CN113754902B - Environment-friendly polyamide flame-retardant master batch and preparation method thereof - Google Patents
Environment-friendly polyamide flame-retardant master batch and preparation method thereof Download PDFInfo
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The application relates to an environment-friendly polyamide flame-retardant master batch and a preparation method thereof, wherein the environment-friendly polyamide flame-retardant master batch comprises the following components: the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of synergist, wherein the polymerized phosphate can generate oxide ceramic after decomposition. The environment-friendly polyamide flame-retardant master batch has good heat stability, melt fluidity, whiteness and flame retardant property, generates no toxic gas in the flame retardant process, meets the environment-friendly requirement, has good flame retardant effect, and can be widely applied to the field of flame-retardant plastic production.
Description
Technical Field
The application relates to the field of flame-retardant modification of high polymer materials, in particular to an environment-friendly polyamide flame-retardant master batch and a preparation method thereof.
Background
Most of the traditional flame-retardant engineering plastics are manufactured by compounding powder flame retardant compositions, halogen-containing flame retardant compositions or nitrogen-phosphorus halogen-free flame retardant compositions with engineering plastics. The powder flame retardant composition can improve the flame retardant effect of engineering plastics, but has large dust in the use process, can generate serious environmental pollution, is easy to generate uneven dispersion phenomenon in the application of the engineering plastics, and influences the use effect. The flame-retardant engineering plastic prepared by compounding the halogen-containing flame retardant composition and the engineering plastic does not meet the instruction requirements of ROHS and REACH because the halogen-containing flame retardant composition contains halogen and heavy metal elements, and the application field of the flame-retardant engineering plastic is limited. The nitrogen-phosphorus halogen-free flame retardant composition has low thermal decomposition temperature and poor heat resistance, so that the nitrogen-phosphorus halogen-free flame retardant composition is difficult to meet the requirements of high-temperature processing flame retardant engineering plastics.
Disclosure of Invention
Based on the above, it is necessary to provide an environment-friendly polyamide flame retardant masterbatch and a preparation method thereof; the environment-friendly polyamide flame-retardant master batch has good thermal stability, generates no toxic gas in the flame-retardant process, meets the environment-friendly requirement, has good flame-retardant effect, and can be widely applied to the field of flame-retardant plastic production.
An environment-friendly polyamide flame-retardant master batch comprises the following components: the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of synergist, wherein the polymerized phosphate can generate oxide ceramic after decomposition.
In one embodiment, the polyamide resin is a powder, and the relative viscosity of the polyamide resin is 2.3-2.45.
In one embodiment, the mass fraction of the polyamide resin in the environment-friendly polyamide flame-retardant masterbatch is 20% -45%, the mass fraction of the halogen-free flame retardant composition in the environment-friendly polyamide flame-retardant masterbatch is 42% -75%, the mass fraction of the dispersing agent in the environment-friendly polyamide flame-retardant masterbatch is 4% -10%, and the mass fraction of the stabilizing agent in the environment-friendly polyamide flame-retardant masterbatch is 1% -3%.
In one embodiment, the alkyl phosphinate has the structure ofWherein R is 1 And R is 2 Each independently selected from one of hydroxyl group, alkyl group having 1-6 carbon atoms, and aryl group having 6-18 carbon atoms, and R 1 And R is 2 At most one hydroxyl group, M is a metal element, n is an integer, and n=1-4.
In one embodiment, the polymeric phosphate comprises at least one of aluminum tripolyphosphate, magnesium tripolyphosphate, zinc tripolyphosphate, titanium tripolyphosphate, and silicon tripolyphosphate.
In one embodiment, the synergist comprises at least one of anhydrous zinc borate, nano silica, and organic montmorillonite.
In one embodiment, the stabilizer comprises at least bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and the mass ratio of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate to N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine is 1:1-3:1.
