CN114133622A - Composite flame retardant and preparation method and application thereof - Google Patents
Composite flame retardant and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of flame retardants, and particularly relates to a composite flame retardant, and a preparation method and application thereof, wherein the composite flame retardant comprises an organic flame retardant, an inorganic flame retardant, a synergist and a biomass flame retardant; the inorganic flame retardant comprises any one of zinc borate, bis (bistrimethylsilyl) amine zinc modified magnesium hydroxide and magnesium hydroxide coated red phosphorus; the biomass flame retardant is prepared by reacting biomass phytic acid and dicyandiamide; the composite flame retardant can be used for preparing flame-retardant high-molecular polymer master batches, can be further prepared into cable materials or fabrics, solves the problems of washability and flame retardance of the fabrics, and makes it possible to effectively improve the flame retardance under the condition of less addition amount.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a composite flame retardant and a preparation method and application thereof.
Background
For a long time, because China has no mandatory flame retardant standard, compared with Euramerican days, the consumption of domestic flame retardant products is very low, taking plastic and rubber products as examples, American flame retardant plastic and rubber products account for about 40% of the total amount of plastic and rubber, and China has less than 2%. The scale of the manufacturers is small, the technology content is low, and the technology level is laggard. In recent years, the annual average growth rate of the production of Chinese flame retardants is estimated to be 15% -20%, which is far higher than the global level of 3% -4%. The yield of the domestic plastic products in 2010 is 5830.38 ten thousand tons, rubber, electronic products and the like are added according to the calculation that the flame retardant plastic accounts for 20 percent of the plastic products and the flame retardant is used in proportion of 10 percent, and the potential market scale of the domestic flame retardant industry in 2015 is about 98 ten thousand tons.
At present, the focus of domestic research and development is on the fields of inorganic flame retardants, red phosphorus microencapsulation, intumescent flame retardants, and the like. Mainly because of the advantages of high phosphorus content, good compatibility, multi-component synergistic effect and the like, the polystyrene series material has high-efficiency flame retardant property. At present, the materials for coating red phosphorus powder are numerous and can be divided into organic coatings such as phenolic resin coated red phosphorus and inorganic coatings such as magnesium hydroxide coated red phosphorus. However, most of the raw materials currently studied are derived from petrochemicals, and at the same time, the addition amount of the inorganic coated red phosphorus is large, which seriously degrades the mechanical properties of the polymer material. And the flame retardant applied to the high molecular fabric at present has poor flame retardant effect and washability, and also contains formaldehyde.
Therefore, the development of a composite flame retardant with environmental protection, mechanical property, flame retardant effect and good washing fastness is urgently needed.
Disclosure of Invention
The invention solves the technical problems in the prior art, and provides a composite flame retardant, a preparation method and application thereof.
The technical scheme of the invention is as follows:
a composite flame retardant comprises the following components: organic flame retardant, inorganic flame retardant, synergist, biomass flame retardant; the inorganic flame retardant comprises any one of zinc borate, bis (bistrimethylsilyl) amine zinc modified magnesium hydroxide and magnesium hydroxide coated red phosphorus; the biomass flame retardant is prepared by reacting biomass phytic acid and dicyandiamide.
Preferably, the synergist is any one or combination of brominated styrene homopolymer, aluminum hypophosphite and melamine polyphosphate.
Preferably, the organic flame retardant is any one or a combination of resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], p-biphenylene tetraphenyl diphosphate and nitrophenoxy cyclotriphosphazene flame retardants.
Preferably, the composite flame retardant comprises the following components in parts by weight: 3-10 parts of organic flame retardant, 20-40 parts of inorganic flame retardant, 3-10 parts of synergist and 10-30 parts of biomass flame retardant; the inorganic flame retardant comprises any one of zinc borate, bis (bistrimethylsilyl) amine zinc modified magnesium hydroxide and magnesium hydroxide magnesium coated red phosphorus; the biomass flame retardant is prepared by reacting phytic acid and dicyandiamide.
Preferably, the mass ratio of the phytic acid to the dicyandiamide is 1: (3-10).
