阅读说明：本技术 含“四位一体”阻燃剂的聚乙烯阻燃复合材料及其制备方法 (Polyethylene flame-retardant composite material containing 'four-in-one' flame retardant and preparation method thereof ) 是由 冯才敏 黄健光 姜佳丽 练翠霞 农彦彦 黄翠虹 马彦 彭建兵 梁敏仪 张浥琨 黄 于 2020-12-11 设计创作，主要内容包括：本发明涉及一种含“四位一体”阻燃剂的聚乙烯阻燃复合材料及其制备方法,包括55-84%的聚乙烯、14.5-35%的膨胀型阻燃剂、1-5%的粉体增效剂、0.1-0.5%的抗氧剂及0.1-5%的润滑剂,它们为质量百分比。其具有改善了阻燃剂的耐热性、耐水性的同时,通过阻燃剂的结构设计与调整,制备高效的阻燃体系等优点。(The invention relates to a polyethylene flame-retardant composite material containing 'four-in-one' flame retardant and a preparation method thereof, which comprises 55-84% of polyethylene, 14.5-35% of intumescent flame retardant, 1-5% of powder synergist, 0.1-0.5% of antioxidant and 0.1-5% of lubricant by mass percentage. The flame retardant has the advantages that the heat resistance and the water resistance of the flame retardant are improved, and meanwhile, an efficient flame retardant system is prepared through the structural design and adjustment of the flame retardant.)

1. The polyethylene flame-retardant composite material containing 'four-in-one' flame retardant is characterized by comprising 55-84% of polyethylene, 14.5-35% of intumescent flame retardant, 1-5% of powder synergist, 0.1-0.5% of antioxidant and 0.1-5% of lubricant by mass percent.

2. The polyethylene flame-retardant composite material containing the 'tetrad' flame retardant as claimed in claim 1, wherein the intumescent flame retardant comprises the 'tetrad' intumescent flame retardant, or the intumescent flame retardant comprises ammonium polyphosphate or melamine polyphosphate or piperazine pyrophosphate or aluminum hypophosphite and the 'tetrad' intumescent flame retardant, and the mass ratio of the ammonium polyphosphate or melamine polyphosphate or piperazine pyrophosphate or aluminum hypophosphite to the 'tetrad' intumescent flame retardant is 10: 1-1: 10; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

3. The flame retardant composite of polyethylene containing "quarternary" flame retardant of claim 1, wherein said lubricant is one or more of polyethylene wax, polypropylene wax, stearic acid, calcium stearate, zinc stearate, and N, N-ethylene bis stearamide.

4. The flame retardant polypropylene composite material containing triazine ring and cage-like structure flame retardant of claim 1, wherein the powder synergist is one or a mixture of two of nano zirconium phosphate, ultra-fine wollastonite, ultra-fine talcum powder, nano zinc oxide, nano lanthanum oxide and nano cerium oxide.

5. The preparation method of the polyethylene flame-retardant composite material containing the 'tetrad' flame retardant according to claim 1, which is characterized by comprising the following steps: firstly, 55 to 85 percent of polyethylene, 0.1 to 5 percent of lubricant and 0.1 to 0.5 percent of antioxidant are put into a high-speed mixer to be dispersed for 2 to 5 minutes at high speed, so as to obtain a resin mixture; then mixing 14.5-40% of intumescent flame retardant and 1-5% of powder synergist at high speed for 5-20 minutes at 50-100 ℃ to obtain an intumescent flame retardant mixture; and then uniformly mixing the intumescent flame retardant mixture and the resin mixture, and finally extruding and granulating by using a double-screw extruder or uniformly mixing by using a double-roller mixing roll to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant, wherein the temperature of each area of the double-screw extruder or the temperature of each area of the double-roller mixing roll is set to be between 130 ℃ and 200 ℃.

Technical Field

The invention relates to the technical field of flame-retardant polyethylene composite materials, in particular to a polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant and a preparation method thereof.

Background

Polyethylene is used as a general plastic with excellent comprehensive performance and cost performance, and is widely applied to the aspects of household appliances, electronics, building materials, packaging materials and the like. However, polyethylene is flammable, the oxygen index is only 17-18%, a large amount of molten drops are generated during combustion, the fire hazard is high, and the like, so that the use of polyethylene in occasions with flame retardant requirements is limited. Therefore, it is highly desirable to modify polyethylene for flame retardancy.

