Nanocomposite plastic flame-retardant master batch and preparation method thereof

Abstract

The application discloses a kind of nanocomposite plastic flame-retardant master batch and preparation method thereof, it is related to plastic master batch technical field, including following by weight parts of raw material is made: carrier resin 40-50 parts, compatible agent 3-5 parts, processing aid 2-4 parts, modified nano inorganic flame retardant 20-30 parts, synergist 5-10 parts;The modified nano inorganic flame retardant is 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, silane coupling agent KH560 co-modified nano inorganic flame retardant.The master batch has excellent flame-retardant performance, good environmental protection performance, sufficient thermal stability, good compatibility with plastic matrix, and low negative impact on its mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plastic masterbatch, in particular to a kind of nanometer composite plastic flame-retardant masterbatch and preparation method thereof. BACKGROUND

[0002] With the wide application of plastic products in various fields, the safety hazard caused by its flammability has been increasingly concerned. In order to improve the flame retardant performance of plastic products, flame-retardant masterbatch emerges as the times require. Traditional flame-retardant masterbatch mostly adopts the way of adding a large amount of flame retardant. However, this method has many drawbacks. For example, the addition of a large amount of flame retardant will cause the mechanical properties of plastic products to decrease, affecting their actual use effect. In addition, the flame-retardant masterbatch on the market also has technical defects such as poor environmental performance, insufficient thermal stability, easy decomposition failure during high-temperature processing, etc.

[0003] Nanomaterials can not only improve the mechanical properties and heat resistance of the polymer matrix, but also improve the flame retardant performance of the matrix when added in the polymer. Therefore, nanomaterials are widely used in polymer materials. However, when they are used alone in plastic materials, the flame retardant performance cannot meet the actual use requirements. In addition, they are prone to agglomeration in the plastic matrix, which affects their large-scale application as a flame-retardant material in practice.

[0004] In order to solve the above problems, a kind of nanometer modified flame-retardant masterbatch is disclosed in Chinese patent CN109957170B. It includes the following components by mass fraction: 10-30 parts of EVA, 10-20 parts of organic kaolin, 10-30 parts of wollastonite powder, 20-30 parts of organic montmorillonite, 30-40 parts of brominated epoxy resin, 3-5 parts of sodium antimonate, and 2-5 parts of coupling agent. Although this flame-retardant masterbatch can improve the flame retardant performance of PBT, it contains halogen and sodium antimonate, which makes its environmental performance insufficient.

[0005] Therefore, it is necessary to develop a kind of nanometer composite plastic flame-retardant masterbatch with excellent flame retardant performance, good environmental performance, sufficient thermal stability, good compatibility with plastic matrix, and low negative impact on the mechanical properties of plastic matrix, as well as its preparation method, which meets the market demand and has wide market value and application prospect, and is of great significance to the development of the field of plastic flame-retardant masterbatch. SUMMARY

[0006] Therefore, the purpose of the present application is to provide a kind of nanometer composite plastic flame-retardant masterbatch with excellent flame retardant performance, good environmental performance, sufficient thermal stability, good compatibility with plastic matrix, and low negative impact on the mechanical properties of plastic matrix, as well as its preparation method.

[0007] In order to achieve the above purpose, the present application provides the following technical solutions:

[0008] The application discloses a kind of nanocomposite plastic flame-retardant master batch, including following raw materials made by weight parts: carrier resin 40-50 parts, compatible agent 3-5 parts, processing aid 2-4 parts, modified nano inorganic flame retardant 20-30 parts, synergist 5-10 parts;The modified nano inorganic flame retardant is 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, silane coupling agent KH560 co-modified nano inorganic flame retardant.

[0009] Preferably, the preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole is described in the following reference: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and characterization of Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [J]. Chemical reagents, 2002 (6): 344-345.

[0010] Preferably, the carrier resin is a mixture of homopolypropylene resin and copolypropylene resin in a mass ratio of 1:1, the homopolypropylene resin is T30S general-purpose homopolypropylene from Shanghai Petrochemical, and the copolypropylene resin is Dalian Hengli K8003 copolypropylene.

[0011] Preferably, the compatible agent is maleic anhydride grafted PP with a PO 1020 brand provided by Exxon.

[0012] Preferably, the processing aid is a mixture of lubricant and antioxidant in a mass ratio of 1:(1-3).

