvent is dimethylbenzene;
methanol;
PA6: CAS number 25038-54-4;
ethanol;
methyl benzoate;
benzamide;
(2) Dropwise adding the solution of phenyl dichlorophosphate to the nano SiO within 20min 2 And phenylbutanol, and reacting at 78deg.C for 10 hr to obtain modified nanometer SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the mass fraction of the phenyl dichlorophosphate in the phenyl dichlorophosphate solution is 25wt%, and the phenyl dichlorophosphate solution and SiO 2 And the mass ratio of the solution of the phenylbutanol to the solution of the phenylbutanol is 7:10, the molar ratio of the phenylbutanol to the phenyl dichlorophosphate is 21:10, and the nano SiO is prepared by the following steps 2 The molar ratio of the catalyst to the phenyl dichlorophosphate is 1:3.5;
(3) Modified nano SiO 2 Heating the mixture of PA6, methanol, ethanol, methyl benzoate and benzamide to 160 ℃ and keeping the temperature for 1.5 hours, and cooling to 32 ℃ at a cooling rate of 0.8 ℃/min to obtain the P/benzene/Si flame-retardant system composite powder; wherein,PA6 and modified nano SiO 2 The mass ratio of the methanol, the ethanol and the methyl benzoate is 10:1, the volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, the addition amount of the benzamide is 3 weight percent of the total addition amount of the methanol, the ethanol and the methyl benzoate, and the mass ratio of the total mass of the methanol, the ethanol and the methyl benzoate to the PA6 is 8:1.
The final yield of the P/benzene/Si flame-retardant system composite powder was 78%, the average particle diameter was 58 μm, the PDI was 0.1, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 31.6%.
Example 6
The preparation method of the P/benzene/Si flame-retardant system composite powder comprises the following steps:
(1) Preparing raw materials;
solution of phenyl dichlorophosphate: the solvent is dimethylbenzene;
nano SiO 2 And phenylbutanol: the solvent is dimethylbenzene;
methanol;
PA6: CAS number 25038-54-4;
ethanol;
methyl benzoate;
benzamide;
(2) Dropwise adding the solution of phenyl dichlorophosphate to the nano SiO within 20min 2 And benzene butanol, reacting at 85deg.C for 12 hr to obtain modified nanometer SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the mass fraction of the phenyl dichlorophosphate in the phenyl dichlorophosphate solution is 25wt%, and the phenyl dichlorophosphate solution and SiO 2 The mass ratio of the solution to the phenylbutanol is 8:10, the molar ratio of the phenylbutanol to the phenyl dichlorophosphate is 13:10, and the nano SiO is prepared by the following steps 2 The molar ratio of the catalyst to the phenyl dichlorophosphate is 1:3.5;
(3) Modified nano SiO 2 Heating the mixture of PA6, methanol, ethanol, methyl benzoate and benzamide to 160 ℃ and keeping the temperature for 2 hours, and cooling to 30 ℃ at a cooling rate of 0.2 ℃/min to obtain P/benzene/Si flame-retardant system composite powder; wherein, PA6 and modified nano SiO 2 The mass ratio of the methanol to the ethanol to the methyl benzoate is 12:1, the volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, and the addition amount of the benzamide is methanol, ethanol and methyl benzoateThe mass ratio of the total mass of methanol, ethanol, methyl benzoate to PA6 was 7:1.
The final yield of the P/benzene/Si flame-retardant system composite powder was 78%, the average particle diameter was 45 μm, the PDI was 0.1, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder was 32%.
Claims (7)
1. A preparation method of P/benzene/Si flame-retardant system composite powder is characterized in that phenyl dichlorophosphate is utilized to prepare nano SiO 2 Covalent connection with phenylbutanol to obtain modified nano SiO 2 Modified nano SiO 2 Mixing PA6, methanol, ethanol, methyl benzoate and benzamide, and preparing P/benzene/Si flame-retardant system composite powder by a dissolution precipitation method; wherein, PA6 and modified nano SiO 2 The mass ratio of the methanol to the ethanol to the methyl benzoate is 10-12:1, the volume ratio of the methanol to the ethanol to the methyl benzoate is 70:25:5, the addition amount of the benzamide is 2-3 wt% of the total addition amount of the methanol to the ethanol to the methyl benzoate, and the mass ratio of the total mass of the methanol to the ethanol to the methyl benzoate to the PA6 is 7-8:1.
2. The preparation method of the P/benzene/Si flame-retardant system composite powder according to claim 1, which is characterized in that the molar ratio of the phenylbutanol to the phenyl dichlorophosphate is 8-9:10, and the nano SiO 2 The molar ratio of the catalyst to the phenyl dichlorophosphate is 1:3.5-4.
3. The method for preparing the P/benzene/Si fire-retardant system composite powder according to claim 2, wherein the modified nano SiO 2 The preparation process of (2) is as follows: dripping the solution containing phenyl dichlorophosphate into the solution simultaneously containing nano SiO within 20 to 35 minutes 2 And benzene butanol, reacting at 60-85 deg.c for 6-12 hr to obtain modified nanometer SiO 2 。
4. The method for preparing a P/benzene/Si flame retardant system composite powder according to claim 3, wherein the mass fraction of phenyl dichlorophosphate in the solution containing phenyl dichlorophosphate is 20-25 wt%The method comprises the steps of carrying out a first treatment on the surface of the Containing SiO 2 And SiO in solution with phenylbutanol 2 The mass fraction of the benzene butanol is 0.9 to 1 weight percent, and the mass fraction of the benzene butanol is 15 to 17 weight percent; solution containing phenyl dichlorophosphate and SiO containing 2 And phenylbutanol in a mass ratio of 7-8:10.
5. The method for preparing a P/benzene/Si flame retardant system composite powder according to claim 3, wherein the solution contains phenyl dichlorophosphate and the SiO-containing solution contains 2 And benzene butanol are each independently selected from toluene and xylene.
6. The preparation method of the P/benzene/Si flame-retardant system composite powder according to claim 1, wherein the specific process for preparing the P/benzene/Si flame-retardant system composite powder by a dissolution precipitation method is as follows: modified nano SiO 2 And heating the mixture of PA6, methanol, ethanol, methyl benzoate and benzamide to 145-160 ℃ and keeping the temperature for 1-2 h, and cooling the mixture to below 40 ℃ at a cooling rate of 0.2-1 ℃/min to obtain the P/benzene/Si flame-retardant system composite powder.
7. The method for preparing the P/benzene/Si fire-retardant system composite powder according to claim 1, wherein the yield of the P/benzene/Si fire-retardant system composite powder is 78-83%, and the yield = mass of the dried P/benzene/Si fire-retardant system composite powder/(mass addition of PA6 + modified nano SiO) 2 The mass addition amount of the (B) is multiplied by 100 percent, the average particle size of the P/benzene/Si flame-retardant system composite powder is 40-60 mu m, the PDI is 0.1-0.15, and the limiting oxygen index of the P/benzene/Si flame-retardant system composite powder is 30-32 percent.
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