Compared with the traditional flame retardant, the halogen-free flame retardant composition comprises the alkyl phosphinate, the polyphosphate and the synergist, wherein the alkyl phosphinate can form a coke layer on the surface of the plastic, so that the decomposition and flame heat transfer inside the plastic are reduced, the halogen-free flame retardant composition becomes a heat insulation protection layer of the plastic, and the polyphosphate and the synergist can form a blocking layer to cover the surface of the plastic at the combustion temperature, so that the effects of blocking heat, air or oxygen are achieved, and the alkyl phosphinate is assisted to realize effective flame retardance. Meanwhile, as the thermal decomposition temperatures of the alkyl phosphinate flame retardant and the polymerized phosphate are relatively high, the polymerized phosphate cannot be decomposed and separated out in the manufacturing and using processes of the environment-friendly polyamide flame retardant master batch, and the product quality and the thermal stability are improved.
In addition, the halogen-free flame retardant composition adopted by the application does not contain halogen and heavy metal elements, so that the environment-friendly polyamide flame retardant master batch is free from toxic gas generation in the flame retardant process, meets the environment-friendly requirement, and can be widely applied to various flame retardant engineering fields.
The application also provides a preparation method of the environment-friendly polyamide flame-retardant master batch, which comprises the following steps:
uniformly mixing polyamide resin, a halogen-free flame retardant composition, a dispersing agent and a stabilizing agent to obtain a mixed material, wherein the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of synergist by mass percent;
and heating, mixing and plasticizing the mixed material, and then extruding and granulating to obtain the environment-friendly polyamide flame-retardant master batch.
In one embodiment, the heating, mixing and plasticizing are performed in a twin-rotor continuous mixer comprising a first temperature control zone and a second temperature control zone.
In one embodiment, the heating temperature of the first temperature control zone is 130 ℃ to 280 ℃ and the heating temperature of the second temperature control zone is 190 ℃ to 340 ℃.
The preparation method of the environment-friendly polyamide flame-retardant master batch adopts the polyamide resin, the halogen-free flame retardant composition, the dispersing agent and the stabilizing agent to compound, and the environment-friendly polyamide flame-retardant master batch is obtained by mixing, plasticizing and extruding granulation of the mixed materials. Compared with the traditional preparation method of melting granulation, the application not only changes the mixed material from solid state to molten state through melting, but also enables the mixed material to be completely melted and fully mixed through further plasticizing, and reaches the forming temperature of granulation. Meanwhile, the plasticizing also enables the mixed material to have good fluidity and plasticity, is favorable for granulation molding, and ensures that all components in the environment-friendly polyamide flame-retardant master batch obtained through granulation are uniformly distributed, so that the environment-friendly polyamide flame-retardant master batch has high quality and good flame-retardant effect.
In addition, the environment-friendly polyamide flame-retardant master batch can be used for preparing plastics, solves the dust emission problem in the production process of flame-retardant engineering plastics because no dust is generated in the production process, simplifies the production process of plastics and is beneficial to improving the production efficiency and the product quality. The environment-friendly polyamide flame-retardant master batch has good thermal stability, and flame-retardant components in the environment-friendly polyamide flame-retardant master batch are not easy to decompose and separate out in the high-temperature processing process, so that the environment-friendly polyamide flame-retardant master batch can be widely applied to the field of flame-retardant plastic production, and particularly can be well applied to flame-retardant plastics which need to be prepared at high temperature, and has wide market prospect.
Detailed Description
The environment-friendly polyamide flame-retardant master batch and the preparation method thereof provided by the application are further described below.
The environment-friendly polyamide flame-retardant master batch provided by the application comprises the following components: the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of synergist, wherein the polymerized phosphate can generate oxide ceramic after decomposition.
Although the halogen flame retardant has good universality and relatively low cost, more smoke, corrosive and toxic gases are generated during combustion, which not only endangers the health of human bodies, but also causes serious damage to the environment. Therefore, the halogen-free flame retardant composition is selected, does not contain halogen and heavy metal elements, so that the environment-friendly polyamide flame retardant master batch generates no toxic gas in the flame retardant process, meets the instruction requirement of European Union regulations, and can be widely applied to various flame retardant engineering fields.
