CN113754902A - 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
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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Abstract
The invention 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 flame retardant comprises polyamide resin, a halogen-free flame retardant composition, a dispersing agent and a stabilizing agent, wherein the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of a synergist by mass, and the oxide ceramic can be generated after the polymerized phosphate is decomposed. The environment-friendly polyamide flame-retardant master batch disclosed by the invention has good thermal stability, melt flowability, whiteness and flame retardance, no toxic gas is generated in the flame-retardant process, the environment-friendly requirement is met, the flame-retardant effect is good, and the environment-friendly polyamide flame-retardant master batch can be widely applied to the field of flame-retardant plastic production.
Description
Technical Field
The invention 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 prepared by compounding a powder flame retardant composition, a halogen-containing flame retardant composition or a nitrogen-phosphorus halogen-free flame retardant composition and engineering plastics. Although the powder flame retardant composition can improve the flame retardant effect of engineering plastics, the powder flame retardant composition has large dust in the using process, can cause serious environmental pollution, is easy to generate uneven dispersion in the application of the engineering plastics and influences the using effect. The flame-retardant engineering plastic prepared by compounding the halogen-containing flame retardant composition and the engineering plastic does not meet the requirements of ROHS and REACH instructions due to the 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 is difficult to adapt to the requirements of high-temperature processing of flame-retardant engineering plastics due to lower thermal decomposition temperature and poorer heat resistance.
Disclosure of Invention
Therefore, 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 requirement of environmental protection, has good flame-retardant effect, and can be widely used in the field of flame-retardant plastic production.
An environment-friendly polyamide flame-retardant master batch comprises the following components: the flame retardant comprises polyamide resin, a halogen-free flame retardant composition, a dispersing agent and a stabilizing agent, wherein the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of a synergist by mass, and the oxide ceramic can be generated after the polymerized phosphate is decomposed.
In one embodiment, the polyamide resin is powder, and the relative viscosity of the polyamide resin is 2.3-2.45.
In one embodiment, the polyamide resin accounts for 20-45% of the environment-friendly polyamide flame-retardant master batch, the halogen-free flame retardant composition accounts for 42-75% of the environment-friendly polyamide flame-retardant master batch, the dispersant accounts for 4-10% of the environment-friendly polyamide flame-retardant master batch, and the stabilizer accounts for 1-3% of the environment-friendly polyamide flame-retardant master batch.
In one embodiment, the alkylphosphinic salt has the structure
Wherein R is1And R2Each independently selected from hydroxyl, alkyl with 1-6 carbon atoms and aryl with 6-18 carbon atoms, and R1And R2At most one hydroxyl group, M is a metal element, n is an integer, and n is 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 diphosphoric acid and N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and the mass ratio of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphoric acid to N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine is 1:1 to 3: 1.
Compared with the traditional flame retardant, the halogen-free flame retardant composition adopted by the invention comprises alkyl phosphinate, polymeric phosphate and a synergist, wherein the alkyl phosphinate can form a coke layer on the surface of the plastic to reduce the decomposition inside the plastic and the flame heat transfer and become a heat insulation protective layer of the plastic, and the polymeric phosphate and the synergist can form a barrier layer to cover the surface of the plastic at a combustion temperature to achieve the effect of blocking heat, air or oxygen and assist the alkyl phosphinate in realizing effective flame retardance. Meanwhile, because the thermal decomposition temperatures of the alkyl phosphinate flame retardant and the polyphosphate are higher, the polyphosphate does not decompose and separate 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 invention does not contain halogen and heavy metal elements, so that the environment-friendly polyamide flame-retardant master batch does not generate toxic gas in the flame-retardant process, meets the environment-friendly requirement, and can be widely applied to various flame-retardant engineering fields.
