阅读说明：本技术 一种含溴低气味复合阻燃剂、制备方法及其在pp中的应用 (Bromine-containing low-odor composite flame retardant, preparation method and application thereof in PP ) 是由 王晓卡 裴广斌 陈红武 王晓川 聂晨晨 于 2020-12-17 设计创作，主要内容包括：本发明涉及高分子材料技术领域,公开了一种抑烟、低气味、增强阻燃剂,其由溴系阻燃剂、次磷酸盐阻燃剂、含氮阻燃剂、三氧化二锑经过水热反应得到,优选与抑烟剂混合使用。该抑烟、低气味、增强阻燃剂气味很低,对PP材料具有较高的阻燃效率,同时能够降低发烟量,提高力学性能和加工性能。(The invention relates to the technical field of high polymer materials, and discloses a smoke-inhibiting low-odor reinforced flame retardant which is prepared by carrying out hydrothermal reaction on a brominated flame retardant, a hypophosphite flame retardant, a nitrogen-containing flame retardant and antimony trioxide, and preferably mixing the brominated flame retardant, the hypophosphite flame retardant, the nitrogen-containing flame retardant and the antimony trioxide for use. The smoke-inhibiting low-odor enhanced flame retardant has low odor, has higher flame-retardant efficiency on PP materials, and can reduce the smoke amount and improve the mechanical property and the processability.)

1. The bromine-containing low-odor composite flame retardant is characterized by being prepared from a brominated flame retardant, a hypophosphite flame retardant, a nitrogen-containing flame retardant and antimony trioxide through a hydrothermal reaction.

2. The bromine-containing low-odor composite flame retardant according to claim 1, wherein four flame retardants are used in amounts by mass: 0.6-10 parts of brominated flame retardant, 1-15 parts of hypophosphite flame retardant, 2-50 parts of nitrogen-containing flame retardant and 0.01-1 part of antimony trioxide.

3. The bromine-containing low-odor composite flame retardant according to claim 2, wherein the four flame retardants are used in amounts of, by mass: 3-8 parts of brominated flame retardant, 5-10 parts of hypophosphite flame retardant, 20-40 parts of nitrogen-containing flame retardant and 0.2-1.0 part of antimony trioxide.

4. The bromine-containing low-odor composite flame retardant as claimed in claim 1, wherein the hydrothermal reaction is carried out at a temperature of from 0.1 to 0.5MPa and from 120 ℃ to 180 ℃.

5. The bromine-containing low-odor composite flame retardant according to claim 1, wherein the bromine-based flame retardant is one or more of decabromodiphenylethane, methyl octabromoether, brominated polystyrene, and brominated triazine; preferably, the hypophosphite flame retardant is one or more of aluminum hypophosphite, diethyl aluminum hypophosphite, calcium hypophosphite, magnesium hypophosphite and ammonium hypophosphite; preferably, the nitrogen-containing flame retardant is one or more of ammonium polyphosphate, melamine cyanurate.

6. The bromine-containing low-odor composite flame retardant according to any one of claims 1 to 5, characterized by further comprising boehmite in an amount of about 0.5 to 2.0 times, preferably 0.8 to 1.3 times, the mass of the flame retardant.

7. The method for preparing the bromine-containing low-odor composite flame retardant according to any one of claims 1 to 5, comprising the steps of:

adding bromine flame retardant, hypophosphite flame retardant, nitrogen-containing flame retardant and antimony trioxide into water to prepare slurry which is solid at 75-250 g/L,

putting the slurry into a high-pressure reaction kettle to carry out hydrothermal reaction for 2-20h at the temperature of 110-;

and carrying out suction filtration, drying and crushing on the slurry after reaction to obtain the bromine-phosphorus-nitrogen-antimony compound.

8. The method of preparing a bromine-containing low-odor composite flame retardant according to claim 7, further comprising adding the bromine-phosphorus-nitrogen-antimony composite to a smoke suppressant, mixing in a high-speed mixer, and drying in a forced air drying oven at 80 ℃ to 155 ℃.

