CN114479446B - Halogen-free flame-retardant glass fiber reinforced nylon and preparation method and application thereof - Google Patents
Halogen-free flame-retardant glass fiber reinforced nylon and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
Abstract
The invention provides halogen-free flame-retardant glass fiber reinforced nylon and a preparation method and application thereof, wherein the halogen-free flame-retardant glass fiber reinforced nylon comprises the following raw materials in percentage by weight: 30-60% of nylon; 20-40% of glass fiber; 10-30% of halogen-free flame-retardant compound; the halogen-free flame-retardant compound comprises an organic phosphorus flame retardant and aluminum phosphite-alkyl aluminum phosphite composite salt, wherein the content of the organic phosphorus flame retardant is 70-90% and the content of the aluminum phosphite-alkyl aluminum phosphite composite salt is 10-30% by taking the mass of the halogen-free flame-retardant compound as 100%. The halogen-free flame-retardant glass fiber reinforced nylon disclosed by the invention adopts the halogen-free flame-retardant compound as the flame retardant, has better flame retardant property and can reach the flame retardant standard of UL94-V0 (1.6 mm).
Description
Technical Field
The invention belongs to the technical field of halogen-free flame retardance, and relates to halogen-free flame-retardant glass fiber reinforced nylon and a preparation method and application thereof.
Background
Glass fiber reinforced nylon (mainly nylon 66 and nylon 6) is widely applied to the fields of mechanical structures, electronic and electric products, sports equipment, textiles and the like due to the performance characteristics of high mechanical strength, outstanding fatigue resistance, corrosion resistance, good heat resistance, smooth surface, weather resistance and the like. The common glass fiber reinforced nylon is a flammable material, and in recent years, with the rapid development of electronic appliances, higher requirements are put forward on the flame retardant property of the glass fiber reinforced nylon applied to the field.
At present, the flame retardance of the glass fiber reinforced nylon material comprises two basic flame retardant systems: halogen-based flame retardant systems and non-halogen flame retardant systems. Because the halogen flame retardant has poor high temperature stability and low electric leakage index and contains harmful substances such as dense smoke, hydrogen bromide and the like in the combustion process, the development of the halogen-free flame retardant which is safe and environment-friendly becomes a consensus in the industry.
At present, the halogen-free flame retardant for glass fiber reinforced nylon engineering plastics which is more applied in the market is a phosphorus-nitrogen compound system based on organic phosphinate. Such as the compounding of diethyl aluminum phosphinate flame retardant and melamine polyphosphate synergist. The compound flame retardant obtained by the method has high phosphorus content and good heat-resistant stability, and can play a synergistic effect of the phosphorus and nitrogen flame retardants in the combustion process, thereby showing higher flame-retardant efficiency. However, the flame retardant also faces some disadvantages in the practical use process, which are mainly shown in the following: 1) The processing temperature of the glass fiber reinforced nylon is high, and the melamine polyphosphate can be decomposed to generate a small amount of acid substances at the high processing temperature, so that equipment is corroded, and the service life of the equipment is shortened; meanwhile, the generation of acidic substances accelerates the decomposition of nylon resin and influences the mechanical properties of nylon products; 2) The nitrogen-containing compound and the melamine polyphosphate synergist are easy to separate out on a mould in the processing process, and the mould needs to be shut down and cleaned after a period of production, so that the production efficiency is influenced; the small amount of melamine polyphosphate can also be separated out on the surface of the product, and the appearance of the product is influenced.
In conclusion, the existing halogen-free flame retardant is used for the glass fiber reinforced nylon engineering plastic, so that the problems of equipment corrosion at high temperature, influence on production efficiency, precipitation of the flame retardant on the surfaces of a mold and a workpiece and the like exist, and the problems bring difficulty to the processing and use of the glass fiber reinforced nylon engineering plastic.
CN103450672A discloses a halogen-free flame-retardant glass fiber reinforced nylon 6 particle and a preparation method thereof, the particle comprises 20-50% of nylon 6 resin, 10-35% of glass fiber, 10-30% of flame-retardant resin, 10-20% of red phosphorus master batch, 0-15% of auxiliary flame retardant, 2-10% of toughening agent, 0.1-1% of antioxidant and 0.2-1.5% of auxiliary processing aid by weight ratio. The product has the characteristics of high strength, high modulus, small creep deformation and small hygroscopicity, has the characteristics of excellent flame retardant property, high mechanical strength, high temperature resistance, light weight and easiness in processing, can meet the requirement of people on environmental protection, and is simple to operate and suitable for industrial production. However, the flame retardant properties of the particles of the invention are yet to be further improved.