The more common and economical method in industry is to use additive flame retardants. The flame retardants most commonly used in polyethylene can be divided into three major classes, halogen-containing flame retardants (especially bromine-containing flame retardants), metal hydroxides and intumescent flame retardants.

The halogen-containing flame retardant has good flame retardant effectFruits, especially brominated flame retardants (e.g. decabromodiphenylethane, etc.) and antimony trioxide (Sb)₂O₃) The compound system has broad-spectrum flame retardant property and is widely applied to flame retardant products of various polymers; however, the flame retardant can release a large amount of toxic and harmful gases (such as halogenated hydrogen, dioxin and the like) during combustion, and seriously endangers life safety and environmental safety.

The metal hydroxide releases water vapor in the combustion process to dilute the combustible gas, and the generated metal oxide covers the surface of the material to play a role in blocking, so that the material has the advantages of no toxicity, no pollution and the like; however, their flame retardant efficiency is low, and it usually needs to add 50-60 wt% to reach the required flame retardant level, and its compatibility with polymer base material is poor, and it has great damage to the mechanical properties of the material, thus limiting its application in materials. The patent CN109111674A and CN109233061A adopt halogen-containing flame retardant or are compounded with inorganic flame retardant to prepare the polyethylene cable material. However, this will produce toxic fumes. Therefore, it is important to develop an environment-friendly, efficient, halogen-free, low-toxicity, low-smoke flame retardant.

The Intumescent Flame Retardant (IFR) takes phosphorus-nitrogen as a main flame retardant element, can form an intumescent compact carbon layer during combustion, and can block the transfer of air, combustible substances and heat, thereby realizing the flame retardant effect, and is considered as the environment-friendly flame retardant with the greatest development prospect. The first-discovered intumescent flame retardant is compounded by ammonium polyphosphate (APP), Pentaerythritol (PER) and Melamine (MEL), and has a good flame retardant effect on polyolefin. Patents CN108084546A and CN101624457A respectively adopt red mud compounded intumescent flame retardant or halogen-containing flame retardant to prepare flame retardant polyethylene, and have better effect. Pentaerythritol and its derivatives have high moisture absorption and are small molecules, and thus tend to exude from the polymer. Therefore, the development of a carbon-forming agent which is hardly soluble in water and has a large molecular weight has been a hot point of research.

Currently used intumescent flame retardants also have the following disadvantages: 1. the flame retardant efficiency is not high, and the addition amount is large; 2) especially, the single-molecule flame retardant has unreasonable element proportion, small adjustable range and insufficient flame retardant performance; 3) the flame retardant has insufficient heat resistance and water resistance. Therefore, the invention aims to improve the heat resistance and the water resistance of the flame retardant, and simultaneously, prepare a high-efficiency flame retardant system through the structural design and adjustment of the flame retardant, reduce the water solubility and the mobility, and make up for the defect of low adjustability of the monomolecular flame retardant.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant and a preparation method thereof, which improve the heat resistance and the water resistance of the flame retardant, improve the flame-retardant efficiency, reduce the water solubility and the mobility and make up the defect of low adjustability of a monomolecular flame retardant through the structural design and adjustment of the flame retardant.

In order to achieve the purpose, the first technical scheme of the invention is a polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant, which is characterized by comprising 55-84% of polyethylene, 14.5-35% of an intumescent flame retardant, 1-5% of a powder synergist, 0.1-0.5% of an antioxidant and 0.1-5% of a lubricant in percentage by mass.

In the technical scheme, the intumescent flame retardant comprises a quaternity intumescent flame retardant, or the intumescent flame retardant comprises ammonium polyphosphate or melamine polyphosphate or piperazine pyrophosphate or aluminum hypophosphite and a quaternity intumescent flame retardant, and the mass ratio of the ammonium polyphosphate or melamine polyphosphate or piperazine pyrophosphate or aluminum hypophosphite to the quaternity intumescent flame retardant is 10: 1-1: 10; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In the technical scheme, the lubricant is one or a mixture of more than two of polyethylene wax, polypropylene wax, stearic acid, calcium stearate, zinc stearate and N, N-ethylene bis-stearic acid amide.