Because the alkyl phosphinate can form a shielding coke layer on the surface of the plastic under the condition of high-temperature combustion, on one hand, the decomposition of the plastic can be relieved, and the generation amount of flammable volatile matters can be reduced; on the other hand, the protective layer effect of heat insulation and oxygen resistance can be formed, and the heat transfer to the inside of the plastic is reduced. At the same time, the alkyl phosphinate releases phosphorus-containing substances under the high temperature condition, and the phosphorus-containing substances can further form PO.PO under the high temperature condition 2 Radical quenchers such as HPO. In the combustion process of the polymer, a large amount of H, HO and O free radicals are generated to promote gas-phase combustion reaction, and at this time, the H, HO and O free radicals are more prone to be captured and quenched by a free radical quencher, so that chain reactions of the H, HO and O free radicals in combustion are blocked, and high-efficiency flame retardance is realized. Thus, the alkyl phosphinate is included as one of the components of the halogen-free flame retardant composition.
In some embodiments, the alkyl phosphinate has the structure ofWherein R is 1 And R is 2 Each independently selected from one of hydroxyl group, alkyl group having 1-6 carbon atoms, and aryl group having 6-18 carbon atoms, and R 1 And R is 2 At most one hydroxyl group, M is a metal element, n is an integer, and n=1-4.
Specifically, the R 1 And R is 2 Preferably one of methyl and ethyl, and M is preferably one of Mg, ca, zn, al, fe, ba, the alkyl phosphinate is preferably magnesium diethyl phosphinate, calcium diethyl phosphinate, zinc diethyl phosphinate, aluminum diethyl phosphinate, iron diethyl phosphinate, barium diethyl phosphinate, magnesium methylethyl phosphinate, calcium methylethyl phosphinate, zinc methylethyl phosphinate, aluminum methylethyl phosphinate, iron methylethyl phosphinate, aluminum methyl ethyl phosphinate, aluminum,At least one of the barium methylethyl phosphinates is further preferably aluminum diethyl phosphinate.
In order to further improve the heat stability of the environment-friendly polyamide flame-retardant master batch, the application combines the polymerized phosphate with high pyrolysis temperature and good heat resistance with the alkyl phosphinate. The polymeric phosphate can simultaneously form pyrophosphoric acid and oxide on the surface of the molten plastic after burning, and at the moment, the oxide is molten oxide ceramic, and can cover the surface of the burnt polymer to form a barrier layer to isolate air and oxygen and assist the alkyl phosphinate to achieve the flame-retardant effect.
In some embodiments, the polymeric phosphate comprises at least one of aluminum tripolyphosphate, magnesium tripolyphosphate, zinc tripolyphosphate, titanium tripolyphosphate, silicon tripolyphosphate, preferably aluminum tripolyphosphate.
In some embodiments, the halogen-free flame retardant composition further comprises a synergist, wherein the synergist comprises at least one of anhydrous zinc borate, nanosilica, organo montmorillonite.
Because the anhydrous zinc borate can absorb a large amount of heat energy released by combustion and generate B under the high temperature condition of more than 300 ℃ when the anhydrous zinc borate is used as a synergist 2 O 3 The barrier layer is covered on the surface of the burnt plastic, achieves the effect of blocking heat, air or oxygen, and is flame-retardant together with alkyl phosphinate and polymerized phosphate.
Because the nano silicon dioxide has the characteristics of low density and high specific surface area, the gas-phase silicon dioxide and the condensed phase silicon dioxide can be gathered on the surface of the burnt plastic as a barrier layer under the high temperature condition, so that the contact between the plastic and flame is reduced.
Thus, in some embodiments, the synergist is preferably at least one of anhydrous zinc borate, nanosilica.