Therefore, it is expected in the art to develop a novel halogen-free flame retardant compound and a halogen-free flame retardant glass fiber reinforced nylon comprising the same.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide halogen-free flame-retardant glass fiber reinforced nylon and a preparation method and application thereof. The halogen-free flame-retardant glass fiber reinforced nylon has better flame retardant property.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a halogen-free flame-retardant glass fiber reinforced nylon, which comprises the following raw materials in percentage by weight:
30-60% of nylon;
20-40% of glass fiber;
10-30% of halogen-free flame-retardant compound;
the halogen-free flame-retardant compound comprises an organic phosphorus flame retardant and aluminum phosphite-alkyl aluminum phosphite composite salt, wherein the content of the organic phosphorus flame retardant is 70-90% (such as 70%, 72%, 75%, 80%, 85%, 90%, 95% or 99% and the like) and the content of the aluminum phosphite-alkyl aluminum phosphite composite salt is 10-30% (such as 10%, 15%, 18%, 20%, 25% or 30% and the like) based on 100% of the mass of the halogen-free flame-retardant compound.
In the invention, the aluminum phosphite-alkyl aluminum phosphite composite salt has the advantages of high flame retardant efficiency, high heat-resistant stability and the like, is compounded with the organic phosphorus flame retardant in a specific proportion for use, shows excellent flame retardant efficiency, and does not precipitate or corrode processing equipment in the processing and using process. Meanwhile, the existence of the aluminum phosphite-alkyl aluminum phosphite composite salt improves the flame retardant efficiency of the halogen-free flame retardant compound and reduces the dosage of the flame retardant. The halogen-free flame-retardant glass fiber reinforced nylon is added with the halogen-free flame-retardant compound, so that the halogen-free flame-retardant glass fiber reinforced nylon has excellent comprehensive performance and better flame retardant property.
In the invention, in the raw materials for preparing the halogen-free flame-retardant glass fiber reinforced nylon, the amount of the nylon can be 30%, 35%, 40%, 45%, 50%, 55%, 60% or the like.
In the invention, in the raw material for preparing the halogen-free flame-retardant glass fiber reinforced nylon, the amount of the glass fiber can be 20%, 25%, 30%, 35% or 40% and the like.
In the invention, in the raw materials for preparing the halogen-free flame-retardant glass fiber reinforced nylon, the dosage of the halogen-free flame-retardant compound can be 10%, 15%, 20%, 25% or 30% and the like.
Preferably, the organophosphorus flame retardant comprises a dialkylhypophosphite and/or DOPO bridging derivative.
Preferably, the dialkylhypophosphite has the structure shown in formula a:
wherein R is 1 、R 2 Each independently selected from any one of ethyl, propyl or butyl, in particular from any one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; y is selected from any one of magnesium, calcium, aluminum or zinc, preferably aluminum or zinc; x is an integer from 2 to 4, for example 2, 3 or 4.
Preferably, the dialkylphosphinate salt is aluminum diethylphosphinate.
Preferably, the DOPO bridging derivative has the structure shown in formula B:
wherein R is 3 、R 4 Each independently selected from hydrogen, C 1 -C 4 Alkyl, nitro (-NO) 2 ) Or amino (-NH) 2 ) Any one of the above; n is an integer from 1 to 4, for example 1, 2, 3 or 4.
Preferably, R 3 、R 4 All are hydrogen, n is 1, namely the DOPO bridging group derivative is the DOPO ethyl bridging group derivative.
Preferably, the aluminum phosphite-alkyl aluminum phosphite complex salt is prepared by method one: and (2) performing a neutralization reaction on phosphorous acid and alkyl phosphorous acid and an aluminum source or performing a neutralization reaction by a method II: phosphite, alkyl phosphite and aluminum salt are subjected to double decomposition reaction to prepare the product.
In a preferred embodiment of the present invention, the aluminum phosphite-alkyl aluminum phosphite complex salt prepared by the method one or the method two is a specific compound formed by an ionic bonding method, unlike a direct physical mixture of aluminum phosphite and alkyl aluminum phosphite. The flame retardant aluminum phosphite flame retardant can ensure the flame retardant efficiency of the original aluminum phosphite, and can reduce the corrosion of the aluminum phosphite to equipment such as a screw rod, a die head and the like in the high-temperature processing and using process.
Preferably, the first method comprises the following steps:
mixing phosphorous acid, alkyl phosphorous acid and water, then adding an aluminum source and a reaction auxiliary agent, heating, reacting and post-treating to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt.
Preferably, the phosphorous acid has a structure represented by C1, and the alkyl phosphorous acid has a structure represented by D1:
wherein R is 5 Is selected from any one of methyl, ethyl, propyl or butyl.
Preferably, the aluminium source comprises any one of alumina, aluminium hydroxide, aluminium oxyhydroxide, pseudoboehmite or boehmite, or a combination of at least two thereof.