The invention 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 a synergist in parts by mass;
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 dual-rotor continuous mixer, which includes a first controlled temperature zone and a second controlled temperature 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 comprises the steps of compounding the polyamide resin, the halogen-free flame retardant composition, the dispersing agent and the stabilizing agent, and mixing, plasticizing, extruding and granulating the mixed materials to obtain the environment-friendly polyamide flame-retardant master batch. Compared with the traditional preparation method of melting granulation, the invention not only changes the mixed material from solid state to molten state through melting, but also leads the mixed material to be completely melted and fully mixed through further plasticizing, and reaches the molding temperature of granulation. Meanwhile, the plasticization also enables the mixed material to have good fluidity and plasticity, thereby being beneficial to granulation and forming, and the components in the environment-friendly polyamide flame-retardant master batch obtained by 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, and no dust is generated in the production process, so that the problem of dust emission in the production process of flame-retardant engineering plastics is solved, the production process of the plastics is simplified, and the production efficiency and the product quality are improved. The environment-friendly polyamide flame-retardant master batch has good thermal stability, and the flame-retardant component in the environment-friendly polyamide flame-retardant master batch is 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 used in the field of flame-retardant plastic production, especially can be well applied to flame-retardant plastic needing high-temperature preparation, and has wide market prospect.
Detailed Description
The environment-friendly polyamide flame-retardant master batch and the preparation method thereof provided by the invention are further explained below.
The environment-friendly polyamide flame-retardant master batch provided by the invention comprises the following components: the flame retardant comprises polyamide resin, a halogen-free flame retardant composition, a dispersing agent and a stabilizing agent, wherein the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of a synergist by mass, and the oxide ceramic can be generated after the polymerized phosphate is decomposed.
Although the halogen flame retardant has good universality and relatively low cost, the halogen flame retardant can generate more smoke, corrosive and toxic gases during combustion, which not only harms human health, but also can cause 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 does not generate toxic gas in the flame-retardant process, meets the instruction requirements 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 combustible volatile matters is reduced; on the other hand, a protective layer effect of heat insulation and oxygen resistance can be formed, and the transmission of heat to the interior of the plastic is reduced. Meanwhile, the alkyl phosphinate releases phosphorus-containing substances at high temperature, and the phosphorus-containing substances further form PO & lt + & gt and PO & lt- & gt at high temperature2Free radical quenchers such as HPO. During the combustion of the polymer, a large amount of H, HO and O radicals are generated to promote the gas-phase combustion reaction, and at the moment, the H, HO and O radicals are more prone to be captured and quenched by a radical quenching agent, so that the chain reaction of the H, HO and O radicals during the combustion is blocked, and the efficient flame retardance is realized. Therefore, alkyl phosphinates were used as one of the components of the halogen-free flame retardant composition.
In some embodiments, the alkylphosphinic salt has the structure
Wherein R is1And R2Each independently selected from hydroxyl, alkyl with 1-6 carbon atoms and aryl with 6-18 carbon atoms, and R1And R2At most one hydroxyl group, M is a metal element, n is an integer, and n is 1-4.
Specifically, the R is1And R2Preferably, each M is independently one selected from a methyl group and an ethyl group, and preferably, one selected from Mg, Ca, Zn, Al, Fe, and Ba, the alkylphosphinic acid salt is preferably at least one selected from magnesium diethylphosphinate, calcium diethylphosphinate, zinc diethylphosphinate, aluminum diethylphosphinate, iron diethylphosphinate, barium diethylphosphinate, magnesium methylethylphosphinate, calcium methylethylphosphinate, zinc methylethylphosphinate, aluminum methylethylphosphinate, iron methylethylphosphinate, and barium methylethylphosphinate, and more preferably, aluminum diethylphosphinate.
In order to further improve the thermal stability of the environment-friendly polyamide flame-retardant master batch, the application combines a polyphosphate with high pyrolysis temperature and good heat resistance with alkyl phosphinate. The polyphosphate can form pyrophosphoric acid and oxide on the surface of burning molten plastic at the same time, and the oxide is molten oxide ceramic and can cover the surface of the burning polymer to form a barrier layer to isolate air and oxygen and assist the alkyl phosphinate to achieve a 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, nano silica, and organo montmorillonite.