[0013] Preferably, the lubricant is zinc stearate, and the antioxidant is at least one of antioxidant 1010 and antioxidant 168.

[0014] Preferably, the synergist is melamine polyphosphate.

[0015] Preferably, the preparation method of the modified nano inorganic flame retardant comprises the following steps:

[0016] Step I: disperse silicon source, iron source, aluminum source, tin source and titanium source in alcohol solvent, stir uniformly, slowly add sodium acetate, transfer the mixture into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and react at 200-225 DEG C for 18-24 h; remove the reaction kettle, wash with anhydrous ethanol and deionized water after the reaction system is cooled to room temperature, then dry in a vacuum drying oven at 85-95 DEG C for 15-22 h, and finally calcine to obtain nanoscale flame-retardant active ingredients;

[0017] Step II: the nanoscale flame-retardant active ingredient and nanometer montmorillonite are mixed uniformly, then dispersed in N-methyl pyrrolidone, then silane coupling agent KH560 is added, stirred at 50-60℃ for 2-4h, then 3,3'-diamino-4,4'-difluorobenzophenone, (3,6-diaminoacridine-9-yl)boric acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole are added, stirred at 70-80℃ for 4-6h, then the solvent is removed by rotary evaporation to obtain the modified nanometer inorganic flame retardant.

[0018] Preferably, the iron source in step I is ferric nitrate; the silicon source is at least one of sodium silicate and silicon tetrachloride; the aluminum source is aluminum nitrate; the tin source is tin chloride; and the titanium source is titanium nitrate.

[0019] Preferably, the mass ratio of the silicon source, iron source, aluminum source, tin source, titanium source, alcohol solvent, and sodium acetate in step I is 1:(0.1-0.3):0.2:0.1:0.2:(10-20):3.

[0020] Preferably, the alcohol solvent in step I is at least one of ethanol, ethylene glycol, and n-butanol.

[0021] Preferably, the temperature of the calcination in step I is 550-750℃, and the time is 3-5h.

[0022] Preferably, the mass ratio of the nanoscale flame-retardant active ingredient, nanometer montmorillonite, N-methyl pyrrolidone, silane coupling agent KH560, 3,3'-diamino-4,4'-difluorobenzophenone, (3,6-diaminoacridine-9-yl)boric acid, and meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole in step II is 3:1:(15-25):1:0.5:(0.1-0.3):0.1.

[0023] Preferably, the particle size of the nanometer montmorillonite is 10-80nm.

[0024] Another object of the present application is to provide a preparation method of the nanocomposite plastic flame-retardant master batch, which comprises the following steps: adding each raw material into a high-speed mixer according to weight parts, mixing at a rotation speed of 800-1200r / min for 15-20min to fully mix each raw material uniformly to obtain a mixture; then adding the mixture into a twin-screw extruder to melt extrude, water-cooling, and granulating to obtain the nanocomposite plastic flame-retardant master batch.

[0025] Preferably, the extrusion temperature of the twin-screw extruder is 210-230℃, and the screw rotation speed is 300-500r / min.

[0026] The beneficial effects produced by the above technical solution are that:

[0027] (1) The preparation method of the nanocomposite plastic flame-retardant master batch provided by the application is simple in process, convenient in operation control, low in dependence on equipment, high in preparation efficiency and finished product qualification rate, suitable for continuous large-scale production, and has high popularization and application value.

[0028] (2) The nanocomposite plastic flame-retardant master batch provided by the application is prepared from the following raw materials in parts by weight: carrier resin 40-50 parts, compatibilizer 3-5 parts, processing aid 2-4 parts, modified nanometer inorganic flame retardant 20-30 parts, and synergist 5-10 parts; the modified nanometer inorganic flame retardant is a 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, and silane coupling agent KH560 co-modified nanometer inorganic flame retardant. By modifying the nanometer inorganic flame retardant, fluorine-containing phenyl sulfone, acridine boronic acid, and cup [4] pyrrole structures are introduced on the surface of the nanometer inorganic flame retardant at the same time. These structures can effectively improve the flame-retardant effect under the multiple effects of electronic effect, steric effect, and conjugation effect, and can also make the nanometer inorganic flame retardant uniformly dispersed in the plastic matrix, effectively enhancing the mechanical properties of the material. Through the mutual cooperation and synergistic effect of the raw materials, the product has excellent flame-retardant performance, good environmental protection performance, sufficient thermal stability, good compatibility with the plastic matrix, and low negative impact on the mechanical properties; a stable heat insulation and oxygen insulation structure is formed during the combustion process, and the addition of the antioxidant prevents the oxidation degradation of the flame-retardant system during long-term use, thereby enhancing the flame-retardant durability of the flame-retardant master batch.