In the technical scheme, the powder synergist is one or a mixture of two of nano zirconium phosphate, superfine wollastonite, superfine talcum powder, nano zinc oxide, nano lanthanum oxide and nano cerium oxide.

In order to achieve the above object, the second technical scheme of the present invention is a preparation method of a polyethylene flame retardant composite material containing a "four-in-one" flame retardant, which is characterized by comprising the following steps: firstly, 55 to 85 percent of polyethylene, 0.1 to 5 percent of lubricant and 0.1 to 0.5 percent of antioxidant are put into a high-speed mixer to be dispersed for 2 to 5 minutes at high speed, so as to obtain a resin mixture; then mixing 14.5-40% of intumescent flame retardant and 1-5% of powder synergist at high speed for 5-20 minutes at 50-100 ℃ to obtain an intumescent flame retardant mixture; and then uniformly mixing the intumescent flame retardant mixture and the resin mixture, and finally extruding and granulating by using a double-screw extruder or uniformly mixing by using a double-roller mixing roll to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant, wherein the temperature of each area of the double-screw extruder or the temperature of each area of the double-roller mixing roll is set to be between 130 ℃ and 200 ℃.

Compared with the prior art, the invention has the advantages that: the heat resistance and the water resistance of the flame retardant are improved, and meanwhile, a high-efficiency flame retardant system is prepared through the structural design and adjustment of the flame retardant.

Detailed Description

The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

Example one

The composite material is a polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant, and comprises 3.295Kg of polyethylene, 1.5Kg of 'four-in-one' intumescent flame retardant, 0.05Kg of powder synergist, 0.005Kg of antioxidant and 0.15Kg of lubricant.

In this embodiment, the intumescent flame retardant comprises a "four-in-one" intumescent flame retardant; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In this example, the lubricant is polyethylene wax.

In this embodiment, the powder synergist is nano lanthanum oxide.

In this example, a preparation method of a polyethylene flame retardant composite material containing a "four-in-one" flame retardant, which comprises adding 3.295Kg of polyethylene pellets, 0.15Kg of polyethylene wax, and 0.005Kg of antioxidant (1010) into a high-speed dispersing agent for premixing for 2 minutes, wherein the rotation speed of the high-speed dispersing machine is 800 rpm, to obtain a resin mixture; then, 1.5kg of 'four-in-one' intumescent flame retardant (FR 1) and 0.05kg of nano lanthanum oxide are accurately weighed respectively and added into the mixer to be mixed for 15 minutes, so that the flame retardant coats the nano lanthanum oxide, and a flame retardant mixture is obtained; then uniformly mixing the two mixtures to obtain an expansion type flame-retardant mixture; finally, the obtained intumescent flame-retardant mixture is put into a double-screw extruder for extrusion, cooling and granulation, and the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is obtained; wherein the temperature of each area of the double-screw extruder is set at 150-190 ℃; the oxygen index of the obtained polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is 32.5%, and the UL-94 test reaches V-0 level (1.6 mm). In practice, a two-roll mixer may be used instead of the twin-screw extruder.

Example two

A polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant is characterized by comprising 2.795kg of polyethylene, 2kg of intumescent flame retardant, 0.05kg of powder synergist, 0.005kg of antioxidant and 0.15kg of lubricant.

In this embodiment, the intumescent flame retardant comprises ammonium polyphosphate and a 'quartet' intumescent flame retardant, the mass of the ammonium polyphosphate is 1kg, and the mass of the 'quartet' intumescent flame retardant is 1 kg; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In this example, the lubricant is polyethylene wax.

In this embodiment, the powder synergist is nano zinc oxide.