When the anhydrous zinc borate is used as a synergist, the anhydrous zinc borate can absorb a large amount of heat energy released by combustion at a high temperature of more than 300 ℃ and generate B2O3Barrier layer covering the surface of burning plastic to block heat, air or oxygenThe flame retardant has the effect of flame retarding together with alkyl phosphinate and polymerized phosphate.
Because the nano-silica has the characteristics of low density and high specific surface area, the gas-phase silica and condensed-phase silica can be used as a barrier layer to be gathered on the surface of burning plastics under the high-temperature condition, and the contact of the plastics and flames 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 fractions of the components of the halogen-free flame retardant composition are further preferably 55-75% of alkyl phosphinate, 22-45% of polymerized phosphate and 5.5-9% of synergist.
In order to uniformly disperse the halogen-free flame retardant composition in a 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, and more preferably 2.37.
Wherein the polyamide resin comprises at least one of polycaprolactam (PA6), polyhexamethylene adipamide (PA66), polyhexamethylene sebacamide (PA610), polyhexamethylene dodecanoamide (PA612), polytetramethylene adipamide (PA46), polyhexamethylene terephthalamide (PA6T) and polyhexamethylene terephthalamide (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 the components to be better dispersed and ensure that the polyamide resin, the halogen-free flame retardant composition and the stabilizer are uniformly distributed, the environment-friendly polyamide flame-retardant master batch also comprises a dispersing agent. In some embodiments, the dispersant comprises at least one of ethylene butyl acrylate glycidyl methacrylate copolymer (PTW), ethylene hard fatty acid amide (EBS).
In order to reduce the phenomenon that the flame-retardant master batch generates ash due to thermal-oxidative aging, the stabilizer at least comprises bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphoric acid (PEP-36) and N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (antioxidant 1098), wherein the stabilizer PEP-36 and the antioxidant 1098 have large molecular weights and have stronger free radical capturing capacity and peroxide decomposition capacity. Specifically, the mass ratio of the PEP-36 to the antioxidant 1098 is 1:1-3:1, and more preferably 2: 1.
It is understood that, on the basis of the stabilizer comprising PEP-36 and antioxidant 1098, the stabilizer of the present invention 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 property of the environment-friendly polyamide flame-retardant master batch and the dispersion effect in plastics during 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 dispersant in the environment-friendly polyamide flame-retardant master batch is preferably 4-10%, and the mass fraction of the stabilizer 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 a plastic product is influenced on one hand, and the plastic product has the problems of cracking, light reflection, reduced impact resistance, reduced tensile strength and the like on the other hand, 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 the dehydration and carbonization of the 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 invention 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 polymerized phosphate and 5-10% of a synergist in parts by mass;
and S2, heating, mixing and plasticizing the mixed material, and then extruding and granulating to obtain the environment-friendly polyamide flame-retardant master batch.
In step S2, a dual-rotor continuous mixer is used to heat, mix and plasticize the mixture, wherein the dual-rotor continuous mixer includes a first temperature control zone and a second temperature control zone, 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 ℃. Specifically, the first temperature control area comprises a first area, a second area and a third area, and the heating temperatures of the first area, the second area and the third area are controlled within the range of 130-280 ℃. The main machine rotating speed of the double-rotor continuous mixing roll is 30Hz-50Hz, the main machine current is 90A-120A, and the feeding operating rotating speed is 3Hz-6 Hz.
And after the step of heating, mixing and plasticizing the mixed material, extruding and granulating by using a single screw extruder, wherein heating areas of the single screw extruder comprise 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 comprises the steps of compounding the polyamide resin, the halogen-free flame retardant composition, the dispersing agent and the stabilizing agent, and mixing, plasticizing, extruding and granulating the mixed materials to obtain the environment-friendly polyamide flame-retardant master batch. Compared with the traditional preparation method of melting granulation, the invention not only changes the mixed material from solid state to molten state through melting, but also leads the mixed material to be completely melted and fully mixed through further plasticizing, and reaches the molding temperature of granulation. Meanwhile, the plasticization also enables the mixed material to have good fluidity and plasticity, granulation molding is facilitated, and all components in the flame-retardant master batch obtained through granulation are uniformly distributed, so that the flame-retardant master batch is high in quality and good in flame-retardant effect.