[0029] (3) The nanometer inorganic flame retardant in the nanocomposite plastic flame-retardant master batch provided by the application is composed of nanometer flame-retardant active components and nanometer montmorillonite, and the nanometer flame-retardant active components are prepared by solvothermal reaction of a silicon source, an iron source, an aluminum source, a tin source, and a titanium source; they cooperate with each other to effectively improve the flame-retardant effect; the synergistic effect of the raw materials effectively realizes multi-dimensional flame retardation. DETAILED DESCRIPTION

[0030] In order to enable the person skilled in the art to better understand the technical solutions of the present application, and to make the above-mentioned features, objects, and advantages of the present application more clear and easy to understand, the present application will be further described below in conjunction with examples. The examples are only used to illustrate the present application and not to limit the scope of the present application.

[0031] Example 1

[0032] A kind of nanocomposite plastic flame-retardant master batch, including the following raw materials made by weight parts: carrier resin 40 parts, compatibility agent 3 parts, processing aid 2 parts, modified nano inorganic flame retardant 20 parts, synergist 5 parts;The modified nano inorganic flame retardant is 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, silane coupling agent KH560 co-modified nano inorganic flame retardant.

[0033] The preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and characterization of Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [J]. Chemical reagents, 2002 (6): 344-345;The carrier resin is homopolymerization polypropylene resin, copolymerization polypropylene resin is mixed by mass ratio 1:1;The homopolymerization polypropylene resin is Shanghai Petrochemical brand T30S general-purpose homopolymerization polypropylene;The copolymerization polypropylene resin is Dalian Hengli K8003 copolymerization polypropylene;The compatibility agent is maleic anhydride grafted PP, and the brand is PO 1020, provided by the United States Exxon;The processing aid is lubricant, antioxidant mixed by mass ratio 1:1;The lubricant is zinc stearate;The antioxidant is antioxidant 1010;The synergist is melamine polyphosphate.

[0034] The preparation method of the modified nano inorganic flame retardant, including the following steps:

[0035] Step I: the silicon source, iron source, aluminum source, tin source, titanium source are dispersed in alcohol solvent, after stirring uniformly, sodium acetate is slowly added, the mixture is transferred to the hydrothermal reaction kettle lined with polytetrafluoroethylene, and is reacted at 200 DEG C for 18h;The reaction kettle is taken out, and after the reaction system is cooled to room temperature, it is washed repeatedly with anhydrous ethanol and deionized water, then it is dried in a vacuum drying oven at 85 DEG C for 15h, and finally it is calcined to obtain nanoscale flame-retardant active ingredient;

[0036] Step II: the nanoscale flame-retardant active ingredient and nanometer montmorillonite are mixed uniformly, then dispersed in N-methyl pyrrolidone, then silane coupling agent KH560 is added, stirred at 50 DEG C for 2h, then 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole are added, and stirred at 70 DEG C for 4h, then the solvent is removed by rotary evaporation to obtain modified nano inorganic flame retardant.

[0037] The iron source in step I is ferric nitrate; the silicon source is sodium silicate; the aluminum source is aluminum nitrate; the tin source is tin chloride; the titanium source is titanium nitrate; the mass ratio of the silicon source, iron source, aluminum source, tin source, titanium source, alcohol solvent, sodium acetate in step I is 1:0.1:0.2:0.1:0.2:10:3; the alcohol solvent in step I is ethanol; the temperature of the calcination in step I is 550 DEG C, and the time is 3h.

[0038] The mass ratio of the nanoscale flame-retardant active ingredient, nanometer montmorillonite, N-methyl pyrrolidone, silane coupling agent KH560, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl)boric acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole in step II is 3:1:15:1:0.5:0.1:0.1; the particle size of the nanometer montmorillonite is 10nm.

[0039] A preparation method of the nanocomposite plastic flame-retardant master batch, comprising the following steps: adding each raw material into a high-speed mixer in weight parts, mixing for 15min at a rotating speed of 800r / min, so that each raw material is fully mixed and uniform, to obtain a mixture; then adding the mixture into a double-screw extruder for melt extrusion, and after water cooling and granulation, a nanocomposite plastic flame-retardant master batch is obtained; the extrusion temperature of the double-screw extruder is 210 DEG C, and the screw rotating speed is 300r / min.