In order to improve the flame-retardant synergistic effect of the halogen-free flame retardant composition, the mass fraction of each component of the halogen-free flame retardant composition is more preferably 55% -75% of alkyl phosphinate, 22% -45% of polymerized phosphate and 5.5% -9% of synergistic agent.
In order to enable the halogen-free flame retardant composition to be uniformly dispersed in the matrix, and the matrix has good fluidity under high-temperature melting, so that the processing and forming of the flame retardant master batch are facilitated, and the product quality of the flame retardant master batch is improved. Therefore, in some embodiments, the polyamide resin is preferably a powder, and the relative viscosity of the polyamide resin is preferably 2.3 to 2.45, more preferably 2.37.
Wherein the polyamide resin comprises at least one of polycaprolactam (PA 6), polyhexamethylene adipamide (PA 66), polyhexamethylene sebacamide (PA 610), polyhexamethylene dodecanoamide (PA 612), polybutylene adipamide (PA 46), polyhexamethylene terephthalamide (PA 6T) and polynaphthalamide (PA 9T). In order to improve the heat resistance and the mechanical property at high temperature of the environment-friendly polyamide flame-retardant master batch, the polyamide resin is preferably at least one of PA6, PA66 and PA 6T.
In order to assist in better dispersion of the components, the polyamide resin, the halogen-free flame retardant composition and the stabilizer are uniformly distributed, and the environment-friendly polyamide flame retardant master batch further comprises a dispersing agent. In some embodiments, the dispersant includes at least one of ethylene-butyl acrylate-glycidyl methacrylate copolymer (PTW), ethylene hard fatty acid amide (EBS).
In order to reduce the phenomenon that flame retardant master batches are grey due to thermal oxidation aging, the stabilizer at least comprises bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (PEP-36) and N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098), wherein the molecular weight of the stabilizer PEP-36 and the molecular weight of the antioxidant 1098 are large, and the stabilizer has stronger free radical capturing capability and peroxide decomposing capability. Specifically, the mass ratio of PEP-36 to antioxidant 1098 is 1:1-3:1, and more preferably 2:1.
It will be appreciated that the stabilizer of the present application may further comprise other antioxidants, such as: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), and the like.
In order to improve the flame retardant performance of the environment-friendly polyamide flame retardant master batch and the dispersion effect in plastics in application, the mass fraction of the polyamide resin in the environment-friendly polyamide flame retardant master batch is preferably 20% -45%, the mass fraction of the halogen-free flame retardant composition in the environment-friendly polyamide flame retardant master batch is preferably 42% -75%, the mass fraction of the dispersing agent in the environment-friendly polyamide flame retardant master batch is preferably 4% -10%, and the mass fraction of the stabilizing agent in the environment-friendly polyamide flame retardant master batch is preferably 1% -3%.
In the application process, if the water content in the flame-retardant master batch is too high, the processing of the plastic product can be influenced on one hand, and on the other hand, the problems of cracking, light reflection, impact resistance, tensile strength reduction and the like of the plastic product can be caused, so that the quality of the plastic product is reduced, and the rejection rate of the plastic product is improved. Meanwhile, the higher water content is not beneficial to dehydration and carbonization of diethyl hypophosphite at high temperature, so that the flame retardant property of the plastic product is reduced. Therefore, the mass fraction of water in the environment-friendly polyamide flame-retardant master batch is less than or equal to 0.3%, and further, the mass fraction of water in the flame-retardant master batch is preferably less than or equal to 0.2%.
The application also provides a preparation method of the environment-friendly polyamide flame-retardant master batch, which comprises the following steps:
s1, uniformly mixing polyamide resin, a halogen-free flame retardant composition, a dispersing agent and a stabilizing agent to obtain a mixed material, wherein the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polyphosphate and 5-10% of synergist by mass percent;
s2, heating, mixing and plasticizing the mixed material, and then extruding and granulating to obtain the environment-friendly polyamide flame-retardant master batch.