In addition, the environment-friendly polyamide flame-retardant master batch can be used for preparing plastics, and no dust is generated in the production process, so that the problem of dust emission in the production process of flame-retardant engineering plastics is solved, the production process of the plastics is simplified, and the production efficiency and the product quality are improved. 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 used in the field of flame-retardant plastic production, and particularly can be well suitable for flame-retardant plastics which need to be prepared at high temperature, such as flame-retardant engineering plastics PA6, PA66, PA6T, PA9T and the like.
The environment-friendly polyamide flame-retardant masterbatch 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.
All the components are put into a mixing device with a stirring device and are fully and uniformly mixed to obtain a mixed material. And conveying the mixed material to a double-rotor mixing roll with continuous mixing for heating, mixing and plasticizing, wherein the heating temperature of a first zone, a second zone and a third zone of a double-rotor zone of the double-rotor mixing roll is controlled to be 160 ℃, the heating temperature of a fourth zone is controlled to be 200 ℃, the rotating speed of a main engine is adjusted to be 34Hz, the current of the main engine is 95A, and the feeding rotating speed of the double-rotor is 5 Hz. And extruding and granulating the mixture after heating, mixing and plasticizing through a single-screw extruder to obtain the flame-retardant master batch, wherein the heating temperature of one zone to four zones of the single-screw extruder is controlled to be 230 ℃, the heating temperature of a screen changing zone is 240 ℃, the heating temperature of a machine head is 220 ℃, the rotating speed is 13Hz, and the current is 94A.
The performance of the prepared flame-retardant master batch is tested, and the 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 were weighed by an automatic metering device, wherein the relative viscosity of PA66 was 2.37.
All the components are put into a mixing device with a stirring device and are fully and uniformly mixed to obtain a mixed material. And conveying the mixed material to a double-rotor mixing roll with continuous mixing for heating, mixing and plasticizing, wherein the heating temperature of a first zone, a second zone and a third zone of a double-rotor zone of the double-rotor mixing roll is controlled at 170 ℃, the heating temperature of a fourth zone is controlled at 220 ℃, the rotating speed of a main engine is adjusted to 34Hz, the current of the main engine is 95A, and the feeding rotating speed of the double-rotor is 5 Hz. And extruding and granulating the mixture after heating, mixing and plasticizing through a single-screw extruder to obtain the flame-retardant master batch, wherein the heating temperature of one zone to four zones of the single-screw extruder is controlled to be 240 ℃, the heating temperature of a screen changing zone is 250 ℃, the heating temperature of a machine head is 240 ℃, the rotating speed is 14Hz, and the current is 96A.
The performance of the prepared flame-retardant master batch is tested, and the specific results are shown in table 1.
Example 3
Example 3 differs from example 1 only in that 23kg of powdered PA6, 42.7kg of aluminum diethylphosphinate, 12.3kg of aluminum tripolyphosphate, 6kg of anhydrous zinc borate, 7kg of PTW, 1.2kg of PEP-36, and 0.6kg of antioxidant 1098 were weighed using an automatic metering device, wherein the relative viscosity of PA6 was 2.37.
The performance of the prepared flame-retardant master batch is tested, and the 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.
All the components are put into a mixing device with a stirring device and are fully and uniformly mixed to obtain a mixed material. And conveying the mixed material to a double-rotor mixing roll with continuous mixing for heating, mixing and plasticizing, wherein the heating temperature of a first zone, a second zone and a third zone of a double-rotor zone of the double-rotor mixing roll is controlled to be 190 ℃, the heating temperature of a fourth zone is controlled to be 280 ℃, the rotating speed of a main engine is adjusted to be 35Hz, the current of the main engine is 97A, and the feeding rotating speed of the double-rotor is 6 Hz. And extruding and granulating the mixture after heating, mixing and plasticizing through a single-screw extruder to obtain the flame-retardant master batch, wherein the heating temperature of one zone to four zones of the single-screw extruder is controlled to be 300 ℃, the heating temperature of a screen changing zone is 320 ℃, the heating temperature of a machine head is 320 ℃, the rotating speed is 15Hz, and the current is 100A.