Under the action of ultrasonic wave, the bis (bis-trimethylsilyl) amine zinc soaks the nano magnesium hydroxide and enters the inner pore canal of the nano magnesium hydroxide, and after cooling treatment, the bis (bis-trimethylsilyl) amine zinc is changed from liquid state to solid state, so that the bis (bis-trimethylsilyl) amine zinc is coated on the surface of the nano magnesium hydroxide and the bis (bis-trimethylsilyl) amine zinc is filled in the nano magnesium hydroxide, thereby obtaining the technical effects of isolating air, reducing surface energy, reducing hydrophilicity and improving compatibility, and realizing the uniform dispersion of the magnesium hydroxide in the polymer and strengthening the flame retardant effect.
The brominated styrene homopolymer can be rapidly decomposed at high temperature, a large amount of hydrogen bromide is generated to dilute the polymer, and the generated combustible gas is decomposed, and meanwhile, when the zinc borate is decomposed at high temperature, a part of zinc enters a gas phase as zinc oxide or zinc hydroxide, so that the combustible gas is diluted. The melamine polyphosphate contains phosphorus and nitrogen, is rapidly decomposed at high temperature to generate a carbon layer, releases nitrogen to dilute combustible gas, and has a synergistic effect with a biomass flame retardant, the biomass flame retardant has good thermal stability and char formation, and the compact carbon layer can cover the surface of a material, so that oxygen is isolated, and further generation of the combustible gas is prevented.
A preparation method of a composite flame retardant comprises the following steps:
step 1, preparation of a biomass flame retardant: mixing a phytic acid aqueous solution and dicyandiamide, heating, condensing, refluxing and reacting to obtain a yellowish, transparent and viscous crude product liquid, precipitating the crude product liquid with absolute ethyl alcohol and acetone, carrying out suction filtration, washing and drying to obtain a biomass flame retardant;
and 2, mixing the inorganic flame retardant and the organic flame retardant, performing ultrasonic dispersion, adding the synergist and the biomass flame retardant, and performing ball milling to obtain the composite flame retardant.
Preferably, in the step 1, the concentration of the phytic acid is 0.5-2 mol/L; the concentration of the dicyandiamide is 0.1-1 mol/L.
Preferably, in the step 1, the heating temperature is 130-150 ℃.
Preferably, in the step 1, the drying temperature is-80 to-50 ℃, and the pressure is 8 pa.
Preferably, in the step 2, the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the preparation method of the magnesium hydroxide coated red phosphorus comprises the following steps: mixing red phosphorus and a dispersing agent, mechanically stirring at room temperature to fully disperse the red phosphorus, adding a magnesium salt solution, controlling the reaction temperature, continuously stirring for reaction, aging a product, performing vacuum filtration, drying a filtered product in an oven, crushing and sieving to obtain the magnesium hydroxide coated red phosphorus.
Preferably, the dispersant comprises at least one of sodium dodecyl benzene sulfonate, sodium hexametaphosphate, sodium dodecyl sulfate, and OP-10.
The composite flame retardant can be used for preparing flame-retardant high-molecular polymer master batches, can be further prepared into cable materials or fabrics, solves the problems of washing resistance and flame retardance of the fabrics, enables the flame retardance to be effectively improved with less addition amount, and can simultaneously obtain the functions of molten drop resistance, reinforcement, ultraviolet resistance, coloring and the like by adopting master batch products in the actual application fields of different flame-retardant high-molecular polymer materials.
The flame-retardant high-molecular polymer master batch is prepared from the composite flame retardant and a high-molecular polymer material.
Preferably, the dosage of the composite flame retardant is 10-30% of the mass of the high molecular polymer material, and preferably 17%
-25%, further preferably 20%.
The invention adopts the composite flame retardant and the high molecular polymer material with specific dosage proportion, is beneficial to improving the dispersion performance of the composite flame retardant and the high molecular polymer material melt, and improves the flame retardant performance and the mechanical strength of the obtained flame retardant high molecular polymer.
Preferably, the high molecular polymer material comprises at least one of polyolefin, polyester, polyamide, and elastic high molecular polymer material.
More preferably, the polyolefin comprises one or more of Polyethylene (PE), Ethylene Vinyl Acetate (EVA), polypropylene (PP), Polystyrene (PS); the polyester comprises one or two of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); the elastic high polymer material comprises one or more of Polyurethane (PU), thermoplastic polyurethane elastomer rubber (TPU) and rubber.
A preparation method of flame-retardant high-molecular polymer master batches comprises the following steps: the composite flame retardant is introduced into a target high molecular polymer material by adopting a melting or banburying method to prepare the flame-retardant high molecular polymer master batch.