In the step S2, a double-rotor continuous mixer is adopted to heat, mix and plasticize the mixed materials, wherein the double-rotor continuous mixer comprises a first temperature control area and a second temperature control area, the heating temperature of the first temperature control area is 130-280 ℃, and the heating temperature of the second temperature control area is 190-340 ℃. Specifically, the first temperature control zone comprises a first zone, a second zone and a third zone, and the heating temperatures of the first zone, the second zone and the third zone are controlled within the range of 130-280 ℃. The main machine rotating speed of the double-rotor continuous mixing mill is 30Hz-50Hz, the main machine current is 90A-120A, and the feeding operation rotating speed is 3Hz-6Hz.
And after the step of heating, mixing and plasticizing the mixed material, extruding and granulating by adopting a single-screw extruder, wherein a heating area of the single-screw extruder comprises a first area, a second area, a third area, a fourth area, a screen changing area and a machine head. The rotating speed of the single screw extruder is 12Hz-16Hz, and the current is 93A-100A.
The preparation method of the environment-friendly polyamide flame-retardant master batch adopts the polyamide resin, the halogen-free flame retardant composition, the dispersing agent and the stabilizing agent to compound, and the environment-friendly polyamide flame-retardant master batch is obtained by mixing, plasticizing and extruding granulation of the mixed materials. Compared with the traditional preparation method of melting granulation, the application not only changes the mixed material from solid state to molten state through melting, but also enables the mixed material to be completely melted and fully mixed through further plasticizing, and reaches the forming temperature of granulation. Meanwhile, the plasticizing also enables the mixed material to have good fluidity and plasticity, is favorable for granulation molding, and ensures that each component in the flame-retardant master batch obtained through granulation is uniformly distributed, so that the flame-retardant master batch has high quality and good flame-retardant effect.
In addition, the environment-friendly polyamide flame-retardant master batch can be used for preparing plastics, solves the dust emission problem in the production process of flame-retardant engineering plastics because no dust is generated in the production process, simplifies the production process of plastics and is beneficial to improving the production efficiency and the product quality. The environment-friendly polyamide flame-retardant master batch has good thermal stability, and flame-retardant components in the environment-friendly polyamide flame-retardant master batch are not easy to decompose and separate out in the high-temperature processing process, so that the environment-friendly polyamide flame-retardant master batch can be widely applied to the field of flame-retardant plastic production, and particularly can be well applied to flame-retardant plastics which need to be prepared at high temperature, such as flame-retardant engineering plastics of PA6, PA66, PA6T, PA T and the like.
Hereinafter, the environment-friendly polyamide flame retardant master batch and the preparation method thereof will be further described by the following specific examples.
Example 1
23kg of powder PA6, 45.8kg of aluminum diethylphosphinate, 15.2kg of aluminum tripolyphosphate, 6kg of anhydrous zinc borate, 7kg of PTW, 2kg of PEP-36 and 1kg of antioxidant 1098 are weighed by an automatic metering device, wherein the relative viscosity of PA6 is 2.37.
And (3) putting all the components into mixing equipment with a stirring device, and fully and uniformly mixing to obtain a mixed material. And conveying the mixed materials into a double-rotor mixer with continuous mixing for heating, mixing and plasticizing, wherein the heating temperatures of a first zone, a second zone and a third zone of a double-rotor zone of the continuous mixing double-rotor mixer are controlled to 160 ℃, the heating temperature of a fourth zone is controlled to 200 ℃, the rotating speed of a main machine is adjusted to 34Hz, the current of the main machine is 95A, and the running rotating speed of double-rotor feeding is 5Hz. Extruding and granulating the heated, mixed and plasticized mixture by a single-screw extruder to obtain the flame-retardant master batch, wherein the heating temperature of one region to four regions of the single-screw extruder is controlled to be 230 ℃, the heating temperature of a screen changing region is controlled to be 240 ℃, the heating temperature of a machine head is controlled to be 220 ℃, the rotating speed is controlled to be 13Hz, and the current is controlled to be 94A.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Example 2
23kg of powder PA66, 36.6kg of aluminum diethylphosphinate, 25.4kg of aluminum tripolyphosphate, 6kg of silicon dioxide, 6kg of EBS, 2kg of PEP-36 and 1kg of antioxidant 1098 are weighed by an automatic metering device, wherein the relative viscosity of PA66 is 2.37.