Preferably, the reaction aid comprises an acid, preferably any one of sulfuric acid, hydrochloric acid or nitric acid.
Preferably, the phosphorous acid is present in a molar amount of 60.0 to 99.8%, e.g., 60.0%, 65.0%, 70.0%, 75.0%, 80.0%, 85.0%, 90.0%, 95.0%, 99.0%, or 99.8%, etc., and the alkyl phosphorous acid is present in a molar amount of 0.2 to 40.0%, e.g., 0.2%, 1.0%, 5.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, or 40.0%, etc., based on 100% of the total molar amount of phosphorous acid and alkyl phosphorous acid; more preferably, the molar content of the phosphorous acid is 80.0-99.5%, and the molar content of the alkyl phosphorous acid is 0.5-20.0%.
If the molar content of the alkyl phosphite is too high, the phosphorus content of the aluminum phosphite-alkyl aluminum phosphite composite salt may be reduced, thereby affecting the flame retardant efficiency of the aluminum phosphite-alkyl aluminum phosphite composite salt.
In the first method provided by the invention, the addition amount of water is not limited, and water can be used for dissolving other raw materials.
Preferably, the ratio of the sum of the moles of phosphorous acid and alkylphosphorous acid to the moles of aluminum ions in the aluminum source is (1.5-1.8): 1, e.g., 1.5.
Preferably, the number of moles of the reaction promoter is 1 to 20% of the number of moles of aluminum ions in the aluminum source, such as 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, or the like. By controlling the addition amount of the reaction auxiliary agent, the PH of the reaction liquid can be controlled to be 2-4, so that the prepared aluminum phosphite-alkyl aluminum phosphite composite salt has proper particle size distribution and apparent density.
Preferably, the temperature is raised to 100-200 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃ and the like.
Preferably, the reaction time is 2-8h, such as 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc. The reaction is usually carried out in an autoclave, and for example, the reaction may be carried out in an autoclave lined with tetrafluoroethylene.
Preferably, the post-treatment comprises filtration, washing and drying.
Preferably, the second method comprises the following steps:
mixing phosphite, alkyl phosphite and water, then adding aluminum salt and a reaction auxiliary agent, heating, reacting and post-treating to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt.
Preferably, the phosphite anion has a structure represented by C2 and the alkylphosphite anion has a structure represented by D2:
wherein R is 6 Is selected from any one of methyl, ethyl, propyl or butyl.
Preferably, the cation of the phosphite is sodium or potassium.
Preferably, the cation of the alkyl phosphite is sodium or potassium.
Preferably, the phosphite is a water-soluble phosphite, including sodium phosphite and/or potassium phosphite.
Preferably, the alkyl phosphite is a water-soluble alkyl phosphite, including sodium alkyl phosphite and/or potassium alkyl phosphite.
Preferably, the aluminium salt comprises any one of aluminium sulphate, aluminium nitrate or aluminium chloride or a combination of at least two thereof.
Preferably, the reaction aid comprises an acid, preferably any one of sulfuric acid, hydrochloric acid or nitric acid.
Preferably, the phosphorous acid salt is present in a molar amount of 60.0 to 99.8% (e.g., 60.0%, 65.0%, 70.0%, 75.0%, 80.0%, 85.0%, 90.0%, 95.0%, 99.0%, or 99.8%, etc.) based on 100% total molar amount of phosphorous acid salt and alkyl phosphorous acid salt, which is present in a molar amount of 0.2% to 40.0%, e.g., 0.2%, 1.0%, 5.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, or 40.0%, etc.
If the molar content of the alkyl phosphite is too high, the phosphorous content of the aluminum phosphite-alkyl aluminum phosphite composite salt may be reduced, thereby affecting the flame retardant efficiency of the aluminum phosphite-alkyl aluminum phosphite composite salt.
In the second method provided by the invention, the addition amount of water is not limited, and water can be used for dissolving other raw materials.
Preferably, the ratio of the sum of the moles of phosphite and alkyl phosphite to the moles of aluminum ions in the aluminum salt is (1.5-1.8): 1, e.g. 1.5.
Preferably, the number of moles of the reaction aid agent is 1-20% of the number of moles of the aluminum ion in the aluminum salt, such as 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, or the like. By controlling the addition amount of the reaction auxiliary agent, the prepared aluminum phosphite-alkyl aluminum phosphite composite salt has proper particle size distribution and apparent density.
Preferably, the temperature rise is to 100-200 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃ and the like.
Preferably, the reaction time is 2-6h, such as 2h, 3h, 4h, 5h or 6h, etc. The reaction is usually carried out in an autoclave, and for example, the reaction may be carried out in an autoclave lined with tetrafluoroethylene.
Preferably, the post-treatment comprises filtration, washing and drying.