[0040] Example 2

[0041] A nanocomposite plastic flame-retardant master batch, comprising the following raw materials made in weight parts: carrier resin 43 parts, compatibilizer 3.5 parts, processing aid 2.5 parts, modified nanometer inorganic flame retardant 23 parts, synergist 6 parts; the modified nanometer inorganic flame retardant is a co-modified nanometer inorganic flame retardant of 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl)boric acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, and silane coupling agent KH560.

[0042] The preparation method of the Meso-tetramethyl-meso-tetrakis-p-aminophenylcalix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and characterization of Meso-tetramethyl-meso-tetrakis-p-aminophenylcalix[4]pyrrole [J]. Chemical reagents, 2002 (6): 344-345; the carrier resin is a homopolypropylene resin mixed with a copolypropylene resin at a mass ratio of 1:1; the homopolypropylene resin is a general-purpose homopolypropylene of T30S brand of Shanghai Petrochemical; the copolypropylene resin is a copolypropylene of K8003 brand of Dalian Hengli; the compatibilizer is maleic anhydride grafted PP, which is PO 1020 provided by the United States Exxon; the processing aid is a mixture of a lubricant and an antioxidant at a mass ratio of 1:1.5; the lubricant is zinc stearate; the antioxidant is antioxidant 168; and the synergist is melamine polyphosphate.

[0043] The preparation method of the modified nano inorganic flame retardant comprises the following steps:

[0044] Step I: disperse the silicon source, iron source, aluminum source, tin source and titanium source in an alcohol solvent, uniformly stir, slowly add sodium acetate, transfer the mixture to a polytetrafluoroethylene-lined hydrothermal reaction kettle, react at 205℃ for 19h, take out the reaction kettle, wash repeatedly with anhydrous ethanol and deionized water after the reaction system is cooled to room temperature, then dry in a vacuum drying oven at 87℃ for 17h, and finally calcine to obtain a nano-scale flame-retardant active ingredient;

[0045] Step II: uniformly mix the nano-scale flame-retardant active ingredient and nano-montmorillonite, disperse in N-methylpyrrolidone, then add silane coupling agent KH560, stir at 53℃ for 2.5h, then add 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridin-9-yl)boronic acid and meso-tetramethyl-meso-tetrakis-p-aminophenylcalix[4]pyrrole, stir at 73℃ for 4.5h, then remove the solvent by rotary evaporation to obtain the modified nano inorganic flame retardant.

[0046] In step I, the iron source is ferric nitrate; the silicon source is silicon tetrachloride; the aluminum source is aluminum nitrate; the tin source is tin chloride; and the titanium source is titanium nitrate; in step I, the mass ratio of the silicon source, iron source, aluminum source, tin source, titanium source, alcohol solvent and sodium acetate is 1:0.15:0.2:0.1:0.2:13:3; in step I, the alcohol solvent is ethylene glycol; and in step I, the calcination temperature is 600℃ and the time is 3.5h.

[0047] The mass ratio of the nanoscale flame-retardant active ingredient, nanometer montmorillonite, N-methyl pyrrolidone, silane coupling agent KH560, 3, 3'-diamino-4, 4'-difluorobenzophenone, (3, 6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole in step II is 3:1:17:1:0.5:0.15:0.1; the particle size of the nanometer montmorillonite is 30 nm.

[0048] A preparation method of the nanocomposite plastic flame-retardant master batch, comprising the following steps: adding each raw material into a high-speed mixer in weight parts, mixing for 17 min at a rotating speed of 900 r / min, so that each raw material is fully mixed and uniform, to obtain a mixture; then the mixture is added into a double screw extruder for melt extrusion, and after water cooling and granulation, the nanocomposite plastic flame-retardant master batch is obtained; the extrusion temperature of the double screw extruder is 215℃, and the screw rotating speed is 350 r / min.

[0049] Example 3

[0050] A nanocomposite plastic flame-retardant master batch, comprising the following raw materials made in weight parts: carrier resin 45 parts, compatibilizer 4 parts, processing aid 3 parts, modified nanometer inorganic flame retardant 25 parts, synergist 7 parts; the modified nanometer inorganic flame retardant is a co-modified nanometer inorganic flame retardant of 3, 3'-diamino-4, 4'-difluorobenzophenone, (3, 6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, and silane coupling agent KH560.