And (3) putting all the components into mixing equipment with a stirring device, and fully and uniformly mixing to obtain a mixed material. And conveying the mixed materials into a double-rotor mixer with continuous mixing for heating, mixing and plasticizing, wherein the heating temperatures of a first zone, a second zone and a third zone of a double-rotor zone of the continuous mixing double-rotor mixer are controlled to 170 ℃, the heating temperature of a fourth zone is controlled to 220 ℃, the rotating speed of a main machine is adjusted to 34Hz, the current of the main machine is 95A, and the running rotating speed of double-rotor feeding is 5Hz. Extruding and granulating the heated, mixed and plasticized mixture by a single-screw extruder to obtain the flame-retardant master batch, wherein the heating temperature of one region to four regions of the single-screw extruder is controlled to be 240 ℃, the heating temperature of a screen changing region is controlled to be 250 ℃, the heating temperature of a machine head is controlled to be 240 ℃, the rotating speed is controlled to be 14Hz, and the current is controlled to be 96A.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Example 3
Example 3 differs from example 1 only in that 23kg of powder PA6, 42.7kg of aluminium diethylphosphinate, 12.3kg of aluminium tripolyphosphate, 6kg of anhydrous zinc borate, 7kg of PTW, 1.2kg of PEP-36, 0.6kg of antioxidant 1098 are weighed using an automatic metering device, where the relative viscosity of PA6 is 2.37.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Example 4
25kg of powder PA6T, 41.6kg of aluminum diethylphosphinate, 18.4kg of aluminum tripolyphosphate, 3kg of anhydrous zinc borate, 3kg of silicon dioxide, 6kg of EBS, 2kg of PEP-36 and 1kg of antioxidant 1098 are weighed by an automatic metering device, wherein the relative viscosity of PA9T is 2.40.
And (3) putting all the components into mixing equipment with a stirring device, and fully and uniformly mixing to obtain a mixed material. And conveying the mixed materials into a double-rotor mixer with continuous mixing for heating, mixing and plasticizing, wherein the heating temperatures of a first zone, a second zone and a third zone of a double-rotor zone of the continuous mixing double-rotor mixer are controlled to be 190 ℃, the heating temperature of a fourth zone is controlled to be 280 ℃, the rotating speed of a main machine is adjusted to be 35Hz, the current of the main machine is 97A, and the feeding operation rotating speed of the double rotors is 6Hz. Extruding and granulating the heated, mixed and plasticized mixture by a single-screw extruder to obtain the flame-retardant master batch, wherein the heating temperature of one region to four regions of the single-screw extruder is controlled to be 300 ℃, the heating temperature of a screen changing region is 320 ℃, the heating temperature of a machine head is 320 ℃, the rotating speed is 15Hz, and the current is 100A.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Example 5
Example 5 differs from example 1 only in that 45kg of powder PA6, 32.2kg of aluminium diethylphosphinate, 12kg of aluminium tripolyphosphate, 4kg of anhydrous zinc borate, 5kg of EBS, 1.2kg of PEP-36, 0.6kg of antioxidant 1098 are weighed using an automatic metering device, wherein the relative viscosity of PA6 is 2.37.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Example 6
Example 6 differs from example 1 only in that 21kg of powder PA6, 38.2kg of zinc diethylphosphinate, 32kg of aluminum tripolyphosphate, 3.8kg of silicon dioxide, 6kg of PTW, 1kg of PEP-36, 0.5kg of antioxidant 1098 are weighed using an automatic metering device, wherein the relative viscosity of PA6 is 2.37.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Example 7
Example 7 differs from example 1 only in that 25kg of powder PA6, 42kg of aluminium diethylphosphinate, 17.8kg of magnesium tripolyphosphate, 5.2kg of anhydrous zinc borate, 8.8kg of EBS, 0.8kg of PEP-36, 0.4kg of antioxidant 1098 are weighed using an automatic metering device, wherein the relative viscosity of PA6 is 2.37.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Example 8
22kg of powder PA66, 49kg of aluminum methylethyl hypophosphite, 14.6kg of titanium tripolyphosphate, 3.4kg of organic montmorillonite, 9.6kg of EBS, 1.1kg of PEP-36 and 0.4kg of antioxidant 1098 are weighed by an automatic metering device, wherein the relative viscosity of PA66 is 2.42.