9. The method of preparing a bromine-containing low-odor composite flame retardant according to claim 8, wherein the smoke suppressant is boehmite.

10. The bromine-containing low-odor composite flame retardant used in PP materials according to claim 6, wherein the composite flame retardant of the present invention is added in an amount of 2 to 20 parts, preferably 4 to 10 parts, per 100 parts of PP materials.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a functional auxiliary agent in the preparation of a high polymer material, and more particularly relates to a flame retardant used in the high polymer material.

Background

Polypropylene (PP) is widely used in the fields of automobiles, medicines, home appliances, food packaging, buildings, etc. because of its small relative density, good chemical properties, good electrical insulation, high temperature resistance, easy processing, and corrosion resistance. However, the oxygen index (LOI) of PP is only about 17.4%, PP is extremely easy to burn, releases a large amount of heat during burning, has a high flame propagation speed, is accompanied by the phenomena of fuming and dripping, is easy to cause a large-area fire, and poses great threat to the life safety of people, so that the application field of PP is limited.

At present, the brominated flame retardant is most widely applied to PP, and has low addition amount, high flame retardant efficiency and small influence on other properties of materials. The octabromoether not only contains aromatic bromine but also contains aliphatic bromine, the flame retardant efficiency of the octabromoether is greatly improved compared with other bromine, CN104277330A discloses that the octabromoether and antimony trioxide are combined to prepare PP flame retardant master batches, and when the flame retardant content of a PP product reaches 4%, the PP can reach the flame retardant grade of V2. But the bromine content is still high, which increases the smoke yield of the PP article.

In addition, bromine-based flame retardants such as octabromoether contain free bromine, which is easily volatilized when heated to form an offensive odor, which affects the use of PP. Usually, paraquat and organic peroxide are added as a flame-retardant synergist to improve the flame-retardant efficiency of the brominated flame retardant and reduce the content of bromine. For example, yangminghui, houxiamin and the like (modern plastic processing application, 2019, 31 (4): 21-24) adopt paraquat, melamine hydrobromide and diethyl aluminum hypophosphite to synergistically retard flame PP, and when the addition amount is about 1-2%, the PP can reach the flame retardation level of V2. However, both the paraquat and the organic peroxide can promote the molecular chain fracture of the PP, thereby influencing the mechanical property and the processing property of the PP. And the flame retardant synergist such as the paraquat and the organic peroxide has high toxicity and can emit unpleasant odor, so that the flame retardant synergist cannot be used in occasions with requirements on the odor.

Therefore, there is still a need in the field of polymer materials to develop a flame retardant that has a low smoke emission, a low odor, and a low decrease in mechanical properties of polymer materials, and does not decrease the flame retardant effect.

Disclosure of Invention

The invention aims to provide a flame retardant which has good flame retardance, small smoke amount, low odor and less reduction of the mechanical property of a high polymer material.

The invention also aims to provide the application of the flame retardant in the manufacturing of PP materials so as to improve the melt strength of the PP materials and meet the requirement of a complex extrusion processing process.

According to the first aspect of the invention, the bromine-containing low-odor composite flame retardant is mainly prepared from a brominated flame retardant, a hypophosphite flame retardant, a nitrogen-containing flame retardant and antimony trioxide through a hydrothermal reaction. In a general embodiment of the present invention, the hydrothermal reaction is carried out in a high pressure autoclave and in the range of 110 ℃ and 200 ℃. The reaction time can be changed within the range of 2-20h according to the pressure and the temperature. The pressure of the hydrothermal reaction may be between 0.1 and 0.7 MPa. The typical embodiment of the present invention, the reaction is carried out at a temperature of 120-150 ℃ for 3-7 hours using a pressure of 0.1-0.5 MPa.

The composite flame retardant of the invention adopts the multielement combination, thereby improving the flame retardant efficiency and reducing the bromine content in the product; moreover, the use of flame-retardant synergists such as paraquat, organic peroxide and the like is avoided, the smell of the product is reduced, and the breakage of a molecular chain of PP in the processing process is also reduced, so that the processing performance and the mechanical property of the high polymer material are improved.