[0051] The preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and characterization of Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [J]. Chemical reagents, 2002 (6): 344-345; the carrier resin is a mixture of homopolymer polypropylene resin and copolymer polypropylene resin in a mass ratio of 1:1; the homopolymer polypropylene resin is a general-purpose homopolymer polypropylene of Shanghai Petrochemical brand T30S; the copolymer polypropylene resin is Dalian Hengli K8003 copolymer polypropylene; the compatibilizer is maleic anhydride grafted PP, and the brand is PO 1020, provided by the United States Exxon; the processing aid is a mixture of lubricant and antioxidant in a mass ratio of 1:2; the lubricant is zinc stearate; the antioxidant is antioxidant 1010; the synergist is melamine polyphosphate.

[0052] The preparation method of the modified nanometer inorganic flame retardant comprises the following steps:

[0053] Step I: disperse the silicon source, iron source, aluminum source, tin source, titanium source in an alcohol solvent, after stirring uniformly, slowly add sodium acetate, transfer the mixture into a polytetrafluoroethylene lined hydrothermal reactor, react at 215℃ for 21h; take out the reactor, after the reaction system is cooled to room temperature, repeatedly wash with anhydrous ethanol and deionized water, then dry in a vacuum drying oven at 90℃ for 19h, finally calcine, to obtain nanoscale flame retardant active ingredient;

[0054] Step II: mix the nanoscale flame retardant active ingredient and nanometer montmorillonite uniformly, then disperse in N-methyl pyrrolidone, then add silane coupling agent KH560 thereto, stir at 55℃ for 3h, then add 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl)boric acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup[4]pyrrole thereto, stir at 75℃ for 5h, then remove the solvent by rotary evaporation, to obtain modified nanometer inorganic flame retardant.

[0055] The iron source in Step I is ferric nitrate; the silicon source is sodium silicate; the aluminum source is aluminum nitrate; the tin source is tin chloride; the titanium source is titanium nitrate; the mass ratio of the silicon source, iron source, aluminum source, tin source, titanium source, alcohol solvent, sodium acetate in Step I is 1:0.2:0.2:0.1:0.2:15:3; the alcohol solvent in Step I is n-butanol; the temperature of the calcination in Step I is 650℃, and the time is 4h.

[0056] The mass ratio of the nanoscale flame retardant active ingredient, nanometer montmorillonite, N-methyl pyrrolidone, silane coupling agent KH560, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl)boric acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup[4]pyrrole in Step II is 3:1:20:1:0.5:0.2:0.1; the particle size of the nanometer montmorillonite is 50nm.

[0057] A preparation method of the nanocomposite plastic flame-retardant master batch, comprising the following steps: adding each raw material into a high-speed mixer according to weight parts, mixing at a rotating speed of 1000r / min for 18min, so that each raw material is fully mixed uniformly to obtain a mixture; then adding the mixture into a double-screw extruder for melt extrusion, and after water cooling and granulation, a nanocomposite plastic flame-retardant master batch is obtained; the extrusion temperature of the double-screw extruder is 220℃, and the screw rotating speed is 400r / min.

[0058] Example 4

[0059] A kind of nanocomposite plastic flame-retardant masterbatch, including the following raw materials made by weight parts: carrier resin 48 parts, compatibility agent 4.5 parts, processing aid 3.5 parts, modified nano inorganic flame retardant 28 parts, synergist 9 parts;The modified nano inorganic flame retardant is 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, silane coupling agent KH560 co-modified nano inorganic flame retardant.

[0060] The preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole synthesis and characterization [J]. Chemical reagents, 2002 (6): 344-345;The carrier resin is homopolymerization polypropylene resin, copolymerization polypropylene resin is mixed by mass ratio 1:1;The homopolymerization polypropylene resin is Shanghai Petrochemical brand T30S general-purpose homopolymerization polypropylene;The copolymerization polypropylene resin is Dalian Hengli K8003 copolymerization polypropylene;The compatibility agent is maleic anhydride grafted PP, and the brand is PO 1020, provided by the United States Exxon;The processing aid is lubricant, antioxidant mixed by mass ratio 1:2.5;The lubricant is zinc stearate;The antioxidant is antioxidant 1010, antioxidant 168 mixed by mass ratio 3:5;The synergist is melamine polyphosphate.