Compared with the prior art, the invention has the advantages that,
1. the composite flame retardant comprises an organic flame retardant, an inorganic flame retardant, a synergist and a biomass flame retardant; the composite flame retardant can form covalent crosslinking with cellulose hydroxyl in a P-O-C form by utilizing a biomass flame retardant, so that high-efficiency flame retardance and durability are endowed to a high-molecular polymer fabric; the composite flame retardant further improves the flame retardance by using the magnesium hydroxide to coat red phosphorus with the inorganic coating flame retardant and utilizing the efficient catalytic carbonization capability of the magnesium hydroxide. Therefore, the composite flame retardant can not only fully utilize the renewability of the biomass material, but also effectively improve the instability of the inorganic flame retardant and exert the effect of the inorganic coating flame retardant to the maximum.
2. The biomass flame retardant in the composite flame retardant is a biomass-based environment-friendly flame retardant, is a multi-activity phosphorus-nitrogen flame retardant, has a phosphorus-nitrogen synergistic flame retardant effect, and exerts the synergistic effect of various components to the maximum.
3. The invention adopts the composite flame retardant for preparing the flame-retardant high-molecular polymer master batch, can be further prepared into cable materials or fabrics, solves the problems of washing resistance and flame retardance of the fabrics, makes the effective improvement of the flame retardance under less addition amount possible, and simultaneously adopts the master batch product to obtain the functions of molten drop resistance, reinforcement, ultraviolet resistance, coloring and the like simultaneously for the practical application fields of different flame-retardant high-molecular polymer materials.
Detailed Description
Example 1:
the composite flame retardant of the embodiment comprises the following components in parts by weight: 5 parts of organic flame retardant, 25 parts of inorganic flame retardant, 3.5 parts of synergist and 20 parts of biomass flame retardant; the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the biomass flame retardant is synthesized by reacting biomass phytic acid and dicyandiamide; the synergist is aluminum hypophosphite and melamine polyphosphate; the organic flame retardant is a nitrophenoxy cyclotriphosphazene flame retardant.
The preparation method of the composite flame retardant of the embodiment comprises the following steps:
(1) preparation of the biomass flame retardant: sequentially adding 0.5-2mol/L phytic acid aqueous solution (the amount of substances added with phytic acid is 0.1mol) and 0.1-1mol/L dicyandiamide aqueous solution (the amount of substances added with dicyandiamide is 0.6mol) into a 250ml three-neck flask, mixing, heating to 130 ℃ under magnetic stirring, carrying out condensation reflux reaction for 2 hours to obtain light yellow transparent viscous crude product liquid, precipitating, filtering and washing the crude product liquid by using absolute ethyl alcohol and acetone, removing unreacted reactants, and drying by using a freeze dryer at-50 ℃ and 8pa to obtain the biomass flame retardant;
(2) preparing magnesium hydroxide coated red phosphorus by adopting a chemical coprecipitation method: mixing red phosphorus and a dispersing agent, mechanically stirring at room temperature to fully disperse the red phosphorus, adding a magnesium salt solution, continuously stirring and reacting for 1h at the reaction temperature of 90 ℃, aging the product for 10h, performing vacuum filtration, drying the filtered product in an oven, crushing and sieving to obtain magnesium hydroxide coated red phosphorus;
(3) mixing 500g of magnesium hydroxide coated red phosphorus and 100g of nitrophenoxy cyclotriphosphazene flame retardant, performing ultrasonic dispersion for 20min, adding 50g of aluminum hypophosphite, 25g of melamine polyphosphate and 400g of biomass flame retardant, and performing ball milling for 2h to obtain the composite flame retardant.
The preparation method of the flame-retardant high-molecular polymer master batch comprises the following steps:
weighing 100g of the prepared composite flame retardant and 1000g of PP blank master batch, carrying out melt blending extrusion, controlling the extrusion temperature at 160 ℃, and carrying out hot air drying and grain cutting to obtain a flame retardant master batch product.
The flame retardant master batch is compounded with a polypropylene cable material by 10 percent of addition amount to obtain a cable material product, and the UL94 test shows that the flame retardant grade is UL94V-0 and the oxygen index test can reach 31.5vol percent.