The aluminum phosphite-aluminum alkyl phosphite composite salt obtained in the above-mentioned first method or second method has an average particle diameter D50 of 2 to 50 μm, for example, 2 μm, 4 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm or 50 μm, and an apparent density of 200 to 700kg/m 3 For example 200kg/m 3 、300kg/m 3 、400kg/m 3 、500kg/m 3 、600kg/m 3 Or 700kg/m 3 And so on. More preferably, the aluminum phosphite-alkyl aluminum phosphite composite salt has an average particle diameter D50 of 4-40 μm and an apparent density of 300-700kg/m 3 . The proper particle size distribution and apparent density are beneficial to the full mixing of the flame retardant and the nylon resin and the uniform dispersion of the flame retardant, and the smooth implementation of the processing process is facilitated.
Preferably, the organophosphorus flame retardant has an average particle diameter D50 of 20 to 50 μm, such as 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm, and the like, and the aluminum phosphite-aluminum alkyl phosphite complex salt has an average particle diameter D50 of 4 to 40 μm, such as 4 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, or 40 μm, and the like. The organic phosphorus flame retardant and the aluminum phosphite-alkyl aluminum phosphite composite salt adopt approximate particle size ranges, so that the powder can be uniformly mixed, the synergistic flame retardant effect can be exerted to the maximum extent, and the use effect of the flame retardant is improved.
Preferably, the halogen-free flame retardant compound also comprises a char-forming agent.
As a preferred technical scheme of the invention, the addition of the char-forming agent can make up the deficiency of the gas-phase flame-retardant efficiency of the organic phosphorus flame retardant, promote the catalytic char formation of the organic phosphorus flame retardant in the combustion process, form a thicker char layer on the surface of the material, obstruct the diffusion of combustible gas, and improve the flame-retardant performance of the material.
Preferably, the char-forming agent is present in an amount of 1-5%, such as 1%, 2%, 3%, 4%, or 5%, etc., based on 100% of the mass of the halogen-free flame retardant formulation.
Preferably, the char-forming agent comprises any one of or a combination of at least two of zinc oxide, zinc borate, zinc stannate, or zirconium phosphate.
Preferably, the average particle diameter D50 of the carbon forming agent is 2-50 μm, such as 2 μm, 4 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, and the like, and the average particle diameter of the carbon forming agent is similar to the average particle diameters of the other two flame retardants, so that the powder can be uniformly mixed, the synergistic flame retardant effect can be exerted to the maximum extent, and the use effect of the flame retardant can be improved.
Preferably, the nylon comprises any one of nylon 6 (PA 6), nylon 66 (PA 66), nylon 11 (PA 11), nylon 12 (PA 12), nylon 46 (PA 46), nylon 610 (PA 610), nylon 612 (PA 612), nylon 1010 (PAl 010), semi-aromatic nylon 6T (PA 6T), or specialty nylon, or a combination of at least two thereof; preferably nylon 6 (PA 6), nylon 66 (PA 66), or semi-aromatic nylon 6T (PA 6T), or a combination of at least two thereof.
The reinforcement used in the formulation system of the present invention is most commonly glass fiber, but is equally applicable to other types of reinforcement, such as carbon fiber, silicon carbide ceramic fiber, aramid fiber, or the like.
In a second aspect, the present invention provides a method for preparing the halogen-free flame retardant glass fiber reinforced nylon of the first aspect, wherein the method comprises the following steps:
(1) Mixing organic phosphorus flame retardant, aluminum phosphite-alkyl aluminum phosphite composite salt and optional char-forming agent according to the formula ratio to obtain a halogen-free flame retardant compound;
(2) Adding the nylon, the glass fiber and the halogen-free flame-retardant compound into an extruder according to the formula ratio, and extruding and granulating to obtain the halogen-free flame-retardant glass fiber reinforced nylon;
preferably, the extruder is a twin screw extruder.
As a preferred technical scheme of the invention, the preparation method of the halogen-free flame-retardant glass fiber reinforced nylon comprises the following steps:
(1) Mixing organic phosphorus flame retardant, aluminum phosphite-alkyl aluminum phosphite composite salt and optional char-forming agent according to the formula ratio to obtain a halogen-free flame retardant compound;
(2) And (2) adding a nylon base material into a hopper by adopting a double-screw extruder, adding glass fiber from a glass fiber inlet, adding the halogen-free flame-retardant compound prepared in the step (1) from a powder feeding hole, starting a host machine and a feeder, and extruding and granulating to obtain the halogen-free flame-retardant glass fiber reinforced nylon.
In a third aspect, the invention provides the application of the halogen-free flame-retardant glass fiber reinforced nylon in the first aspect in electronic appliances, sports equipment or textiles.