[0061] The preparation method of the modified nano inorganic flame retardant includes the following steps:

[0062] Step I: the silicon source, iron source, aluminum source, tin source, titanium source are dispersed in alcohol solvent, after stirring uniformly, sodium acetate is slowly added, the mixture is transferred to the polytetrafluoroethylene lined hydrothermal reactor, and is reacted at 220 DEG C for 23 h;The reaction kettle is taken out, and after the reaction system is cooled to room temperature, it is washed repeatedly with anhydrous ethanol and deionized water, then dried in a vacuum drying oven at 93 DEG C for 21 h, and finally calcined to obtain nanoscale flame retardant active ingredient;

[0063] Step II: the nanoscale flame retardant active ingredient and nanometer montmorillonite are mixed uniformly, then dispersed in N-methyl pyrrolidone, then silane coupling agent KH560 is added, stirred at 58 DEG C for 3.5 h, then 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl) boronic acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole are added, and stirred at 70-80 DEG C for 5.5 h, then the solvent is removed by rotary evaporation to obtain modified nano inorganic flame retardant.

[0064] The iron source in step I is ferric nitrate; the silicon source is sodium silicate; the aluminum source is aluminum nitrate; the tin source is tin chloride; the titanium source is titanium nitrate; the mass ratio of the silicon source, iron source, aluminum source, tin source, titanium source, alcohol solvent, sodium acetate in step I is 1:0.25:0.2:0.1:0.2:18:3; the alcohol solvent in step I is a mixture of ethanol, ethylene glycol and n-butanol in a mass ratio of 1:1:2; the calcination temperature in step I is 740 DEG C, and the time is 4.5 h.

[0065] The mass ratio of the nanoscale flame-retardant active ingredient, nanometer montmorillonite, N-methyl pyrrolidone, silane coupling agent KH560, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl)boric acid, and meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole in step II is 3:1:23:1:0.5:0.25:0.1; the particle size of the nanometer montmorillonite is 70 nm.

[0066] A preparation method of the nanocomposite plastic flame-retardant master batch, comprising the following steps: adding each raw material into a high-speed mixer in weight parts, mixing at a rotating speed of 1100 r / min for 19 min to fully mix and uniformly mix each raw material to obtain a mixed material; then adding the mixed material into a double-screw extruder to perform melt extrusion, and after water cooling and granulation, a nanocomposite plastic flame-retardant master batch is obtained; the extrusion temperature of the double-screw extruder is 225 DEG C, and the screw rotating speed is 450 r / min.

[0067] Example 5

[0068] A nanocomposite plastic flame-retardant master batch, comprising the following raw materials made in weight parts: carrier resin 50 parts, compatibilizer 5 parts, processing aid 4 parts, modified nanometer inorganic flame retardant 30 parts, and synergist 10 parts; the modified nanometer inorganic flame retardant is a co-modified nanometer inorganic flame retardant of 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl)boric acid, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, and silane coupling agent KH560.

[0069] The preparation method of the Meso-tetramethyl-meso-tetrakis-p-aminophenylcalix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and characterization of Meso-tetramethyl-meso-tetrakis-p-aminophenylcalix[4]pyrrole [J]. Chemical reagents, 2002 (6): 344-345; the carrier resin is a homopolypropylene resin mixed with a copolypropylene resin at a mass ratio of 1:1; the homopolypropylene resin is a general-purpose homopolypropylene of T30S brand of Shanghai Petrochemical; the copolypropylene resin is a copolypropylene of K8003 brand of Dalian Hengli; the compatibilizer is maleic anhydride grafted PP, which is PO 1020 provided by the United States Exxon; the processing aid is a mixture of a lubricant and an antioxidant at a mass ratio of 1:3; the lubricant is zinc stearate; the antioxidant is antioxidant 1010; the synergist is melamine polyphosphate.