In the present invention, it is important to carry out hydrothermal reaction of the composite components of the flame retardant. The inventor finds out through comparison that the composite flame retardant subjected to the hydrothermal reaction can obviously improve the smell of the flame retardant, and the flame retardant performance is also improved. The inventors have not clarified the mechanism of this action, and guessed a possibility that the bromine element in the flame retardant interacts with the amino group in the nitrogen-containing flame retardant or even this phosphate group in the hypophosphite flame retardant, thereby immobilizing free bromine; in addition, the full fusion of all the components of the flame retardant during the hydrothermal reaction can further improve the flame retardant efficiency of the flame retardant.

In a typical embodiment of the present invention, four flame retardants are used in amounts by mass: 0.6-10 parts of brominated flame retardant, 1-15 parts of hypophosphite flame retardant, 2-50 parts of nitrogen-containing flame retardant and 0.01-1 part of antimony trioxide. In the present invention, the amount of the brominated flame retardant is not more than 10 parts by weight as is sufficient for the purpose of use, but may be any amount (e.g., natural number) of 10 to 20 parts when necessary. The amount of the brominated flame retardant is preferably not less than 2 parts by weight, preferably between 3 and 8 parts by weight. The amount of hypophosphite flame retardant is typically between 5 and 10 parts by weight. The nitrogen-containing flame retardant is typically between 10 and 45 parts by weight, preferably between 25 and 40 parts by weight. The amount of antimony trioxide is generally between 0.2 and 1.2, preferably not more than 1.0, more preferably between 0.5 and 1.0.

The present invention does not exclude the possibility of adding other components to the above-mentioned components, for example, other types of flame retardants or adjuvants may be added to further optimize the flame retardant performance or to impart new functions, although the examples of the present invention do not provide examples of introducing other components, and other improvements may be easily made on the basis of the teaching of the present invention by those skilled in the art, which should fall within the scope of the present invention as defined by the claims.

In the present invention, the bromine-based flame retardant is preferably one or more of decabromodiphenylethane, methyl octabromoether, brominated polystyrene, and brominated triazine, but the present invention is not limited thereto. Suitable hypophosphite flame retardants are preferably one or more of aluminum hypophosphite, diethyl aluminum hypophosphite, calcium hypophosphite, magnesium hypophosphite, ammonium hypophosphite, although the invention is not limited thereto. Suitable nitrogen-containing flame retardants are preferably one or more of ammonium polyphosphate, melamine cyanurate, but the invention is not limited thereto.

In the present invention, the composite flame retardant is preferably used together with a smoke suppressant. The preferred smoke suppressant is boehmite, and the boehmite is used in an amount of about 0.5 to 4.0 times, preferably in an amount of 0.8 to 1.3 times, and more preferably in an amount of 0.9 to 1.1 times the mass of the flame retardant. Compared with the traditional molybdenum-series smoke suppressant, magnesium hydroxide, aluminum hydroxide and the like, the boehmite and bromine-phosphorus-nitrogen-antimony compound have good synergistic effect, so that the smoke generation amount of a product can be reduced, and the flame retardant efficiency of the flame retardant can be improved; meanwhile, since boehmite has a certain reinforcing effect, the flexural modulus and the impact strength of PP are improved.

In order to prepare the composite flame retardant, a brominated flame retardant, a hypophosphite flame retardant, a nitrogen-containing flame retardant and antimony trioxide are added into water to prepare slurry which is solid at 75g/L-250g/L, and then the slurry is put into a high-pressure reaction kettle to carry out hydrothermal reaction for 2-20h at the temperature of 110-; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound; and finally, adding the mixed bromine-phosphorus-nitrogen-antimony compound into a smoke suppressant, mixing in a high-speed mixer, and drying in a forced air drying oven at the temperature of 80-155 ℃ to obtain the composite flame retardant with low odor, low smoke generation and enhanced performance.