Compared with the prior art, the invention at least has the following beneficial effects:
the aluminum phosphite-alkyl aluminum phosphite composite salt has good heat stability, no acidic substance is generated at high temperature, the corrosion to equipment is low, the aluminum phosphite-alkyl aluminum phosphite composite salt is compounded with an organic phosphorus flame retardant in a specific proportion for use, excellent flame retardant efficiency is shown, the aluminum phosphite-alkyl aluminum phosphite composite salt has good compatibility with a nylon base material, and no precipitation and no corrosion to processing equipment are caused in the processing and using process. The halogen-free flame-retardant glass fiber reinforced nylon is added with the halogen-free flame-retardant compound, so that the halogen-free flame-retardant glass fiber reinforced nylon has excellent comprehensive performance and better flame retardant performance (flame retardant property: V-0).
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The methyl phosphorous acid and the ethyl phosphorous acid used in the preparation examples are obtained by respectively catalyzing dimethyl methyl phosphite and diethyl ethyl phosphite by concentrated sulfuric acid and hydrolyzing. Otherwise, the raw materials were purchased commercially unless otherwise specified.
The aluminium diethylphosphinate used in the examples according to the invention had an average particle size D50 of 32 μm, the DOPO ethyl bridge derivative had an average particle size D50 of 21 μm, the zinc borate had an average particle size D50 of 10 μm and the zirconium phosphate had an average particle size D50 of 11 μm.
Preparation example 1
In the present preparation example, there is provided a method for preparing an aluminum phosphite-alkyl aluminum phosphite composite salt, the method comprising the steps of:
adding 332.3g of phosphorous acid, 49.7g of ethyl phosphorous acid and 1.6kg of water into a stainless steel autoclave lined with tetrafluoroethylene, starting stirring, adding 234.7g of aluminum hydroxide and 6.0g of 98% concentrated sulfuric acid after the phosphorous acid and the ethyl phosphorous acid are dissolved, sealing the reaction kettle, heating to 200 ℃, stirring at a high speed, finishing the reaction after reacting for 2 hours, cooling, filtering the slurry, washing with deionized water, and drying at 150 ℃ to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt with the average particle size D50 of 12 microns.
Preparation example 2
In the present preparation example, there is provided a method for preparing an aluminum phosphite-alkyl aluminum phosphite composite salt, the method comprising the steps of:
adding 221.5g of phosphorous acid, 74.2g of ethyl phosphorous acid and 1.5kg of water into a stainless steel autoclave lined with tetrafluoroethylene, starting stirring, adding 175.5g of aluminum hydroxide and 30.0g of 98% concentrated sulfuric acid after the phosphorous acid and the ethyl phosphorous acid are dissolved, sealing the reaction kettle, heating to 150 ℃, stirring at a high speed, finishing the reaction after reacting for 6 hours, cooling, filtering the slurry, washing with deionized water, and drying at 150 ℃ to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt with the average particle size D50 of 20 mu m.
Preparation example 3
In the present preparation example, there is provided a method for preparing an aluminum phosphite-alkyl aluminum phosphite composite salt, the method comprising the steps of:
into a stainless steel autoclave lined with tetrafluoroethylene, 1155.0g of sodium phosphite (Na) was charged 2 HPO 3 ·5H 2 O), 8.32g of sodium ethylphosphite (C) 2 H 5 PO 3 Na 2 ) 5.0kg of water, stirring to fully dissolve sodium phosphite and ethyl sodium phosphite, and adding 945.6g of aluminum sulfate [ Al ] 2 (SO 4 ) 3 ·16H 2 O]60.0g of 98 percent sulfuric acid, sealing the reaction kettle, heating to 100 ℃, stirring at high speed for reaction for 8 hours, ending the reaction, cooling, filtering the slurry, washing with deionized water, and drying at 150 ℃ to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt with the average particle size D50 of 32 mu m.
Preparation example 4
In the present preparation example, there is provided a method for preparing an aluminum phosphite-alkyl aluminum phosphite composite salt, the method comprising the steps of:
583.2g of sodium phosphite (Na) were added to a stainless steel autoclave lined with tetrafluoroethylene 2 HPO 3 ·5H 2 O), 104.5g sodium ethylphosphite (C) 2 H 5 PO 3 Na 2 ) 5.4kg of water, stirring is started to fully dissolve sodium phosphite and sodium ethylphosphite, and then 708.8g of aluminum sulfate [ Al ] is added 2 (SO 4 ) 3 ·16H 2 O]22.5g of 98% concentrated sulfuric acid, sealing the reaction kettle, heating to 160 ℃, stirring at high speed for reaction for 2 hours, ending the reaction, cooling, filtering the slurry, washing with deionized water, and drying at 150 ℃ to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt. The average particle diameter D50 was 21 μm.