Example 2:
the composite flame retardant of the embodiment comprises the following components in parts by weight: 5 parts of organic flame retardant, 25 parts of inorganic flame retardant, 10 parts of synergist and 20 parts of biomass flame retardant; the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the biomass flame retardant is synthesized by reacting biomass phytic acid and dicyandiamide; the synergist is aluminum hypophosphite and melamine polyphosphate; the organic flame retardant is a nitrophenoxy cyclotriphosphazene flame retardant.
The preparation method of the composite flame retardant of the embodiment comprises the following steps:
(1) preparation of the biomass flame retardant: sequentially adding 0.5-2mol/L phytic acid aqueous solution (the amount of substances added with phytic acid is 0.1mol) and 0.1-1mol/L dicyandiamide aqueous solution (the amount of substances added with dicyandiamide is 0.6mol) into a 250ml three-neck flask, mixing, heating to 130 ℃ under magnetic stirring, carrying out condensation reflux reaction for 2 hours to obtain light yellow transparent viscous crude product liquid, precipitating, filtering and washing the crude product liquid by using absolute ethyl alcohol and acetone, removing unreacted reactants, and drying by using a freeze dryer at-50 ℃ and 8pa to obtain the biomass flame retardant;
(2) preparing magnesium hydroxide coated red phosphorus by adopting a chemical coprecipitation method: mixing red phosphorus and a dispersing agent, mechanically stirring at room temperature to fully disperse the red phosphorus, adding a magnesium salt solution, continuously stirring and reacting for 1h at the reaction temperature of 90 ℃, aging the product for 10h, performing vacuum filtration, drying the filtered product in an oven, crushing and sieving to obtain magnesium hydroxide coated red phosphorus;
(3) mixing 500g of magnesium hydroxide coated red phosphorus and 100g of nitrophenoxy cyclotriphosphazene flame retardant, performing ultrasonic dispersion for 20min, adding 100g of aluminum hypophosphite, 100g of melamine polyphosphate and 400g of biomass flame retardant, and performing ball milling for 2h to obtain the composite flame retardant.
The preparation method of the flame-retardant high-molecular polymer master batch comprises the following steps:
weighing 100g of the prepared composite flame retardant and 1000g of HDPE blank master batch, carrying out melt blending extrusion, controlling the extrusion temperature at 160 ℃, and carrying out hot air drying and grain cutting to obtain a flame retardant master batch product.
The flame retardant master batch is compounded with a polyethylene cable material by 10 percent of addition amount to obtain a cable material product, and the UL94 test shows that the flame retardant grade is UL94V-0 and the oxygen index test can reach 35.5vol percent.
Example 3:
the composite flame retardant of the embodiment comprises the following components in parts by weight: 5 parts of organic flame retardant, 25 parts of inorganic flame retardant, 3.5 parts of synergist and 20 parts of biomass flame retardant; the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the biomass flame retardant is synthesized by reacting biomass phytic acid and dicyandiamide; the synergist is aluminum hypophosphite and melamine polyphosphate; the organic flame retardant is a nitrophenoxy cyclotriphosphazene flame retardant.
The preparation method of the composite flame retardant of the embodiment comprises the following steps:
(1) preparation of the biomass flame retardant: sequentially adding 0.5-2mol/L phytic acid aqueous solution (the amount of substances added with phytic acid is 0.1mol) and 0.1-1mol/L dicyandiamide aqueous solution (the amount of substances added with dicyandiamide is 0.6mol) into a 250ml three-neck flask, mixing, heating to 130 ℃ under magnetic stirring, carrying out condensation reflux reaction for 2 hours to obtain light yellow transparent viscous crude product liquid, precipitating, filtering and washing the crude product liquid by using absolute ethyl alcohol and acetone, removing unreacted reactants, and drying by using a freeze dryer at-50 ℃ and 8pa to obtain the biomass flame retardant;
(2) preparing magnesium hydroxide coated red phosphorus by adopting a chemical coprecipitation method: mixing red phosphorus and a dispersing agent, mechanically stirring at room temperature to fully disperse the red phosphorus, adding a magnesium salt solution, continuously stirring and reacting for 1h at the reaction temperature of 90 ℃, aging the product for 10h, performing vacuum filtration, drying the filtered product in an oven, crushing and sieving to obtain magnesium hydroxide coated red phosphorus;
(3) mixing 500g of magnesium hydroxide coated red phosphorus and 100g of nitrophenoxy cyclotriphosphazene flame retardant, performing ultrasonic dispersion for 20min, adding 50g of aluminum hypophosphite, 25g of melamine polyphosphate and 400g of biomass flame retardant, and performing ball milling for 2h to obtain the composite flame retardant.