One typical application of the composite flame retardant according to the present invention is for flame retarding of PP materials. When the flame retardant is used, 2-4 parts of PP material is added to 100 parts of PP material, the flame retardant level of PP can reach V2, and the flame retardant efficiency is high. Usually, a proper amount of dispersing agent and compatilizer is added to promote uniform dispersion and compatibility of the flame retardant in the main material. The composite flame retardant of the invention is used for PP materials and shows improved bending strength, bending modulus, impact strength, melt flow rate and melt flow rate after multiple processing.

It is easy to understand that the composite flame retardant of the invention is also applicable to other organic polymer materials.

Detailed Description

The scheme of the invention is illustrated below by means of specific examples and comparative examples, in which:

the method for detecting the melt flow rate of the flame-retardant reinforced PP material comprises the following steps: adding the flame-retardant reinforced PP material into the double screw again to extrude and granulate, repeating the experiment for 5 times, and detecting the melt flow rate by using an MZ-2028 melt flow rate instrument of Jiangsu Mingzhu experiment mechanical Co., Ltd; the detection standard is GB/T3682.1-2018, the temperature is 190 ℃, and the weight is 5 kg.

The PP test sample strip is obtained by injection molding of a MA900S/280 injection molding machine of Haitian Plastic machine group, Inc.; evaluating the odor of the flame-retardant reinforced PP material by a tester for a sample strip which is just taken out from an injection mold; the bending strength and the bending modulus of the PP material are detected by an MZ-4000D electronic universal tester of Jiangsu Mingzhu experiment machinery, Inc., the detection standard is GB/T9341-2008, the spline size is 4mm 9.85mm 80mm, and the experiment speed is 10 mm/min; the impact strength is detected by an MZ-2054 simple beam impact tester of Suminzhu experimental machinery, Inc., the detection standard is GB/T1043-93, the spline size is 4mm 9.85mm 80mm, and the impact energy is 7.5J; the vertical burning is according to GB/T2048-2008, the size of the sample strip is 13mm by 3mm by 120 mm; the smoke quantity is detected by a JSC-2 plastic smoke density test device of Nanjing Jiangning analytical instrument, Inc., the detection standard is GB/T8323-2008, the sample size is 75mm multiplied by 3mm, and the sample is in a flame state; the limiting oxygen index (LOI) was determined by jf-3 oximeter of Ningbo Yinzhou Jinrui instrument and Equipment Co., Ltd. the detection standard was GB / t2406.2-2009, and the spline shape was type IV.

Example 1:

1. firstly, weighing 6 parts of methyl octabromoether, 8.5 parts of aluminum hypophosphite, 35 parts of melamine and 0.5 part of antimony trioxide, adding the weighed materials into water to prepare slurry with solid content of 150g/L, and then putting the slurry into a high-pressure reaction kettle for hydrothermal reaction for 5 hours at the temperature of 150 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 50 parts of boehmite, putting the boehmite into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and preserving heat for 2h at 105 ℃ to obtain the composite flame retardant.

100 parts of PP (T03S), 0.5 part of EBS (ethylene bis stearamide), 5 parts of compatilizer (maleic anhydride grafted modified polypropylene) and 4 parts of composite flame retardant are added into a high-speed mixer to be mixed for 5min, and then a double-screw extrusion granulator is used for extrusion and granulation to obtain the flame-retardant reinforced PP material.

Example 2:

1. firstly, 3 parts of methyl octabromoether, 4.8 parts of aluminum hypophosphite, 17 parts of melamine and 0.2 part of antimony trioxide are weighed and added into water to prepare slurry with the solid content of 150g/L, and then the slurry is put into a high-pressure reaction kettle to carry out hydrothermal reaction for 5 hours at the temperature of 150 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 75 parts of boehmite, putting the boehmite into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and preserving heat for 2h at 105 ℃ to obtain the composite flame retardant.

100 parts of PP (T03S), 0.5 part of EBS, 5 parts of compatilizer (maleic anhydride grafted modified polypropylene) and 15 parts of composite flame retardant are added into a high-speed mixer to be mixed for 5min, and then a double-screw extrusion granulator is used for extrusion granulation to obtain the flame-retardant reinforced PP material.