Preparation example 5
In the present preparation example, there is provided a method for preparing an aluminum phosphite-alkyl aluminum phosphite composite salt, the method comprising the steps of:
to a stainless steel autoclave lined with tetrafluoroethylene 777 was added9g sodium phosphite (Na) 2 HPO 3 ·5H 2 O), 127.9g of sodium methylphosphite (CH) 3 PO 3 Na 2 ) 5.0kg of water, stirring to fully dissolve the sodium phosphite and the sodium methylphosphite, and adding 945.8g of aluminum sulfate [ Al ] into the solution 2 (SO 4 ) 3 ·16H 2 O]61.0g of 98 percent sulfuric acid, sealing the reaction kettle, heating to 170 ℃, stirring at high speed for reaction for 4 hours, ending the reaction, cooling, filtering the slurry, washing with deionized water, and drying at 150 ℃ to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt with the average particle size D50 of 18 mu m.
Examples 1 to 5
Mixing part of the aluminum phosphite-alkyl aluminum phosphite composite salt prepared in the preparation examples 1-5 with an organic phosphorus flame retardant and an optional char forming agent respectively to obtain a halogen-free flame retardant compound, carrying out a corrosivity test on the obtained compound, preparing raw materials according to a formula shown in the table 1, fully drying the raw materials, adding the raw materials into a double-screw extruder for extrusion granulation, and preparing a standard sample strip (the thickness of the sample strip is 1.6 mm) on an injection molding machine.
Comparative examples 1 to 4
The aluminum phosphate-alkyl aluminum phosphite complex salts in examples 1-4 were each replaced with an equal amount of commercially available melamine polyphosphate.
Comparative example 5
The comparative example differs from example 5 only in that the aluminum phosphite-alkyl aluminum phosphite complex salt was added in an amount of 7 parts by weight and the aluminum diethylphosphinate was added in an amount of 12.5 parts by weight.
Comparative example 6
The comparative example differs from example 5 only in that the amount of PA66 was 58 parts by weight, the amount of glass fiber was 35 parts by weight, the amount of aluminum phosphite-aluminum alkyl phosphite complex salt added was 1 part by weight, and the amount of aluminum diethylphosphinate added was 5.5 parts by weight.
Comparative example 7
This comparative example differs from example 5 only in that the aluminum diethylphosphinate was replaced by an equal amount of melamine cyanurate.
The performance of the halogen-free flame-retardant glass fiber reinforced nylon provided in the examples and comparative examples was tested by the following methods:
(1) And (3) corrosion test: arranging a metal copper block on a die head, contacting a high-temperature material with the metal block in the die head, and testing the loss X% of the metal after 50Kg material granulation, wherein the higher the loss is, the worse the corrosion resistance is;
the calculation formula of X% is:
wherein, w 1 Weight of copper ingot before corrosion test, w 2 The weight of the copper block after the corrosion resistance experiment;
(2) And (3) testing the flame retardant property: the test was carried out by the UL 94V 0 (1.6 mm) method, with 6 bars per group.
The raw materials and amounts (parts by weight) used in the examples and comparative examples, and the test results are shown in table 1.
TABLE 1
Wherein, preparation example 1 in Table 1 refers to the addition of the aluminum phosphite-alkyl aluminum phosphite composite salt prepared in preparation example 1, and other similar expressions have the same meanings and are not explained one by one.
As can be seen from Table 1, the halogen-free flame-retardant glass fiber reinforced nylon provided by the embodiment of the invention has a good flame-retardant effect (V-0), and has low corrosion to equipment in the granulation process.
Compared with the examples 1 to 4, the halogen-free flame-retardant glass fiber reinforced nylon provided in the comparative examples 1 to 4 has significantly increased corrosion to equipment during granulation, and the flame-retardant effect of the halogen-free flame-retardant glass fiber reinforced nylon provided in the comparative examples 1 to 2 is reduced.
Compared with example 5, the flame retardant effect of the halogen-free flame retardant glass fiber reinforced nylon provided in comparative example 5 is reduced, and compared with example 5, the flame retardant effects of the halogen-free flame retardant glass fiber reinforced nylon provided in comparative examples 6 to 7 are all obviously reduced.
The applicant states that the present invention is illustrated by the above examples to the halogen-free flame-retardant glass fiber reinforced nylon of the present invention, and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. the present invention is not meant to be implemented by relying on the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (43)
1. The halogen-free flame-retardant glass fiber reinforced nylon is characterized in that the halogen-free flame-retardant glass fiber reinforced nylon comprises the following raw materials in percentage by weight:
30-60% of nylon;
20-40% of glass fiber;
10-30% of halogen-free flame-retardant compound;
the halogen-free flame retardant compound consists of an organic phosphorus flame retardant and aluminum phosphite-alkyl aluminum phosphite composite salt, wherein the content of the organic phosphorus flame retardant is 70-90% and the content of the aluminum phosphite-alkyl aluminum phosphite composite salt is 10-30% by taking the mass of the halogen-free flame retardant compound as 100%;
the organophosphorus flame retardant consists of dialkyl hypophosphite and/or DOPO bridging group derivatives.