The preparation method of the flame-retardant high-molecular polymer master batch comprises the following steps:
weighing 150g of the prepared composite flame retardant and 500g of HDPE blank master batch, carrying out melt blending extrusion, controlling the extrusion temperature at 160 ℃, and carrying out hot air drying and grain cutting to obtain a flame retardant master batch product.
The flame retardant master batch is compounded with a polyethylene cable material by 10 percent of addition amount to obtain a cable material product, and the UL94 test shows that the flame retardant grade is UL94V-0 and the oxygen index test can reach 30vol percent.
Example 4:
the composite flame retardant of the embodiment comprises the following components in parts by weight: 5 parts of organic flame retardant, 25 parts of inorganic flame retardant, 3.5 parts of synergist and 20 parts of biomass flame retardant; the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the biomass flame retardant is synthesized by reacting biomass phytic acid and dicyandiamide; the synergist is aluminum hypophosphite and melamine polyphosphate; the organic flame retardant is a nitrophenoxy cyclotriphosphazene flame retardant.
The preparation method of the composite flame retardant of the embodiment comprises the following steps:
(1) preparation of the biomass flame retardant: sequentially adding 0.5-2mol/L phytic acid aqueous solution (the amount of substances added with phytic acid is 0.1mol) and 0.1-1mol/L dicyandiamide aqueous solution (the amount of substances added with dicyandiamide is 0.6mol) into a 250ml three-neck flask, mixing, heating to 130 ℃ under magnetic stirring, carrying out condensation reflux reaction for 2 hours to obtain light yellow transparent viscous crude product liquid, precipitating, filtering and washing the crude product liquid by using absolute ethyl alcohol and acetone, removing unreacted reactants, and drying by using a freeze dryer at-50 ℃ and 8pa to obtain the biomass flame retardant;
(2) preparing magnesium hydroxide coated red phosphorus by adopting a chemical coprecipitation method: mixing red phosphorus and a dispersing agent, mechanically stirring at room temperature to fully disperse the red phosphorus, adding a magnesium salt solution, continuously stirring and reacting for 1h at the reaction temperature of 90 ℃, aging the product for 10h, performing vacuum filtration, drying the filtered product in an oven, crushing and sieving to obtain magnesium hydroxide coated red phosphorus;
(3) mixing 500g of magnesium hydroxide coated red phosphorus and 100g of nitrophenoxy cyclotriphosphazene flame retardant, performing ultrasonic dispersion for 20min, adding 50g of aluminum hypophosphite, 25g of melamine polyphosphate and 400g of biomass flame retardant, and performing ball milling for 2h to obtain the composite flame retardant.
The preparation method of the flame-retardant high-molecular polymer master batch comprises the following steps:
weighing 75g of the prepared dry powder biomass graphene modified flame retardant and 500g of nitrile rubber blank master batch, blending in an open mill, performing thin-pass rubber mixing in the open mill, reducing the milling distance (0.5-1.0mm) at the milling temperature (30-40 ℃), plasticating in sections, wherein each section of time is 25min, and standing for 3-4 hours in the middle. And (4) granulating the internally mixed sizing material, and drying by hot air to obtain the flame retardant master batch product.
The flame retardant master batch and PET blank slices are mixed in a double-screw extruder in an adding amount of 10% and are directly subjected to melt spinning to obtain a flame-retardant elasticated modified polyester fiber product, and the UL-94 test shows that the flame retardant grade is UL94V-0 and the oxygen index test can reach 30 vol%.
Example 5:
the composite flame retardant of the embodiment comprises the following components in parts by weight: 5 parts of organic flame retardant, 25 parts of inorganic flame retardant, 3.5 parts of synergist and 20 parts of biomass flame retardant; the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the biomass flame retardant is synthesized by reacting biomass phytic acid and dicyandiamide; the synergist is aluminum hypophosphite and melamine polyphosphate; the organic flame retardant is a nitrophenoxy cyclotriphosphazene flame retardant.