In this example, which is a preparation method of polyethylene flame retardant composite material containing "four-in-one" flame retardant, 2.795Kg of polyethylene pellets, 0.005Kg of antioxidant (1010) and 0.15Kg of polyethylene wax were added into a high-speed dispersant for premixing for 3 minutes, and the rotation speed of the high-speed disperser was 1000 rpm, to obtain a resin mixture; then, 1.0kg of ammonium polyphosphate (APP), 1.0kg of 'four-in-one' flame retardant (FR 2) and 0.05kg of nano zinc oxide are respectively and accurately weighed and added into other mixers to be heated and mixed for 20 minutes, so that in-situ coating of the nano zinc oxide is realized, and an intumescent flame retardant mixture is obtained; uniformly mixing the two mixtures to obtain a flame-retardant composite material mixture, and finally putting the obtained intumescent flame-retardant mixture in a double-screw extruder for extrusion, cooling and granulation to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant; wherein, the temperature of each area of the double-screw extruder is set at 160-190 ℃; the oxygen index of the obtained polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is 38.8%, and the UL-94 test reaches V-0 level (0.8 mm). In practice, a two-roll mixer may be used instead of the twin-screw extruder.

EXAMPLE III

A polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant is characterized by comprising 3.34kg of polyethylene, 1.5kg of intumescent flame retardant, 0.05kg of powder synergist, 0.01kg of antioxidant and 0.1kg of lubricant.

In this example, the intumescent flame retardant comprises melamine polyphosphate and a "quarternary" intumescent flame retardant, the mass of melamine polyphosphate is 1.35kg, and the mass of the "quarternary" intumescent flame retardant is 0.15 kg; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In this example, the lubricant is N, N-ethylene bis stearamide.

In this embodiment, the powder synergist is nano cerium oxide.

In this example, a preparation method of a polyethylene flame retardant composite material containing a "four-in-one" flame retardant, first adding 3.34Kg of polyethylene pellets, 0.010Kg of antioxidant (168) and 0.10k of N, N-Ethylene Bis Stearamide (EBS) into a high-speed mixer to premix for 5 minutes, wherein the rotation speed of the high-speed mixer is 1200 r/min, so as to obtain a resin mixture; then, 1.35kg of melamine polyphosphate (MPP), 0.15kg of 'four-in-one' flame retardant (FR 3) and 0.05kg of nano cerium oxide are respectively and accurately weighed and added into other high-speed mixers for heating and premixing for 10 minutes to realize in-situ coating of the nano cerium oxide and obtain an intumescent flame retardant mixture; uniformly mixing the two mixtures to obtain a flame-retardant composite material mixture; and finally, extruding, cooling and granulating the intumescent flame-retardant mixture in a double-screw extruder to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant. Wherein the temperature of each zone of the double-screw extruder is 150 ℃ and 200 ℃.

The oxygen index of the obtained polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is 34.2%, and the UL-94 test reaches V-0 level (1.6 mm). In practice, a two-roll mixer may be used instead of the twin-screw extruder.

Example four

A polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant is characterized by comprising 3.89kg of polyethylene, 1kg of intumescent flame retardant, 0.05kg of powder synergist, 0.01kg of antioxidant and 0.05kg of lubricant.

In this example, the intumescent flame retardant comprises piperazine pyrophosphate with a "quadbit" intumescent flame retardant, the mass of the piperazine pyrophosphate being 0.75kg, the mass of the "quadbit" intumescent flame retardant being 0.25 kg; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In this example, the lubricant is calcium stearate.

In this embodiment, the powder synergist is nano lanthanum oxide.

In this embodiment, a preparation method of a polyethylene flame retardant composite material containing a "four-in-one" flame retardant is provided, first adding 3.89Kg of polyethylene powder, 0.01Kg of antioxidant 264 and 0.05Kg of calcium stearate into a high-speed dispersion machine for premixing for 4 minutes, wherein the rotation speed of the high-speed dispersion machine is 1000 rpm, so as to obtain a resin mixture; respectively and accurately weighing 0.75kg of piperazine pyrophosphate, 0.25kg of 'four-in-one' flame retardant (FR 4) and 0.05kg of nano lanthanum oxide, adding the materials into other high-speed mixers, heating and premixing for 8 minutes to realize in-situ coating of the nano lanthanum oxide and obtain an intumescent flame retardant mixture; uniformly mixing the two mixtures to obtain a flame-retardant composite material mixture; and finally, extruding, cooling and granulating in a double-screw extruder to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant. Wherein the temperature of each zone of the double-screw extruder is set at 130-180 ℃.

The oxygen index of the obtained polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is 32.5%, and the UL-94 test reaches V-0 level (1.6 mm). In practice, a two-roll mixer may be used instead of the twin-screw extruder.