2. The halogen-free flame retardant glass fiber reinforced nylon of claim 1, wherein the dialkylphosphinate has a structure represented by formula a:
the compound of the formula A is shown in the specification,
wherein R is 1 、R 2 Each independently selected from any one of ethyl, propyl or butylSeed growing; y is selected from any one of magnesium, calcium, aluminum or zinc; x is an integer from 2 to 4.
3. The halogen-free flame-retardant glass fiber reinforced nylon according to claim 2, wherein Y is aluminum or zinc.
4. The halogen free flame retardant glass fiber reinforced nylon of claim 2, wherein the dialkylphosphinate salt is aluminum diethylphosphinate.
5. The halogen-free flame retardant glass fiber reinforced nylon of claim 1, wherein the DOPO bridging derivative has a structure represented by formula B:
in the formula B, the compound is shown in the specification,
wherein R is 3 、R 4 Each independently selected from hydrogen and C 1 -C 4 Any one of alkyl, nitro or amino groups of (1); n is an integer of 1 to 4.
6. The halogen-free flame-retardant glass fiber reinforced nylon according to claim 5, wherein R is R 3 、R 4 Are both hydrogen and n is 1.
7. The halogen-free flame retardant glass fiber reinforced nylon of claim 1, wherein the aluminum phosphite-alkyl aluminum phosphite composite salt is prepared by the following steps: and (2) performing a neutralization reaction on phosphorous acid and alkyl phosphorous acid and an aluminum source or performing a neutralization reaction by a method II: phosphite, alkyl phosphite and aluminum salt are subjected to double decomposition reaction to prepare the product.
8. The halogen-free flame-retardant glass fiber reinforced nylon according to claim 7, wherein the first method comprises the following steps:
mixing phosphorous acid, alkyl phosphorous acid and water, then adding an aluminum source and a reaction auxiliary agent, heating, reacting and post-treating to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt.
9. The halogen-free flame retardant glass fiber reinforced nylon of claim 8, wherein the phosphorous acid has a structure represented by C1, and the alkyl phosphorous acid has a structure represented by D1:
C1 D1
wherein R is 5 Is selected from any one of methyl, ethyl, propyl or butyl.
10. The halogen-free flame-retardant glass fiber reinforced nylon of claim 8, wherein the aluminum source comprises any one of alumina, aluminum hydroxide, aluminum oxyhydroxide, pseudo-boehmite, or a combination of at least two thereof.
11. The halogen-free, flame-retardant glass fiber reinforced nylon of claim 8, wherein the reaction aid comprises an acid.
12. The halogen-free flame retardant glass fiber reinforced nylon of claim 11, wherein the reaction auxiliary agent is any one of sulfuric acid, hydrochloric acid or nitric acid.
13. The halogen-free flame retardant glass fiber reinforced nylon according to claim 8, wherein the molar content of phosphorous acid is 60.0-99.8% and the molar content of alkyl phosphorous acid is 0.2-40.0%, based on 100% of the total molar content of phosphorous acid and alkyl phosphorous acid.
14. The halogen-free flame retardant glass fiber reinforced nylon of claim 8, wherein the ratio of the sum of the moles of phosphorous acid and alkyl phosphorous acid to the moles of aluminum ions in the aluminum source is (1.5-1.8): 1.
15. The halogen-free flame-retardant glass fiber reinforced nylon of claim 8, wherein the molar number of the reaction assistant is 1-20% of the molar number of the aluminum ions in the aluminum source.
16. The halogen-free flame-retardant glass fiber reinforced nylon according to claim 8, wherein the temperature rise is to 100-200 ℃.
17. The halogen-free flame retardant glass fiber reinforced nylon of claim 8, wherein the reaction time is 2-8 h.
18. The halogen-free flame retardant glass fiber reinforced nylon of claim 8 wherein the post-treatment comprises filtering, washing and drying.
19. The halogen-free flame retardant glass fiber reinforced nylon of claim 7, wherein the second method comprises the following steps:
mixing phosphite, alkyl phosphite and water, then adding aluminum salt and a reaction auxiliary agent, heating, reacting and post-treating to obtain the aluminum phosphite-alkyl aluminum phosphite composite salt.