Example 3:

1. firstly, 10 parts of methyl octabromoether, 8.5 parts of aluminum hypophosphite, 40 parts of melamine and 1 part of antimony trioxide are weighed and added into water to prepare slurry with solid content of 150g/L, and then the slurry is put into a high-pressure reaction kettle to carry out hydrothermal reaction for 5 hours at the temperature of 150 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 50 parts of boehmite, putting the boehmite into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and preserving heat for 2h at 105 ℃ to obtain the composite flame retardant.

The preparation process of the flame retardant reinforced PP material is the same as that of example 1.

Example 4:

1. firstly, weighing 2 parts of methyl octabromoether, 4 parts of aluminum hypophosphite, 10 parts of melamine and 0.1 part of antimony trioxide, adding the mixture into water to prepare slurry with solid content of 150g/L, and then putting the slurry into a high-pressure reaction kettle for hydrothermal reaction for 5 hours at 105 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 50 parts of boehmite, putting the boehmite into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and preserving heat for 2h at 105 ℃ to obtain the composite flame retardant.

The preparation process of the flame retardant reinforced PP material is the same as that of example 2.

Example 5:

1. firstly, weighing 6 parts of decabromodiphenylethane, 8.5 parts of aluminum hypophosphite, 35 parts of melamine and 0.5 part of antimony trioxide, adding the materials into water to prepare slurry with the solid content of 150g/L, and then putting the slurry into a high-pressure reaction kettle for hydrothermal reaction for 5 hours at the temperature of 150 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 50 parts of boehmite, putting the boehmite into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and preserving heat for 2h at 105 ℃ to obtain the composite flame retardant.

The preparation process of the flame retardant reinforced PP material is the same as that of example 1.

Example 6:

1. firstly, weighing 6 parts of methyl octabromoether, 8.5 parts of diethyl aluminum hypophosphite, 35 parts of melamine and 1.2 parts of antimony trioxide according to the following components, adding the components into water to prepare slurry with the solid content of 150g/L, and then putting the slurry into a high-pressure reaction kettle to carry out hydrothermal reaction for 5 hours at 105 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 50 parts of boehmite, putting the boehmite into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and preserving heat for 2h at 105 ℃ to obtain the composite flame retardant.

The preparation process of the flame retardant reinforced PP material is the same as that of example 1.

Example 7:

1. firstly, 0.6 part of methyl octabromoether, 8.5 parts of aluminum hypophosphite, 40 parts of melamine and 0.06 part of antimony trioxide are weighed and added into water to prepare slurry with the solid content of 150g/L, and then the slurry is put into a high-pressure reaction kettle to carry out hydrothermal reaction for 5 hours at the temperature of 150 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 50 parts of boehmite, putting the boehmite into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and preserving heat for 2h at 105 ℃ to obtain the composite flame retardant.

The preparation process of the flame retardant reinforced PP material is the same as that of example 1.

Example 8:

1. firstly, 10 parts of methyl octabromoether, 15 parts of aluminum hypophosphite, 20 parts of melamine and 1 part of antimony trioxide are weighed and added into water to prepare slurry with the solid content of 150g/L, and then the slurry is put into a high-pressure reaction kettle to carry out hydrothermal reaction for 5 hours at the temperature of 105 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 50 parts of boehmite, putting the boehmite into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and preserving heat for 2h at 105 ℃ to obtain the composite flame retardant.

The preparation process of the flame retardant reinforced PP material is the same as that of example 1.

Example 9:

firstly, weighing 6 parts of methyl octabromoether, 8.5 parts of aluminum hypophosphite, 35 parts of melamine and 0.5 part of antimony trioxide, adding the weighed materials into water to prepare slurry with the solid content of 150g/L, and then putting the slurry into a high-pressure reaction kettle to carry out hydrothermal reaction for 5 hours at the temperature of 150 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

the preparation process of the flame-retardant reinforced PP material corresponding to the bromine-phosphorus-nitrogen-antimony compound is as follows: 100 parts of PP (T03S), 0.5 part of EBS, 5 parts of compatilizer (maleic anhydride grafted modified polypropylene) and 2 parts of composite flame retardant are added into a high-speed mixer to be mixed for 5min, and then a double-screw extrusion granulator is used for extrusion granulation to obtain the flame-retardant reinforced PP material. .