The performance of the prepared flame-retardant master batch is tested, and the specific results are shown in table 1.
Example 5
Example 5 differs from example 1 only in that 45kg of powdered PA6, 32.2kg of aluminum diethylphosphinate, 12kg of aluminum tripolyphosphate, 4kg of anhydrous zinc borate, 5kg of EBS, 1.2kg of PEP-36, and 0.6kg of antioxidant 1098 were weighed using an automatic metering device, wherein the relative viscosity of PA6 was 2.37.
The performance of the prepared flame-retardant master batch is tested, and the specific results are shown in table 1.
Example 6
Example 6 differs from example 1 only in that 21kg of powdered PA6, 38.2kg of zinc diethylphosphinate, 32kg of aluminum tripolyphosphate, 3.8kg of silica, 6kg of PTW, 1kg of PEP-36, and 0.5kg of antioxidant 1098 were weighed using an automatic metering device, wherein the relative viscosity of PA6 was 2.37.
The performance of the prepared flame-retardant master batch is tested, and the specific results are shown in table 1.
Example 7
Example 7 differs from example 1 only in that 25kg of powdered PA6, 42kg of aluminum diethylphosphinate, 17.8kg of magnesium tripolyphosphate, 5.2kg of anhydrous zinc borate, 8.8kg of EBS, 0.8kg of PEP-36, and 0.4kg of antioxidant 1098 were weighed using an automatic metering device, wherein the relative viscosity of PA6 was 2.37.
The performance of the prepared flame-retardant master batch is tested, and the specific results are shown in table 1.
Example 8
22kg of powder PA66, 49kg of methyl ethyl aluminum 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.
All the components are put into a mixing device with a stirring device and are fully and uniformly mixed to obtain a mixed material. And conveying the mixed material to a double-rotor mixing roll with continuous mixing for heating, mixing and plasticizing, wherein the heating temperature of a first zone, a second zone and a third zone of a double-rotor zone of the double-rotor mixing roll is controlled at 170 ℃, the heating temperature of a fourth zone is controlled at 220 ℃, the rotating speed of a main engine is adjusted to 34Hz, the current of the main engine is 95A, and the feeding rotating speed of the double-rotor is 5 Hz. And extruding and granulating the mixture after heating, mixing and plasticizing through a single-screw extruder to obtain the flame-retardant master batch, wherein the heating temperature of one zone to four zones of the single-screw extruder is controlled to be 240 ℃, the heating temperature of a screen changing zone is 250 ℃, the heating temperature of a machine head is 240 ℃, the rotating speed is 14Hz, and the current is 96A.
The performance of the prepared flame-retardant master batch is tested, and the 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, and 0.5kg of antioxidant 1098 were weighed using an automatic metering device, wherein the relative viscosity of PA6 was 2.37.
The performance of the prepared flame-retardant master batch is tested, and the 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 performance of the prepared flame-retardant master batch is tested, and the 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 performance of the prepared flame-retardant master batch is tested, and the specific results are shown in table 1.
Comparative example 3
Comparative example 3 differs from example 1 only in that 12.2kg of iron tripolyphosphate was used instead of 12.2kg of aluminium tripolyphosphate.
The performance of the prepared flame-retardant master batch is tested, and the 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 is used instead of 6kg of anhydrous zinc borate.
The performance of the prepared flame-retardant master batch is tested, and the 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 in place of 2kg of PEP-36 and 1kg of antioxidant 1010 was used in place of 1kg of antioxidant 1098.
The performance of the prepared flame-retardant master batch is tested, and the 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 performance of the prepared flame-retardant master batch is tested, and the specific results are shown in table 1.
TABLE 1
From the test data in table 1, it can be seen that the 2% thermal weight loss temperature of the flame-retardant master batch in comparative examples 1-2 is about 8 ℃ lower than the 2% thermal weight loss temperature of example 1, and the residual rate is about 4% lower. The reason is that the thermal decomposition temperature of MPP and MCA is not high, the heat resistance is poor, MPP and MCA are easy to separate out and decompose in the manufacturing and using processes of the flame-retardant master batch, the quality and the thermal stability of the flame-retardant master batch are influenced, and the normal production of the flame-retardant polyamide is seriously influenced, so that the application of products is extremely influenced.