And (3) putting all the components into mixing equipment with a stirring device, and fully and uniformly mixing to obtain a mixed material. And conveying the mixed materials into a double-rotor mixer with continuous mixing for heating, mixing and plasticizing, wherein the heating temperatures of a first zone, a second zone and a third zone of a double-rotor zone of the continuous mixing double-rotor mixer are controlled to 170 ℃, the heating temperature of a fourth zone is controlled to 220 ℃, the rotating speed of a main machine is adjusted to 34Hz, the current of the main machine is 95A, and the running rotating speed of double-rotor feeding is 5Hz. Extruding and granulating the heated, mixed and plasticized mixture by a single-screw extruder to obtain the flame-retardant master batch, wherein the heating temperature of one region to four regions of the single-screw extruder is controlled to be 240 ℃, the heating temperature of a screen changing region is controlled to be 250 ℃, the heating temperature of a machine head is controlled to be 240 ℃, the rotating speed is controlled to be 14Hz, and the current is controlled to be 96A.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Example 9
Example 9 differs from example 1 only in that 24kg of powder PA6, 45kg of magnesium diethylphosphinate, 16kg of zinc tripolyphosphate, 6.5kg of anhydrous zinc borate, 7.1kg of EBS, 0.7kg of PEP-36, 0.5kg of antioxidant 1098 are weighed using an automatic metering device, wherein the relative viscosity of PA6 is 2.37.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Comparative example 1
Comparative example 1 differs from example 1 only in that 12.2kg of melamine polyphosphate (MPP) was used instead of 12.2kg of aluminium tripolyphosphate.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Comparative example 2
Comparative example 2 differs from example 1 only in that 12.2kg of Melamine Cyanurate (MCA) was used instead of 12.2kg of aluminium tripolyphosphate.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Comparative example 3
Comparative example 3 differs from example 1 only in that 12.2kg of ferric tripolyphosphate was used instead of 12.2kg of aluminum tripolyphosphate.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Comparative example 4
Comparative example 4 differs from example 1 only in that 6kg of zinc borate pentahydrate was used instead of 6kg of zinc borate anhydrous.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Comparative example 5
Comparative example 5 differs from example 1 only in that 2kg of antioxidant 168 was used instead of 2kg of PEP-36 and 1kg of antioxidant 1010 was used instead of 1kg of antioxidant 1098.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
Comparative example 6
Comparative example 6 differs from example 1 only in that 1kg of antioxidant 1010 was used instead of 1kg of antioxidant 1098.
The prepared flame-retardant master batch is subjected to performance test, and specific results are shown in table 1.
TABLE 1
As can be seen from the test data in Table 1, the flame retardant masterbatch in comparative examples 1-2 has a 2% weight loss temperature about 8℃lower than the 2% weight loss temperature of example 1, and a residual ratio about 4% lower. The MPP and the MCA are easy to separate out and decompose in the manufacturing and using processes of the flame-retardant master batch due to low thermal decomposition temperature and poor heat resistance of the MPP and the MCA, so that the quality and the thermal stability of the flame-retardant master batch are affected, and the normal production of the flame-retardant polyamide and the application of products are seriously affected.