[0070] The preparation method of the modified nano inorganic flame retardant comprises the following steps:

[0071] Step I: disperse the silicon source, iron source, aluminum source, tin source and titanium source in an alcohol solvent, stir uniformly, slowly add sodium acetate, transfer the mixture to a polytetrafluoroethylene-lined hydrothermal reaction kettle, react at 225℃ for 24h; take out the reaction kettle, wash repeatedly with anhydrous ethanol and deionized water after the reaction system is cooled to room temperature, then dry in a vacuum drying box at 95℃ for 22h, and finally calcine to obtain a nano-sized flame-retardant active ingredient;

[0072] Step II: mix the nano-sized flame-retardant active ingredient and nano-montmorillonite uniformly, disperse in N-methylpyrrolidone, then add silane coupling agent KH560, stir at 60℃ for 4h, then add 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridin-9-yl)boronic acid and meso-tetramethyl-meso-tetrakis-p-aminophenylcalix[4]pyrrole, stir at 80℃ for 6h, then remove the solvent by rotary evaporation to obtain the modified nano inorganic flame retardant.

[0073] The iron source in step I is ferric nitrate; the silicon source is sodium silicate; the aluminum source is aluminum nitrate; the tin source is tin chloride; the titanium source is titanium nitrate; the mass ratio of the silicon source, iron source, aluminum source, tin source, titanium source, alcohol solvent and sodium acetate in step I is 1:0.3:0.2:0.1:0.2:20:3; the alcohol solvent in step I is ethanol; the calcination temperature in step I is 750℃, and the time is 5h.

[0074] The mass ratio of the nanoscale flame-retardant active ingredient, nanometer montmorillonite, N-methyl pyrrolidone, silane coupling agent KH560, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridine-9-yl)boric acid and meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole in step II is 3:1:25:1:0.5:0.3:0.1; the particle size of the nanometer montmorillonite is 80 nm.

[0075] A preparation method of the nanocomposite plastic flame-retardant master batch, comprising the following steps: adding each raw material into a high-speed mixer in weight parts, mixing for 20 min at a rotating speed of 1200 r / min, so that each raw material is fully mixed and uniform, to obtain a mixture; then adding the mixture into a double-screw extruder for melt extrusion, and obtaining the nanocomposite plastic flame-retardant master batch after water cooling and granulation; the extrusion temperature of the double-screw extruder is 230 ℃, and the screw rotating speed is 500 r / min.

[0076] Comparative Example 1

[0077] A nanocomposite plastic flame-retardant master batch and a preparation method thereof, which are basically the same as those in Example 1, except that an equal amount of a silicon source is used instead of a tin source, and an equal amount of 3,3'-diamino-4,4'-difluorodiphenyl sulfone is used instead of (3,6-diaminoacridine-9-yl)boric acid.

[0078] Comparative Example 2

[0079] A nanocomposite plastic flame-retardant master batch and a preparation method thereof, which are basically the same as those in Example 1, except that an equal amount of a tin source is used instead of an iron source, and an equal amount of (3,6-diaminoacridine-9-yl)boric acid is used instead of 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0080] Comparative Example 3

[0081] A nanocomposite plastic flame-retardant master batch and a preparation method thereof, which are basically the same as those in Example 1, except that an equal amount of an iron source is used instead of a tin source, and meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole is not added.

[0082] The nanocomposite plastic flame-retardant master batches prepared in Examples 1-5 and Comparative Examples 1-3 are respectively subjected to performance testing, and the test results are shown in Table 1, and the test methods are as follows: the master batches prepared in each example are pressed into sample pieces on an injection molding machine, the vertical combustion performance is tested according to GB / T2408-2008, the thermal stability is that each product is respectively placed in an aging oven at 85 ℃ for artificial accelerated aging for 100 h, and after cooling to room temperature, the vertical combustion performance is detected again, and the flame-retardant grade is evaluated according to UL-94.

[0083] Table 1: Performance test results of nanocomposite plastic flame-retardant master batch

[0084]

[0085] As can be seen from Table 1, the nanocomposite plastic flame-retardant masterbatch disclosed in the embodiments of the present application has better flame-retardant effect and thermal stability compared with the comparative examples; the combination use of the silicon source, tin source, iron source, (3,6-diaminoacridin-9-yl)boronic acid, 3,3'-diamino-4,4'-difluorodiphenyl sulfone and meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole is beneficial to improving the above-mentioned properties.

[0086] The above shows and describes the basic principles, main features and advantages of the present application. It should be understood by those skilled in the art that the present application is not limited to the above-mentioned embodiments, and the above-mentioned embodiments and descriptions in the specification are only the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection required by the present application is defined by the appended claims and their equivalents.