The preparation method of the composite flame retardant of the embodiment comprises the following steps:
(1) preparation of the biomass flame retardant: sequentially adding 0.5-2mol/L phytic acid aqueous solution (the amount of substances added with phytic acid is 0.1mol) and 0.1-1mol/L dicyandiamide aqueous solution (the amount of substances added with dicyandiamide is 0.6mol) into a 250ml three-neck flask, mixing, heating to 130 ℃ under magnetic stirring, carrying out condensation reflux reaction for 2 hours to obtain light yellow transparent viscous crude product liquid, precipitating, filtering and washing the crude product liquid by using absolute ethyl alcohol and acetone, removing unreacted reactants, and drying by using a freeze dryer at-50 ℃ and 8pa to obtain the biomass flame retardant;
(2) preparing magnesium hydroxide coated red phosphorus by adopting a chemical coprecipitation method: mixing red phosphorus and a dispersing agent, mechanically stirring at room temperature to fully disperse the red phosphorus, adding a magnesium salt solution, continuously stirring and reacting for 1h at the reaction temperature of 90 ℃, aging the product for 10h, performing vacuum filtration, drying the filtered product in an oven, crushing and sieving to obtain magnesium hydroxide coated red phosphorus;
(3) mixing 500g of magnesium hydroxide coated red phosphorus and 100g of nitrophenoxy cyclotriphosphazene flame retardant, performing ultrasonic dispersion for 20min, adding 50g of aluminum hypophosphite, 25g of melamine polyphosphate and 400g of biomass flame retardant, and performing ball milling for 2h to obtain the composite flame retardant.
The preparation method of the flame-retardant high-molecular polymer master batch comprises the following steps:
weighing 150g of prepared dry powder biomass graphene modified flame retardant and 1000g of nitrile rubber blank master batch, blending in an open mill, performing thin rubber mixing in the open mill, reducing the milling distance (0.5-l.0mm) at the milling temperature (30-40 ℃), plasticating in sections, wherein each section of time is 25min, and standing for 3-4 hours in the middle. And (4) granulating the internally mixed sizing material, and drying by hot air to obtain the flame retardant master batch product. The flame retardant master batch and PET blank slices are mixed in a double-screw extruder in an adding amount of 10% and are directly subjected to melt spinning to obtain a flame-retardant elasticated modified polyester fiber product, and the UL-94 test shows that the flame retardant grade is UL94V-0 and the oxygen index test can reach 28 vol%.
Example 6:
the composite flame retardant of the embodiment comprises the following components in parts by weight: 5 parts of organic flame retardant, 25 parts of inorganic flame retardant, 3.5 parts of synergist and 20 parts of biomass flame retardant; the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the biomass flame retardant is synthesized by reacting biomass phytic acid and dicyandiamide; the synergist is aluminum hypophosphite and melamine polyphosphate; the organic flame retardant is a nitrophenoxy cyclotriphosphazene flame retardant.
The preparation method of the composite flame retardant of the embodiment comprises the following steps:
(1) preparation of the biomass flame retardant: sequentially adding 0.5-2mol/L phytic acid aqueous solution (the amount of substances added with phytic acid is 0.1mol) and 0.1-1mol/L dicyandiamide aqueous solution (the amount of substances added with dicyandiamide is 0.6mol) into a 250ml three-neck flask, mixing, heating to 130 ℃ under magnetic stirring, carrying out condensation reflux reaction for 2 hours to obtain light yellow transparent viscous crude product liquid, precipitating, filtering and washing the crude product liquid by using absolute ethyl alcohol and acetone, removing unreacted reactants, and drying by using a freeze dryer at-50 ℃ and 8pa to obtain the biomass flame retardant;
(2) preparing magnesium hydroxide coated red phosphorus by adopting a chemical coprecipitation method: mixing red phosphorus and a dispersing agent, mechanically stirring at room temperature to fully disperse the red phosphorus, adding a magnesium salt solution, continuously stirring and reacting for 1h at the reaction temperature of 90 ℃, aging the product for 10h, performing vacuum filtration, drying the filtered product in an oven, crushing and sieving to obtain magnesium hydroxide coated red phosphorus;
(3) mixing 500g of magnesium hydroxide coated red phosphorus and 100g of nitrophenoxy cyclotriphosphazene flame retardant, performing ultrasonic dispersion for 20min, adding 50g of aluminum hypophosphite, 25g of melamine polyphosphate and 400g of biomass flame retardant, and performing ball milling for 2h to obtain the composite flame retardant.