The flame retardant master batch of comparative example 3 uses iron tripolyphosphate instead of aluminum tripolyphosphate, and the heat resistance of the iron tripolyphosphate is reduced because the iron tripolyphosphate cannot form molten oxide ceramic under the high-temperature combustion condition. The flame retardant master batch of comparative example 4 adopts zinc pentahydrate borate instead of anhydrous zinc borate, and the heat stability of the flame retardant master batch is reduced due to a large number of bubbles generated in the master batch caused by the evaporation of water in the zinc pentahydrate borate in the process of melting and granulating.
The whiteness of the flame retardant master batches in comparative examples 5 to 6 was about 15% lower than that of example 1 because the high temperature antioxidant effect of the antioxidants 1010 and 168 was poor, resulting in the flame retardant master batches becoming grey, whereas example 1 overcomes this disadvantage by using PEP-36 and the antioxidants 1098.
Therefore, the environment-friendly polyamide flame-retardant master batch disclosed by the application has better melt fluidity, thermal stability, whiteness and flame retardant property, and a flame-retardant system, a dispersion system and a stabilization system of the environment-friendly polyamide flame-retardant master batch are better than those of the traditional polyamide resin flame-retardant master batch.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (6)
1. The environment-friendly polyamide flame-retardant masterbatch is characterized by comprising the following components: the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of synergist, wherein the polymerized phosphate can generate oxide ceramic after decomposition;
wherein the alkyl phosphinate has the structure ofWherein R is 1 And R is 2 Each independently selected from one of hydroxyl group, alkyl group having 1-6 carbon atoms, and aryl group having 6-18 carbon atoms, and R 1 And R is 2 At most one hydroxyl group, M is a metal element, n is an integer,n=1-4；
the polyphosphate comprises at least one of aluminum tripolyphosphate, magnesium tripolyphosphate, zinc tripolyphosphate, titanium tripolyphosphate and silicon tripolyphosphate;
the synergist comprises at least one of anhydrous zinc borate, nano silicon dioxide and organic montmorillonite;
the stabilizer at least comprises bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and the mass ratio of the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate to the N, N-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine is 1:1-3:1.
2. The environment-friendly polyamide flame-retardant master batch according to claim 1, wherein the polyamide resin is powder, and the relative viscosity of the polyamide resin is 2.3-2.45.
3. The environment-friendly polyamide flame-retardant masterbatch according to claim 1, wherein the mass fraction of the polyamide resin in the environment-friendly polyamide flame-retardant masterbatch is 20% -45%, the mass fraction of the halogen-free flame retardant composition in the environment-friendly polyamide flame-retardant masterbatch is 42% -75%, the mass fraction of the dispersing agent in the environment-friendly polyamide flame-retardant masterbatch is 4% -10%, and the mass fraction of the stabilizing agent in the environment-friendly polyamide flame-retardant masterbatch is 1% -3%.
4. A method for preparing the environment-friendly polyamide flame-retardant masterbatch according to any one of claims 1-3, which is characterized by comprising the following steps:
uniformly mixing polyamide resin, a halogen-free flame retardant composition, a dispersing agent and a stabilizing agent to obtain a mixed material, wherein the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of synergist by mass percent;
and heating, mixing and plasticizing the mixed material, and then extruding and granulating to obtain the environment-friendly polyamide flame-retardant master batch.
5. The method for preparing the environment-friendly polyamide flame retardant masterbatch according to claim 4, wherein the heating, mixing and plasticizing are performed in a double-rotor continuous mixer, and the double-rotor continuous mixer comprises a first temperature control area and a second temperature control area.
6. The method for preparing the environment-friendly polyamide flame-retardant master batch according to claim 5, wherein the heating temperature of the first temperature control zone is 130-280 ℃, and the heating temperature of the second temperature control zone is 190-340 ℃.
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