EXAMPLE five

A polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant is characterized by comprising 3.085kg of polyethylene, 1.5kg of intumescent flame retardant, 0.25kg of powder synergist, 0.015kg of antioxidant and 0.15kg of lubricant.

In this example, the intumescent flame retardant comprises aluminium hypophosphite and a "quartet" intumescent flame retardant, the mass of the aluminium phosphate being 0.3kg, the mass of the "quartet" intumescent flame retardant being 1.2 kg; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In this example, the lubricant is stearic acid.

In this embodiment, the powder synergist is wollastonite.

In this example, it is a preparation method of polyethylene flame retardant composite material containing "four-in-one" flame retardant, firstly adding 3.085Kg of polyethylene pellets, 0.015Kg of antioxidant (mixture of 168 and 1098) and 0.15Kg of stearic acid into a high speed dispersion machine, premixing for 6 minutes, the rotation speed of the high speed dispersion machine is 1100 r/min, obtaining resin mixture; respectively and accurately weighing 0.3kg of aluminum hypophosphite, 1.20kg of 'four-in-one' flame retardant (FR 5) and 0.25kg of needle-shaped wollastonite (3000 meshes), adding the weighed materials into other high-speed mixers, premixing for 8 minutes, realizing in-situ coating of the wollastonite, and obtaining an intumescent flame retardant mixture; uniformly mixing the two mixtures to obtain a flame-retardant composite material mixture; and finally, extruding, cooling and granulating in a double-screw extruder to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant. Wherein the temperature of each zone of the double-screw extruder is set at 140-200 ℃.

The oxygen index of the obtained polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is 34.1%, and the UL-94 test reaches V-0 level (1.6 mm). In practice, a two-roll mixer may be used instead of the twin-screw extruder.

EXAMPLE six

A polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant is characterized by comprising 2.835kg of polyethylene, 1.5kg of intumescent flame retardant, 0.5kg of powder synergist, 0.015kg of antioxidant and 0.15kg of lubricant.

In this example, the intumescent flame retardant comprises ammonium polyphosphate and a "quartet" intumescent flame retardant, the mass of the ammonium polyphosphate is 1.25kg, and the mass of the "quartet" intumescent flame retardant is 0.25 kg; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In this example, the lubricant is stearic acid.

In this embodiment, the powder synergist is ultrafine talc powder.

In this example, it is a preparation method of polyethylene flame retardant composite material containing "four-in-one" flame retardant, firstly adding 2.835Kg of polyethylene pellets, 0.015Kg of antioxidant (mixture of 168 and 1010) and 0.15Kg of stearic acid into a high speed dispersion machine, premixing for 6 minutes, the rotation speed of the high speed dispersion machine is 1000 r/min, obtaining resin mixture; respectively and accurately weighing 1.25kg of ammonium polyphosphate, 0.25kg of 'four-in-one' flame retardant (FR 6) and 0.5kg of superfine talcum powder, adding the materials into the high-speed mixer, heating and premixing for 8 minutes to realize in-situ coating of the talcum powder, and obtaining an intumescent flame retardant mixture; uniformly mixing the two mixtures to obtain a flame-retardant composite material mixture; finally, extruding, cooling and granulating in a double-screw extruder to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant; wherein, the temperature of each area of the double-screw extruder is set at 150-200 ℃; the oxygen index of the obtained polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is 35.3%, and the UL-94 test reaches V-0 level (0.8 mm). In practice, a two-roll mixer may be used instead of the twin-screw extruder.

EXAMPLE seven

A polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant is characterized by comprising 3.285kg of polyethylene, 1.5kg of intumescent flame retardant, 0.05kg of powder synergist, 0.015kg of antioxidant and 0.15kg of lubricant.

In this embodiment, the intumescent flame retardant comprises ammonium polyphosphate and a 'quadbit' intumescent flame retardant, the mass of the ammonium polyphosphate is 1.2kg, and the mass of the 'quadbit' intumescent flame retardant is 0.3 kg; wherein:

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In this example, the lubricant is stearic acid.