The preparation method of the flame-retardant high-molecular polymer master batch comprises the following steps:
weighing 100g of prepared composite flame retardant and 400g of nitrile rubber blank master batch, blending in an open mill, carrying out thin-pass rubber mixing in the open mill, carrying out simplified temperature (30-40 ℃), reducing the distance (0.5-l.0mm), plasticating in sections, standing for 3-4 hours in the middle, granulating the rubber material subjected to internal mixing, and drying by hot air to obtain the flame retardant master batch product.
The flame retardant master batch and PET blank slices are mixed in a double-screw extruder in an adding amount of 10% and are directly subjected to melt spinning to obtain a flame-retardant elasticated modified polyester fiber product, and the UL-94 test shows that the flame retardant grade is UL94V-0 and the oxygen index test can reach 29 vol%.
Example 7
In the same way as example 6, the inorganic flame retardant is selected from zinc borate or magnesium hydroxide modified by zinc bis (bistrimethylsilyl) amine, and UL-94 tests show that the flame retardant rating is UL94V-0 and the oxygen index test can reach more than 29 vol%.
Example 8
In the same way as example 6, the synergist is brominated styrene homopolymer, and UL-94 test shows that the flame retardant rating is UL94V-0 and the oxygen index test can reach more than 29 vol%.
Example 9
In the same manner as in example 6, the organic flame retardant selected from resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], p-biphenylene tetraphenyl diphosphate or nitrophenoxy cyclotriphosphazene flame retardants was tested to UL-94, which showed a flame retardant rating of UL94V-0 and an oxygen index of 29 vol% or more.
Example 10
As in example 6, the following were used:
the components in parts by weight are as follows: 3 parts of organic flame retardant, 20 parts of inorganic flame retardant, 3 parts of synergist and 10-parts of biomass flame retardant;
the UL-94 test shows that the flame retardant rating is UL94V-0 and the oxygen index test can reach more than 29 vol%.
Example 11
As in example 6, the following were used:
the components in parts by weight are as follows: 10 parts of organic flame retardant, 40 parts of inorganic flame retardant, 10 parts of synergist and 30 parts of biomass flame retardant;
the UL-94 test shows that the flame retardant rating is UL94V-0 and the oxygen index test can reach more than 29 vol%.
Example 12
In the same way as example 6, the mass ratio of the phytic acid to the dicyandiamide is 1:3, and the UL-94 test shows that the flame retardant rating is UL94V-0 and the oxygen index test can reach more than 29 vol%.
Example 13
In the same way as example 6, the mass ratio of the phytic acid to the dicyandiamide is 1:10, and the UL-94 test shows that the flame retardant rating is UL94V-0 and the oxygen index test can reach more than 29 vol%.
Example 13
In example 6, similar technical effects can be obtained when the heating temperature is 130-150 ℃, and the drying temperature is-80-50 ℃.
Comparative example 1
This comparative example differs from example 1 in that: the composite flame retardant comprises the following components in parts by weight: 5 parts of organic flame retardant, 25 parts of inorganic flame retardant and 20 parts of biomass flame retardant; the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the biomass flame retardant is synthesized by reacting biomass phytic acid and dicyandiamide; the organic flame retardant is a nitrophenoxy cyclotriphosphazene flame retardant.
Weighing nanometer Al (OH)3And (3) performing melt blending extrusion on 100g of the inorganic flame retardant and 500g of HDPE blank master batch, controlling the extrusion temperature at 160 ℃, and performing hot air drying and grain cutting to obtain a flame retardant master batch product.
The flame retardant master batch is compounded with a polyethylene cable material by 10 percent of addition amount to obtain a cable material product, and the UL94 test shows that the flame retardant grade is UL94V-2 and the oxygen index test can reach 27vol percent.
Comparative example 2
This comparative example differs from example 1 in that: the composite flame retardant comprises the following components in parts by weight: 5 parts of organic flame retardant, 25 parts of inorganic flame retardant and 3.5 parts of synergist; the inorganic flame retardant is magnesium hydroxide coated red phosphorus; the synergist is aluminum hypophosphite and melamine polyphosphate; the organic flame retardant is a nitrophenoxy cyclotriphosphazene flame retardant.
Weighing 100g of the composite flame retardant and 500g of HDPE blank master batch, carrying out melt blending extrusion, controlling the extrusion temperature at 160 ℃, and carrying out hot air drying and grain cutting to obtain a flame retardant master batch product.