Claims

1. A nanocomposite plastic flame retardant masterbatch, characterized in that, It is made from the following raw materials in parts by weight: 40-50 parts of carrier resin, 3-5 parts of compatibilizer, 2-4 parts of processing aid, 20-30 parts of modified nano-inorganic flame retardant, and 5-10 parts of synergist; the modified nano-inorganic flame retardant is 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridin-9-yl)boronic acid, meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, and silane coupling agent KH560 co-modified nano-inorganic flame retardant.

2. The nanocomposite plastic flame retardant masterbatch according to claim 1, characterized in that, The carrier resin is a mixture of homopolymer polypropylene resin and copolymer polypropylene resin in a mass ratio of 1:1; the homopolymer polypropylene resin is Shanghai Petrochemical's T30S general-purpose homopolymer polypropylene; and the copolymer polypropylene resin is Dalian Hengli's K8003 copolymer polypropylene.

3. The nanocomposite plastic flame retardant masterbatch according to claim 1, characterized in that, The compatibilizer is maleic anhydride-grafted PP, with the brand name PO 1020.

4. The nanocomposite plastic flame retardant masterbatch according to claim 1, characterized in that, The processing aid is a mixture of lubricant and antioxidant in a mass ratio of 1:(1-3); the lubricant is zinc stearate; and the antioxidant is at least one of antioxidant 1010 and antioxidant 168.

5. The nanocomposite plastic flame retardant masterbatch according to claim 1, characterized in that, The synergist is melamine polyphosphate.

6. The nanocomposite plastic flame retardant masterbatch according to claim 1, characterized in that, The preparation method of the modified nano-inorganic flame retardant includes the following steps: Step 1: Disperse silicon, iron, aluminum, tin, and titanium sources in an alcohol solvent, stir until homogeneous, slowly add sodium acetate, transfer the mixture to a hydrothermal reactor lined with polytetrafluoroethylene, and react at 200-225℃ for 18-24 hours; remove the reactor, and after the reaction system cools to room temperature, wash repeatedly with anhydrous ethanol and deionized water, then dry in a vacuum drying oven at 85-95℃ for 15-22 hours, and finally calcine to obtain nanoscale flame-retardant active ingredients; Step II: After mixing the nano-sized flame retardant active ingredients and nano-montmorillonite evenly, disperse them in N-methylpyrrolidone, then add silane coupling agent KH560, stir at 50-60℃ for 2-4h, then add 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridin-9-yl)boronic acid, meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, stir at 70-80℃ for 4-6h, then remove the solvent by rotary evaporation to obtain the modified nano-inorganic flame retardant.

7. The nanocomposite plastic flame retardant masterbatch according to claim 6, characterized in that, In step I, the iron source is ferric nitrate; the silicon source is at least one of sodium silicate and silicon tetrachloride; the aluminum source is aluminum nitrate; the tin source is tin chloride; and the titanium source is titanium nitrate. The mass ratio of the silicon source, iron source, aluminum source, tin source, titanium source, alcohol solvent, and sodium acetate in step I is 1:(0.1~0.3):0.2:0.1:0.2:(10~20):

3. The alcohol solvent in step I is at least one of ethanol, ethylene glycol, and n-butanol. The calcination temperature in step I is 550~750℃, and the time is 3-5 hours.

8. The nanocomposite plastic flame retardant masterbatch according to claim 6, characterized in that, The mass ratio of the nano-sized flame retardant active ingredient, nano-montmorillonite, N-methylpyrrolidone, silane coupling agent KH560, 3,3'-diamino-4,4'-difluorodiphenyl sulfone, (3,6-diaminoacridin-9-yl)boronic acid, and meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole in step II is 3:1:(15-25):1:0.5:(0.1-0.3):0.1; the particle size of the nano-montmorillonite is 10-80 nm.

9. A method for preparing a nanocomposite plastic flame-retardant masterbatch according to any one of claims 1-8, characterized in that, The process includes the following steps: adding each raw material according to its weight into a high-speed mixer and mixing it at a speed of 800-1200 r / min for 15-20 min to ensure that the raw materials are fully and evenly mixed to obtain a mixture; then adding the mixture into a twin-screw extruder for melt extrusion, and after water cooling and granulation, obtaining nano-composite plastic flame retardant masterbatch.

10. The method for preparing the nanocomposite plastic flame retardant masterbatch according to claim 9, characterized in that, The extrusion temperature of the twin-screw extruder is 210-230℃, and the screw speed is 300-500 r / min.

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