20. The halogen-free flame retardant glass fiber reinforced nylon of claim 19, wherein the phosphite anion has a structure represented by C2, and the alkyl phosphite anion has a structure represented by D2:
C2 D2
wherein R is 6 Is selected from any one of methyl, ethyl, propyl or butyl.
21. The halogen free flame retardant glass fiber reinforced nylon of claim 19, wherein the cation of phosphite is sodium or potassium.
22. The halogen free flame retardant glass fiber reinforced nylon of claim 19, wherein the cation of the alkyl phosphite is sodium or potassium.
23. The halogen free flame retardant glass fiber reinforced nylon of claim 19, wherein the phosphite is a water soluble phosphite including sodium phosphite and/or potassium phosphite.
24. The halogen free flame retardant glass fiber reinforced nylon of claim 19, wherein the alkyl phosphite is a water soluble alkyl phosphite including sodium alkyl phosphite and/or potassium alkyl phosphite.
25. The halogen free flame retardant glass fiber reinforced nylon of claim 19, wherein the aluminum salt comprises any one of aluminum sulfate, aluminum nitrate or aluminum chloride or a combination of at least two thereof.
26. The halogen free flame retardant glass fiber reinforced nylon of claim 19, wherein the reaction aid comprises an acid.
27. The halogen-free flame retardant glass fiber reinforced nylon of claim 26, wherein the reaction auxiliary agent is any one of sulfuric acid, hydrochloric acid or nitric acid.
28. The halogen-free flame retardant glass fiber reinforced nylon of claim 19, wherein the molar content of phosphite is 60.0-99.8% and the molar content of alkyl phosphite is 0.2-40.0%, based on 100% of the total molar content of phosphite and alkyl phosphite.
29. The halogen free flame retardant glass fiber reinforced nylon of claim 19, wherein the ratio of the sum of the moles of phosphite and alkyl phosphite to the moles of aluminum ions in the aluminum salt is (1.5-1.8): 1.
30. The halogen-free flame-retardant glass fiber reinforced nylon of claim 19, wherein the molar number of the reaction assistant is 1-20% of the molar number of the aluminum ions in the aluminum salt.
31. The halogen-free flame-retardant glass fiber reinforced nylon of claim 19, wherein the temperature rise is from 100 ℃ to 200 ℃.
32. The halogen-free flame retardant glass fiber reinforced nylon of claim 19 wherein the reaction time is 2-6 hours.
33. The halogen free, flame retardant glass fiber reinforced nylon of claim 19 wherein the post-treatment comprises filtering, washing and drying.
34. The halogen-free flame-retardant glass fiber reinforced nylon according to claim 1, wherein the organophosphorus flame retardant has an average particle diameter D50 of 20 to 50 μm, and the aluminum phosphite-aluminum alkyl phosphite composite salt has an average particle diameter D50 of 2 to 50 μm.
35. The halogen-free flame-retardant glass fiber reinforced nylon according to claim 1, wherein the halogen-free flame-retardant compound further comprises a char-forming agent.
36. The halogen-free flame-retardant glass fiber reinforced nylon according to claim 35, wherein the char-forming agent is present in an amount of 1-5% based on 100% by mass of the halogen-free flame-retardant compound.
37. The halogen free, flame retardant glass fiber reinforced nylon of claim 35 wherein the char former comprises any one of zinc oxide, zinc borate, zinc stannate, or zirconium phosphate, or a combination of at least two thereof.
38. The halogen-free flame-retardant glass fiber reinforced nylon according to claim 35, wherein the char-forming agent has an average particle diameter D50 of 2 to 50 μm.
39. The halogen free flame retardant glass fiber reinforced nylon of claim 1, wherein the nylon comprises any one of nylon 6, nylon 66, nylon 11, nylon 12, nylon 46, nylon 610, nylon 612, nylon 1010, semi-aromatic nylon 6T or specialty nylon or a combination of at least two thereof.
40. The halogen free flame retardant glass fiber reinforced nylon of claim 39, wherein the nylon is any one of nylon 6, nylon 66 or semi-aromatic nylon 6T or a combination of at least two thereof.
41. The method for preparing halogen free flame retardant glass fiber reinforced nylon according to any of claims 1-40, wherein the method comprises the following steps:
(1) Mixing the organic phosphorus flame retardant, aluminum phosphite-alkyl aluminum phosphite composite salt and optional char-forming agent according to the formula ratio to obtain a halogen-free flame-retardant compound;
(2) Adding the nylon, the glass fiber and the halogen-free flame-retardant compound into an extruder according to the formula ratio, and extruding and granulating to obtain the halogen-free flame-retardant glass fiber reinforced nylon.
42. The method of claim 41, wherein the extruder is a twin screw extruder.
43. Use of the halogen free flame retardant glass fiber reinforced nylon of any of claims 1-40 in electronics, sports equipment or textiles.
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