Comparative example 1:

1. firstly, weighing 6 parts of methyl octabromoether, 8.5 parts of aluminum hypophosphite, 35 parts of melamine and 0.5 part of antimony trioxide according to the following components, adding the components into water to prepare slurry with the solid content of 150g/L, and then putting the slurry into a high-pressure reaction kettle to carry out hydrothermal reaction for 5 hours at the temperature of 150 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

2. weighing 50 parts of magnesium hydroxide, putting the magnesium hydroxide into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, mixing for 5min at a high speed, and then putting the mixture into a forced air drying oven, and keeping the temperature of the mixture at 105 ℃ for 2h to obtain the composite flame retardant.

The preparation process of the flame retardant reinforced PP material is the same as that of example 1.

Comparative example 2:

firstly, 40 parts of methyl octabromoether, 15 parts of antimony trioxide and 45 parts of boehmite are added into a high-speed mixer and mixed for 30min to obtain the bromine-antimony composite flame retardant.

The preparation process of the flame-retardant reinforced PP material corresponding to the bromine-antimony composite flame retardant is as follows: 100 parts of PP (T03S), 0.5 part of EBS, 5 parts of compatilizer (maleic anhydride grafted modified polypropylene) and 8 parts of composite flame retardant are added into a high-speed mixer to be mixed for 5min, and then a double-screw extrusion granulator is used for extrusion granulation to obtain the flame-retardant reinforced PP material.

Comparative column 3:

firstly, 25 parts of melamine hydrobromide, 15 parts of aluminum hypophosphite, 10 parts of paraquat and 50 parts of boehmite are prepared; then all the components of the composite flame retardant are put into a high-speed mixer to be mixed for 30min to obtain the paraquat synergistic bromine-nitrogen-phosphorus composite flame retardant.

The preparation process of the flame-retardant reinforced PP material corresponding to the paraquat synergistic bromine-nitrogen-phosphorus composite flame retardant is the same as that in the specific example 1.

Comparative example 4:

firstly, weighing 6 parts of methyl octabromoether, 8.5 parts of aluminum hypophosphite, 35 parts of melamine and 0.5 part of antimony trioxide, adding the weighed materials into water to prepare slurry with the solid content of 150g/L, and then putting the slurry into a high-pressure reaction kettle to carry out hydrothermal reaction for 5 hours at the temperature of 150 ℃; carrying out suction filtration, drying and crushing on the slurry after reaction to obtain a bromine-phosphorus-nitrogen-antimony compound;

comparative example 4:

1. firstly, weighing 6 parts of methyl octabromoether, 8.5 parts of aluminum hypophosphite, 35 parts of melamine and 1.2 parts of antimony trioxide according to the following components, and putting the components into a high-speed mixer for mixing for 30min to obtain a bromine-nitrogen-phosphorus-antimony composite flame retardant;

2. weighing 50 parts of boehmite, putting into a high-speed mixer, adding the bromine-nitrogen-phosphorus-antimony composite flame retardant, and mixing for 5min at a high speed to obtain the smoke-suppressing composite flame retardant.

The preparation process of the flame-retardant reinforced PP material corresponding to the smoke-suppressing composite flame retardant is the same as that of the specific example 1.

The PP material samples were tested for vertical burn rating, oxygen index and smoke generation and odor using the above-described instruments and standards, and the results are shown in Table 1.

TABLE 1 flame retardancy and odor of examples 1 to 6 and comparative examples 1 to 5

Mechanical property parameters of each PP material sample were measured using the aforementioned instruments and standards, and the results are shown in Table 2.

TABLE 1 processability and mechanical Properties of the samples of examples 1 to 6 and comparative examples 1 to 5