The flame retardant master batch is compounded with a polyethylene cable material by 10 percent of addition amount to obtain a cable material product, and the UL94 test shows that the flame retardant grade is UL94V-1 and the oxygen index test can reach 27vol percent.
According to the embodiment and the comparative example, the invention can effectively improve the anti-dripping characteristic and the oxygen index of the obtained composite high polymer material product under the condition of low actual using amount of the composite flame retardant, and obviously improve the flame retardant property.
For the above tests, under the same conditions except that no flame retardant is added, the flame retardant rating is UL94VHB, and the oxygen index is below 25 vol%; even if the flame retardant material is added, the flame retardant rating is up to UL94V-2, and the oxygen index is not higher than 27 vol%.
The invention adopts the composite flame retardant for preparing the flame-retardant high-molecular polymer master batch, can be further prepared into cable materials or fabrics, solves the problems of washing resistance and flame retardance of the fabrics, makes the effective improvement of the flame retardance under less addition amount possible, and simultaneously adopts the master batch product to obtain the functions of molten drop resistance, reinforcement, ultraviolet resistance, coloring and the like simultaneously for the practical application fields of different flame-retardant high-molecular polymer materials.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
Claims (10)
1. The composite flame retardant is characterized by comprising the following components: organic flame retardant, inorganic flame retardant, synergist, biomass flame retardant; the inorganic flame retardant comprises any one of zinc borate, bis (bistrimethylsilyl) amine zinc modified magnesium hydroxide and magnesium hydroxide coated red phosphorus; the biomass flame retardant is prepared by reacting biomass phytic acid and dicyandiamide.
2. The composite flame retardant of claim 1, wherein the synergist is any one or a combination of brominated styrene homopolymer, aluminum hypophosphite and melamine polyphosphate.
3. The composite flame retardant of claim 1, wherein the organic flame retardant is any one or a combination of resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], p-biphenylene tetraphenyl diphosphate, or nitrophenoxy cyclotriphosphazene flame retardants.
4. The composite flame retardant of claim 1, comprising the following components in parts by weight: 3-10 parts of organic flame retardant, 20-40 parts of inorganic flame retardant, 3-10 parts of synergist and 10-30 parts of biomass flame retardant; the inorganic flame retardant comprises any one of zinc borate, bis (bistrimethylsilyl) amine zinc modified magnesium hydroxide and magnesium hydroxide magnesium coated red phosphorus; the biomass flame retardant is prepared by reacting phytic acid and dicyandiamide.
5. The composite flame retardant of claim 1, wherein the mass ratio of the phytic acid to the dicyandiamide is 1: (3-10).
6. The method for preparing the composite flame retardant of any one of claims 1 to 4, comprising the steps of:
step 1, preparation of a biomass flame retardant: mixing a phytic acid aqueous solution and dicyandiamide, heating, condensing, refluxing and reacting to obtain a yellowish, transparent and viscous crude product liquid, precipitating the crude product liquid with absolute ethyl alcohol and acetone, carrying out suction filtration, washing and drying to obtain a biomass flame retardant;
and 2, mixing the inorganic flame retardant and the organic flame retardant, performing ultrasonic dispersion, adding the synergist and the biomass flame retardant, and performing ball milling to obtain the composite flame retardant.
7. The preparation method according to claim 6, wherein in the step 1, the concentration of the phytic acid aqueous solution is 0.5 to 2 mol/L; the concentration of the dicyandiamide is 0.1-1 mol/L.
8. The preparation method according to claim 6, wherein in the step 2, the inorganic flame retardant is magnesium hydroxide-coated red phosphorus; the preparation method of the magnesium hydroxide coated red phosphorus comprises the following steps: mixing red phosphorus and a dispersing agent, mechanically stirring at room temperature to fully disperse the red phosphorus, adding a magnesium salt solution, controlling the reaction temperature, continuously stirring for reaction, aging a product, performing vacuum filtration, drying a filtered product in an oven, crushing and sieving to obtain the magnesium hydroxide coated red phosphorus.
9. The method of claim 8, wherein the dispersant comprises at least one of sodium dodecylbenzene sulfonate, sodium hexametaphosphate, sodium dodecyl sulfate, and OP-10.
10. The flame-retardant high-molecular polymer master batch is characterized by being prepared from the composite flame retardant and the high-molecular polymer material according to any one of claims 1 to 4, wherein the using amount of the composite flame retardant is 10 to 30 percent of the mass of the high-molecular polymer material.
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