The flame-retardant master batch of comparative example 3 employs ferric tripolyphosphate instead of aluminum tripolyphosphate, and since ferric tripolyphosphate cannot form fused oxide ceramic under high-temperature combustion conditions, its heat resistance is reduced to some extent. The flame-retardant master batch of comparative example 4 uses zinc borate pentahydrate instead of anhydrous zinc borate, and since water in the zinc borate pentahydrate evaporates during the melt granulation process, a large amount of bubbles are generated in the master batch, so that the thermal stability is reduced.
The whiteness of the flame-retardant master batch in the comparative examples 5 to 6 is about 15 percent lower than that of the flame-retardant master batch in the example 1, which is caused by the fact that the flame-retardant master batch is grayed due to poor high-temperature antioxidant effects of the antioxidant 1010 and the antioxidant 168, and the example 1 adopts PEP-36 and the antioxidant 1098 to overcome the defect.
Therefore, the environment-friendly polyamide flame-retardant master batch disclosed by the invention has better melt flowability, thermal stability, whiteness and flame retardant property, and a flame retardant system, a dispersion system and a stable system of the environment-friendly polyamide flame-retardant master batch are all superior to those of the traditional polyamide resin flame-retardant master batch.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The environment-friendly polyamide flame-retardant master batch is characterized by comprising the following components: the flame retardant comprises polyamide resin, a halogen-free flame retardant composition, a dispersing agent and a stabilizing agent, wherein the halogen-free flame retardant composition comprises 50-75% of alkyl phosphinate, 20-45% of polymerized phosphate and 5-10% of a synergist by mass, and the oxide ceramic can be generated after the polymerized phosphate is decomposed.
2. The environment-friendly polyamide flame-retardant masterbatch 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 master batch according to claim 1, wherein the polyamide resin accounts for 20-45% by mass of the environment-friendly polyamide flame-retardant master batch, the halogen-free flame retardant composition accounts for 42-75% by mass of the environment-friendly polyamide flame-retardant master batch, the dispersant accounts for 4-10% by mass of the environment-friendly polyamide flame-retardant master batch, and the stabilizer accounts for 1-3% by mass of the environment-friendly polyamide flame-retardant master batch.
4. The environment-friendly polyamide flame-retardant masterbatch according to claim 1, wherein the alkyl phosphinate salt has a structure of
Wherein R is1And R2Each independently selected from hydroxyl, alkyl with 1-6 carbon atoms and aryl with 6-18 carbon atoms, and R1And R2At most one hydroxyl group, M is a metal element, n is an integer, and n is 1-4.
5. The environmentally friendly polyamide flame retardant masterbatch of claim 1, wherein the polyphosphate comprises at least one of aluminum tripolyphosphate, magnesium tripolyphosphate, zinc tripolyphosphate, titanium tripolyphosphate, and silicon tripolyphosphate.
6. The environment-friendly polyamide flame-retardant masterbatch according to claim 1, wherein the synergist comprises at least one of anhydrous zinc borate, nano silica and organic montmorillonite.
7. The environment-friendly polyamide flame-retardant masterbatch according to claim 1, wherein the stabilizer comprises at least bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphoric acid and N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and the mass ratio of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphoric acid to N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine is 1:1 to 3: 1.
8. The preparation method of the environment-friendly polyamide flame-retardant master batch as claimed in any one of claims 1 to 7, 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 a synergist in parts by mass;
and heating, mixing and plasticizing the mixed material, and then extruding and granulating to obtain the environment-friendly polyamide flame-retardant master batch.
9. The method for preparing the environment-friendly polyamide flame-retardant masterbatch according to claim 8, 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 zone and a second temperature-control zone.
10. The method for preparing the environment-friendly polyamide flame-retardant masterbatch according to claim 9, wherein 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 ℃.
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