In this embodiment, the powder synergist is nano zirconium phosphate and nano lanthanum oxide, the mass of the nano zirconium phosphate is 0.03kg, and the mass of the nano lanthanum oxide is 0.02 kg.

In this example, it is a preparation method of polyethylene flame retardant composite material containing "four-in-one" flame retardant, firstly adding 3.285Kg of polyethylene pellets, 0.015Kg of antioxidant (mixture of 168 and 1010) and 0.15Kg of stearic acid into a high speed dispersion machine, premixing for 6 minutes, the rotation speed of the high speed dispersion machine is 1000 r/min, obtaining resin mixture; respectively and accurately weighing 1.2kg of ammonium polyphosphate, 0.3kg of 'four-in-one' flame retardant (FR 7), 0.03kg of nano zirconium phosphate and 0.02kg of nano lanthanum oxide, adding the materials into the high-speed mixer, heating and premixing for 8 minutes to realize in-situ coating of the nano zirconium phosphate and the nano lanthanum oxide, and obtaining an intumescent flame retardant mixture; uniformly mixing the two mixtures to obtain a flame-retardant composite material mixture; finally, extruding, cooling and granulating in a double-screw extruder to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant; wherein, the temperature of each area of the double-screw extruder is set at 150-200 ℃; the oxygen index of the obtained polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is 35.7%, and the UL-94 test reaches V-0 level (1.6 mm). In practice, a two-roll mixer may be used instead of the twin-screw extruder.

Example eight

A polyethylene flame-retardant composite material containing a 'four-in-one' flame retardant is characterized by comprising 3.525kg of polyethylene, 1.25kg of intumescent flame retardant, 0.07kg of powder synergist, 0.005kg of antioxidant and 0.15kg of lubricant.

In this embodiment, the intumescent flame retardant comprises a "four-in-one" intumescent flame retardant;

the structural formula of the flame retardant containing the four-in-one is as follows:

in the formula: y is NH or O;

r1 is one of a straight or branched chain alkyl group containing 1 to 18 carbons, or R1 is one of p-phenyl, m-phenyl or o-phenyl;

r2 is an aminosilane coupling agent which is gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, aminopropylsilane hydrolysate, gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltrimethoxysilane, N-beta- (aminoethyl) -aminopropyltriethoxysilane, gamma-divinyltriaminopropylmethyldimethoxysilane, gamma-divinyltriaminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diamidopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-, One or the mixture of bis- (gamma-trimethoxysilylpropyl) amine, bis- (gamma-triethoxysilylpropyl) amine, gamma-piperazinylpropylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane and gamma-diethylaminomethyltriethoxysilane; the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, and the polymerization degree n is more than or equal to 1500; the polymerization degree n of the polyphosphoric acid melamine is more than or equal to 1000.

In this example, the lubricant is polyethylene wax.

In this embodiment, the powder synergist is nano zinc oxide and nano cerium oxide, the mass of the nano zinc oxide is 0.05kg, and the mass of the nano cerium oxide is 0.02 kg.

In this example, which is a preparation method of polyethylene flame retardant composite material containing "four-in-one" flame retardant, 3.525Kg of polyethylene pellets, 0.005Kg of antioxidant (1010) and 0.15Kg of polyethylene wax were added to the high speed dispersant for premixing for 2 minutes, and the rotation speed of the high speed disperser was 800 rpm to obtain a resin mixture; then accurately weighing 1.25kg of monomolecular flame retardant (FR 8), 0.05kg of nano zinc oxide and 0.02kg of nano cerium oxide respectively, adding into other mixers, heating and mixing for 15 minutes to realize in-situ coating of the nano zinc oxide and the nano cerium oxide, and obtaining an intumescent flame retardant mixture; uniformly mixing the two mixtures to obtain a flame-retardant composite material mixture; and finally, putting the obtained intumescent flame-retardant mixture in a double-screw extruder for extrusion, cooling and granulation to obtain the polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant. Wherein the temperature of each area of the double-screw extruder is set at 150-190 ℃; the oxygen index of the obtained polyethylene flame-retardant composite material containing the 'four-in-one' flame retardant is 32.6 percent, and the UL-94 test reaches V-0 level (1.6 mm); in practice, a two-roll mixer may be used instead of the twin-screw extruder.

The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention.