CN111607221B - In-situ coated red phosphorus flame retardant, flame-retardant polyamide material based on in-situ coated red phosphorus flame retardant and preparation method of flame-retardant polyamide material - Google Patents
In-situ coated red phosphorus flame retardant, flame-retardant polyamide material based on in-situ coated red phosphorus flame retardant and preparation method of flame-retardant polyamide material Download PDFInfo
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Abstract
The invention discloses an in-situ coated red phosphorus flame retardant, a flame-retardant polyamide material based on the in-situ coated red phosphorus flame retardant and a preparation method thereof, wherein red phosphorus powder and caprolactam monomers are used as raw materials, caprolactam monomers are activated, caprolactam is subjected to surface reaction polymerization on the red phosphorus powder in the presence of a cocatalyst to prepare a microcapsule coated red phosphorus flame retardant, and the microcapsule coated red phosphorus flame retardant is extruded by a double screw extruder according to the weight ratio of 40-68% of polyamide, 6-12% of the in-situ coated red phosphorus flame retardant, 20-50% of glass fiber, 0.2-1.0% of a stabilizer and 0.1-0.7% of a lubricant to prepare the flame-retardant polyamide material, so that the prepared in-situ coated red phosphorus flame retardant and flame-retardant polyamide material both contain fewer phosphate groups to produce, the problem of red phosphorylation in the traditional flame-retardant polyamide material is solved, and the safety risk caused by phosphoric acid deposition can be obviously reduced when the microcapsule coated red phosphorus flame retardant is used in the field of electronic and electrical appliances.
Description
Technical Field
The invention relates to an in-situ coated red phosphorus flame retardant, a flame-retardant polyamide material based on the in-situ coated red phosphorus flame retardant and a preparation method thereof, in particular to a polyamide in-situ coated red phosphorus flame retardant, a flame-retardant polyamide composite material added with the flame retardant and a preparation method thereof, and belongs to the field of halogen-free flame-retardant polyamide material manufacturing.
Background
Polyamide materials are increasingly used in electrified working environments such as automotive appliances, electric tools and the like, and the risks of fire caused by electric leakage, short circuits, electric arcs, electric sparks and the like are great. Thus, flame retardant polyamides have been developed in succession around the world since the 70 s. Flame retardant systems for polyamides have previously been dominated by halogens, especially bromine-containing flame retardants, but halogen flame retardants face serious environmental problems in application. Flame retardant plastics, such as halogen containing compounds, release relatively large amounts of toxic fumes upon exposure to a fire.
In the prior art, the red phosphorus flame retardant is added into the polyamide material to achieve good flame retardant effect, and the smoke quantity is low, so that the halogen-free environment-friendly trend is met. However, red phosphorus flame retardants are susceptible to disproportionation reactions of red phosphorus at high temperatures, in air, in high humidity and in alkaline environments to form phosphine and phosphoric acid of various valence states. Phosphoric acid can corrode metal elements and at the same time, the generated phosphoric acid can deposit on the surfaces of electronic and electric products, and the arc tracking resistance of the products is reduced. Currently, there are various methods for reducing red phosphorus reaction, in order to isolate oxygen, silicone oil, paraffin oil, etc. are coated on the surface of red phosphorus, or a low molecular weight polymer is coated on the surface of red phosphorus. However, such liquid substances and low molecular weight substances are likely to precipitate under high temperature conditions, resulting in a decrease in insulating properties of the product. In addition, the red phosphorus powder is coated in situ by a learner with inorganic hydroxide, and the phosphine release of the prepared red phosphorus flame retardant is reduced, for example, patent document CN104448934a (patent document 2015.03.25 of an inorganic material coated flame retardant microcapsule and a preparation method thereof). However, the inorganic material-coated flame retardant is subjected to a strong shearing force when it is extruded through a twin screw, and the coating layer thereof is easily broken. Still other scholars have studied double coated red phosphorus powder of organic and inorganic substances, which has a complicated production process, for example, patent document CN108912671a (a melamine modified lignin/magnesium hydroxide double coated Hong Lin flame retardant and its application in PA6 resin, 2018.08.09). In addition, the melamine coating layer is poor in thermal stability, the coating layer is also easily damaged, and the effect of preventing phosphoric acid precipitation is not satisfactory.
Disclosure of Invention
The invention aims to provide an in-situ coated red phosphorus flame retardant, which can effectively reduce the concentration of phosphate ions by activating a caprolactam monomer and then carrying out reaction polymerization on the surface of red phosphorus powder to obtain a microcapsule coated red phosphorus flame retardant.
The invention further aims to provide a flame-retardant polyamide material based on the in-situ coated red phosphorus flame retardant, which is prepared from the polyamide in-situ coated red phosphorus flame retardant, polyamide, glass fiber and the like as raw materials, so that the degree of acidification of red phosphorus in the existing flame-retardant polyamide material is reduced, and the safety risk caused by phosphoric acid deposition is reduced when the flame-retardant polyamide material is used in the field of electronic and electric appliances.
The invention further aims to provide a preparation method of the flame-retardant polyamide material based on the in-situ coated red phosphorus flame retardant, which adopts the existing double-screw extruder for extrusion, and the in-situ coated red phosphorus flame retardant is added into the double-screw extruder through side feeding, so that the flame-retardant polyamide material with better rigidity and better flame retardant property can be prepared.
The invention is realized by the following technical scheme: the in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials, activating the caprolactam monomer, and then reacting and polymerizing caprolactam on the surface of the red phosphorus powder in the presence of a cocatalyst.
The activation is to heat caprolactam monomer in a reaction kettle, add alkaline catalyst when the temperature reaches 130-140 ℃, stir, react and dehydrate, keep the vacuum degree at 0.09-0.1 MPa for 15-20 min, and restore normal pressure, wherein the dosage of the alkaline catalyst is 0.05-0.15% of the mass of caprolactam monomer. Wherein the alkaline catalyst can be metallic sodium, sodium alkoxide, sodium hydroxide, sodium carbonate, etc.
Adding activated caprolactam, red phosphorus powder and a cocatalyst into an internal mixer, preserving heat for 30-60 min at 160-180 ℃, controlling the rotation speed of the internal mixer to be 10-200 rpm, processing for 5-10 min, and discharging, wherein the consumption of the cocatalyst is 1.5-3.5% of the mass of the caprolactam. Wherein the cocatalyst can be citalopram, various isocyanatoles, carbamic acid derivatives, carbonic acid, and carboxylic acid.
The average grain diameter of the red phosphorus powder is 1-200 mu m, and the mass ratio of the caprolactam to the red phosphorus powder is 1: (1.5-5.7), wherein the red phosphorus powder accounts for 60-85% of the content of the in-situ coated red phosphorus flame retardant. Wherein the red phosphorus may be untreated red phosphorus or red phosphorus treated with a low molecular weight liquid substance (e.g., silicone oil, paraffin oil, etc.).
The flame-retardant polyamide material based on the in-situ coated red phosphorus flame retardant comprises the following raw materials in percentage by weight:
polyamide: 40-68%;
in-situ coating of red phosphorus flame retardant: 6-12%;
glass fiber: 20-50%;
stabilizing agent: 0.2 to 1.0 percent;
and (3) a lubricant: 0.1 to 0.7 percent,
the in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials, activating the caprolactam monomer, and then reacting and polymerizing caprolactam on the surface of the red phosphorus powder in the presence of a cocatalyst.
The polyamide is selected from one or a mixture of nylon 6 and nylon 66, and the relative viscosity index of the polyamide is 2.0-2.9.
The glass fiber is glass fiber treated by at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
The invention adopts an antioxidant as a stabilizer, wherein the antioxidant is an organic compound or an inorganic compound which can inhibit or delay the thermal oxidation of high polymers and other organic compounds in a certain environment, and can be generally divided into a main antioxidant, an auxiliary antioxidant and a carbon free radical scavenger according to different effects, and the processing stability of the material can be greatly improved through the mutual synergistic effect of the main antioxidant and the auxiliary antioxidant.
In the present invention, the stabilizer is at least one selected from the group consisting of N, N' -bis- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (1098), tris [2, 4-di-t-butylphenyl ] phosphite (168) and bis (2, 4-di-t-butyl) quaternium diphosphite (S-9228).
In the invention, the lubricant is added to improve lubricity, reduce friction, reduce damage of a red phosphorus powder coating layer in an extrusion process, and obtain a modified polyamide material with less acid precipitation and better surface, so the lubricant is at least one selected from zinc stearate, calcium stearate, ethylene bis-stearamide, polyethylene wax and oxidized polyethylene wax.
The preparation method of flame-retardant polyamide material based on in-situ coated red phosphorus flame retardant comprises mixing polyamide, stabilizer and lubricant, feeding into a twin-screw extruder via a main feeder, adding in-situ coated red phosphorus flame retardant into the third section of the twin-screw extruder via a second feeder, adding glass fiber into the fifth section of the twin-screw extruder via the third feeder, controlling extrusion temperature at 230-275 deg.C, screw rotation speed at 100-500 rpm,
polyamide: 40-68%;
in-situ coating of red phosphorus flame retardant: 6-12%;
glass fiber: 20-50%;
stabilizing agent: 0.2 to 1.0 percent;
and (3) a lubricant: 0.1 to 0.7 percent,
the in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials, activating the caprolactam monomer, and then reacting and polymerizing caprolactam on the surface of the red phosphorus powder in the presence of a cocatalyst.
Compared with the prior art, the invention has the following advantages:
(1) The invention takes caprolactam monomer and red phosphorus powder as raw materials to prepare an in-situ coated red phosphorus flame retardant, and specifically adopts caprolactam melt polymerization to coat the red phosphorus powder, wherein the concentration of phosphate radical contained in the flame retardant is only 30-40 mg/L.
(2) The in-situ coated red phosphorus flame retardant prepared by the invention has the advantages that the coating layer is melt polymerized polyamide, the compatibility of the coating layer with nylon 66 and nylon 6 is good, and the prepared flame retardant nylon material has more excellent comprehensive performance.
(3) According to the invention, the flame-retardant polyamide material is prepared by taking the in-situ coated red phosphorus flame retardant, polyamide, glass fiber and the like as raw materials, and the phosphate ion concentration of the flame-retardant polyamide material is obviously reduced compared with that of the conventional common flame-retardant polyamide material, so that the acidification of red phosphorus is effectively controlled, and therefore, the safety risk caused by the deposition of phosphoric acid can be reduced when the flame-retardant polyamide material is used in the field of electronic and electric appliances.
(4) In the preparation process of the invention, the in-situ coated red phosphorus flame retardant is added into the double-screw extruder in a side feeding manner, so that the coating layer of the in-situ coated red phosphorus flame retardant can be prevented from being damaged by shearing in the screw.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1:
the embodiment provides an in-situ coated red phosphorus flame retardant.
The in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials and carrying out an activated molecular stage and an in-situ coated red phosphorus powder stage, and is specifically summarized as follows:
activation of the molecular stage: and (3) putting the caprolactam monomer into a reaction kettle, heating and melting, adding sodium hydroxide according to the mass of 0.08% of the caprolactam monomer when the temperature reaches 130 ℃, uniformly stirring, dehydrating in a reaction way, keeping the vacuum degree at 0.09MPa for 20min, stopping vacuumizing, and recovering the normal pressure.
In-situ coating of red phosphorus powder: pumping the activated caprolactam into a mixing tank, adding untreated red phosphorus powder with the average particle diameter of 200 mu m and polyisocyanate, uniformly mixing, adding the materials into an internal mixer, preserving heat at 160 ℃ for 30min, controlling the rotating speed of the internal mixer to be 10rpm after the materials are solidified, and discharging after processing for 10min to obtain the microcapsule coated red phosphorus flame retardant, namely the in-situ coated red phosphorus flame retardant.
In the above stage, the cool usage amount of the polyisocyanate is 2.0% of the mass of the caprolactam, the red phosphorus powder accounts for 60% of the content of the flame retardant of the in-situ coated red phosphorus, and the mass ratio of the red phosphorus powder to the caprolactam is 1.5:1.
example 2:
the embodiment provides an in-situ coated red phosphorus flame retardant.
The in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials and carrying out an activated molecular stage and an in-situ coated red phosphorus powder stage, and is specifically summarized as follows:
activation of the molecular stage: and (3) putting the caprolactam monomer into a reaction kettle, heating and melting, adding sodium hydroxide according to the mass of 0.12% of the caprolactam when the temperature reaches 140 ℃, stirring uniformly, dehydrating in a reaction way, keeping the vacuum degree at 0.1Mpa for 15min, stopping vacuumizing, and recovering normal pressure.
In-situ coating of red phosphorus powder: pumping the activated caprolactam into a mixing tank, adding liquid substances with average grain diameter of 5 mu m and low molecular weight, such as red phosphorus powder treated by silicone oil, paraffin oil and the like, and polyisocyanate, uniformly mixing, adding the materials into an internal mixer, preserving heat at 180 ℃ for 60min, controlling the rotating speed of the internal mixer to 200rpm after the materials are solidified, and discharging after processing for 5min to obtain the microcapsule-coated red phosphorus flame retardant, namely the in-situ coated red phosphorus flame retardant.
In the stage, the consumption of the cocatalyst is 3.0% of the mass of the caprolactam, the red phosphorus powder accounts for 85% of the content of the in-situ coated red phosphorus flame retardant, and the mass ratio of the red phosphorus powder to the caprolactam is 5.7:1.
example 3:
the embodiment provides an in-situ coated red phosphorus flame retardant.
The in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials and carrying out an activated molecular stage and an in-situ coated red phosphorus powder stage, and is specifically summarized as follows:
activation of the molecular stage: and (3) putting the caprolactam into a reaction kettle, heating and melting, adding sodium hydroxide according to the mass of 0.10% of the caprolactam when the temperature reaches 140 ℃, stirring uniformly, reacting and dehydrating, keeping the vacuum degree at 0.09MPa for 20min, stopping vacuumizing, and recovering normal pressure.
In-situ coating of red phosphorus powder: pumping the activated caprolactam monomer into a mixing tank, adding liquid substances with average grain diameter of 20 mu m and low molecular weight, such as silicone oil, paraffin oil and the like, uniformly mixing the treated red phosphorus powder and polyisocyanate, adding the materials into an internal mixer, preserving heat at 170 ℃ for 40min, controlling the rotating speed of the internal mixer to 80rpm after the materials are solidified, and discharging after processing for 9min to obtain the microcapsule-coated red phosphorus flame retardant, namely the in-situ coated red phosphorus flame retardant.
In the stage, the consumption of the cocatalyst is 2.5% of the mass of the caprolactam, the red phosphorus powder accounts for 60% of the content of the in-situ coated red phosphorus flame retardant, and the mass ratio of the red phosphorus powder to the caprolactam is 1.5:1.
example 4:
the embodiment provides an in-situ coated red phosphorus flame retardant.
The in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials and carrying out an activated molecular stage and an in-situ coated red phosphorus powder stage, and is specifically summarized as follows:
activation of the molecular stage: and (3) putting the caprolactam monomer into a reaction kettle, heating and melting, adding sodium hydroxide according to the mass of 0.08% of the caprolactam when the temperature reaches 130 ℃, stirring uniformly, dehydrating in a reaction way, keeping the vacuum degree at 0.09MPa for 16min, stopping vacuumizing, and recovering normal pressure.
In-situ coating of red phosphorus powder: pumping the activated caprolactam into a mixing tank, adding untreated red phosphorus powder with the average particle diameter of 120 mu m and polyisocyanate, uniformly mixing, adding the materials into an internal mixer, preserving heat at 180 ℃ for 50min, controlling the rotating speed of the internal mixer to be 150rpm after the materials are solidified, and discharging after processing for 6min to obtain the microcapsule coated red phosphorus flame retardant, namely the in-situ coated red phosphorus flame retardant.
In the stage, the consumption of the cocatalyst is 2.2% of the mass of the caprolactam, the red phosphorus powder accounts for 80% of the content of the in-situ coated red phosphorus flame retardant, and the mass ratio of the red phosphorus powder to the caprolactam is 4:1.
example 5:
the embodiment provides an in-situ coated red phosphorus flame retardant.
The in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials and carrying out an activated molecular stage and an in-situ coated red phosphorus powder stage, and is specifically summarized as follows:
activation of the molecular stage: and (3) putting the caprolactam monomer into a reaction kettle, heating and melting, adding sodium hydroxide according to the mass of 0.09% of the caprolactam when the temperature reaches 130 ℃, stirring uniformly, dehydrating in a reaction way, keeping the vacuum degree at 0.09MPa for 15min, stopping vacuumizing, and recovering normal pressure.
In-situ coating of red phosphorus powder: pumping the activated caprolactam into a mixing tank, adding liquid substances with the average grain diameter of 50 mu m and low molecular weight, such as red phosphorus powder treated by silicone oil, paraffin oil and the like, and polyisocyanate, uniformly mixing, adding the materials into an internal mixer, preserving heat at 160 ℃ for 45min, controlling the rotating speed of the internal mixer to be 100rpm after the materials are solidified, and discharging after processing for 5min to obtain the microcapsule-coated red phosphorus flame retardant, namely the in-situ coated red phosphorus flame retardant.
In the stage, the consumption of the cocatalyst is 2.8% of the mass of the caprolactam, the red phosphorus powder accounts for 80% of the content of the in-situ coated red phosphorus flame retardant, and the mass ratio of the red phosphorus powder to the caprolactam is 4:1.
example 6:
the embodiment provides an in-situ coated red phosphorus flame retardant.
The in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials and carrying out an activated molecular stage and an in-situ coated red phosphorus powder stage, and is specifically summarized as follows:
activation of the molecular stage: and (3) putting the caprolactam monomer into a reaction kettle, heating and melting, adding sodium carbonate according to the mass of 0.11% of the caprolactam when the temperature reaches 135 ℃, uniformly stirring, dehydrating in a reaction way, keeping the vacuum degree at 0.09MPa for 18min, stopping vacuumizing, and recovering the normal pressure.
In-situ coating of red phosphorus powder: pumping the activated caprolactam into a mixing tank, adding untreated red phosphorus powder with the average particle diameter of 1 mu m and citalopram, uniformly mixing, adding the materials into an internal mixer, preserving heat for 55min at 175 ℃, controlling the rotating speed of the internal mixer to be 150rpm after the materials are solidified, and discharging after processing for 8min to obtain the microcapsule coated red phosphorus flame retardant, namely the in-situ coated red phosphorus flame retardant.
In the stage, the consumption of the cocatalyst is 2.6% of the mass of the caprolactam, the red phosphorus powder accounts for 80% of the content of the in-situ coated red phosphorus flame retardant, and the mass ratio of the red phosphorus powder to the caprolactam is 4:1.
comparative example 1:
a common red phosphorus flame-retardant master batch is used, and the red phosphorus flame-retardant master batch is carried by PA6, and the red phosphorus content of the master batch is 50 percent.
The in-situ coated red phosphorus flame retardant prepared in the above examples 1 to 6 and the ordinary red phosphorus flame retardant master batch related to comparative example 1 were subjected to phosphate ion test, test method: adding the red phosphorus flame-retardant master batch or the red phosphorus flame retardant into a 500ml conical flask, adding 200ml deionized water, and soaking for 2 hours. Then, after adding 2.5 hours at 100 ℃, the mixture is left for 24 hours to normal temperature, filtered, and the filtrate is tested by an ion chromatograph. The test results are shown in table 1 below.
TABLE 1
Example 7:
the embodiment provides a flame-retardant polyamide material based on an in-situ coated red phosphorus flame retardant.
The flame-retardant polyamide material is prepared by the following method: nylon 66 with a relative viscosity of 2.8, stabilizer 1098, stabilizer 168 and calcium stearate were mixed and fed into a twin screw extruder from a main feeder, an in-situ coated red phosphorus flame retardant was added through a second feeder at the third stage of the twin screw extruder (as described in example 1), glass fibers treated with a silane coupling agent were added through the third feeder at the fifth stage of the twin screw extruder, and the extrusion temperature was controlled at 250 to 275 ℃ and the screw speed was 350rpm.
Example 8:
the embodiment provides a flame-retardant polyamide material based on an in-situ coated red phosphorus flame retardant.
The flame-retardant polyamide material is prepared by the following method: nylon 66 with relative viscosity of 2.8, stabilizer 1098, stabilizer 168 and calcium stearate are mixed and fed into a twin-screw extruder by a main feeder, an in-situ coated red phosphorus flame retardant (as described in example 2) is added in a third section of the twin-screw extruder by a second feeder, glass fiber treated with a titanate coupling agent is added in a fifth section of the twin-screw extruder by the third feeder, and the extrusion temperature is controlled to 250-275 ℃ and the screw speed is controlled to 400rpm.
Example 9:
the embodiment provides a flame-retardant polyamide material based on an in-situ coated red phosphorus flame retardant.
The flame-retardant polyamide material is prepared by the following method: nylon 66 with relative viscosity of 2.4, stabilizer 1098, stabilizer 168 and calcium stearate are mixed and fed into a twin-screw extruder by a main feeder, an in-situ coated red phosphorus flame retardant (as described in example 3) is added in a third section of the twin-screw extruder by a second feeder, glass fibers treated with a silane coupling agent and an aluminate coupling agent are added in a fifth section of the twin-screw extruder by the third feeder, and the extrusion temperature is controlled to 250-275 ℃ and the screw rotation speed is controlled to 450rpm.
Example 10:
the embodiment provides a flame-retardant polyamide material based on an in-situ coated red phosphorus flame retardant.
The flame-retardant polyamide material is prepared by the following method: nylon 66 with relative viscosity of 2.4, stabilizer 1098, stabilizer 168 and calcium stearate are mixed and fed into a twin-screw extruder by a main feeder, an in-situ coated red phosphorus flame retardant (as described in example 4) is added in a third section of the twin-screw extruder by a second feeder, glass fiber treated with a silane coupling agent and a titanate coupling agent is added in a fifth section of the twin-screw extruder by the third feeder, and the extrusion temperature is controlled to 250-275 ℃ and the screw speed is controlled to 350rpm.
Example 11:
the embodiment provides a flame-retardant polyamide material based on an in-situ coated red phosphorus flame retardant.
The flame-retardant polyamide material is prepared by the following method: nylon 6 with relative viscosity of 2.0, nylon 66 with relative viscosity of 2.5, stabilizer 1098, stabilizer 168 and calcium stearate are mixed and fed into a twin-screw extruder by a main feeder, an in-situ coated red phosphorus flame retardant is added in a third section of the twin-screw extruder by a second feeder (as described in example 5), glass fiber treated with a silane coupling agent is added in a fifth section of the twin-screw extruder by the third feeder, and the extrusion temperature is controlled to 250-275 ℃ and the screw speed is controlled to 100rpm.
Example 12
The embodiment provides a flame-retardant polyamide material based on an in-situ coated red phosphorus flame retardant.
The flame-retardant polyamide material is prepared by the following method: nylon 6 having a relative viscosity of 2.9, stabilizer 1098, stabilizer 168 and calcium stearate were mixed and fed into a twin screw extruder from a main feeder, an in-situ coated red phosphorus flame retardant was added through a second feeder at the third stage of the twin screw extruder (as described in example 6), and glass fiber treated with a silane coupling agent was added through the third feeder at the fifth stage of the twin screw extruder, and the extrusion temperature was controlled at 230 to 250℃and the screw speed was 500rpm.
Comparative example 2:
comparative example 2 the same preparation as in example 6 was used, using a red phosphorus flame retardant masterbatch with a PA6 carrier having a red phosphorus content of 50% instead of the in-situ coated red phosphorus flame retardant.
The weight ratios of the specific raw material components used in the above examples 7 to 12 and comparative example 2 are shown in the following table 2:
TABLE 2
The flame retardant polyamide materials prepared in examples 7 to 12 and comparative example 2 were respectively tested for flexural strength, impact strength and flame retardant property according to GB/T9341-2000 standard, and flame retardant property according to GB/T2408 standard. Phosphate ion test method: 50g of modified material is taken and added into a 500ml conical flask, 200ml of deionized water is added, and the mixture is soaked for 2 hours. Then, the mixture was left at 100℃for 2.5 hours and 24 hours, and then tested by ion chromatography. The test results are shown in table 3 below.
TABLE 3 Table 3
From the experimental data of table 2 above, it can be seen that: compared with the traditional red phosphorus flame-retardant reinforced polyamide material, the flame-retardant polyamide material prepared by adopting the specific raw material composition and the process control condition has obviously reduced phosphate content, excellent mechanical property and very stable flame-retardant effect.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation, etc. of the above embodiment according to the technical matter of the present invention fall within the scope of the present invention.
Claims (9)
1. An in-situ coated red phosphorus flame retardant, which is characterized in that: the in-situ coated red phosphorus flame retardant is prepared by taking red phosphorus powder and caprolactam monomer as raw materials, activating the caprolactam monomer, then reacting and polymerizing caprolactam on the surface of the red phosphorus powder in the presence of a cocatalyst to prepare microcapsule coated red phosphorus flame retardant,
the activation is a process of heating caprolactam monomer in a reaction kettle, adding an alkaline catalyst, stirring, reacting for dehydration, maintaining vacuum, recovering normal pressure,
the average grain diameter of the red phosphorus powder is 1-200 mu m, and the mass ratio of the caprolactam to the red phosphorus powder is 1: (1.5-5.7), wherein the red phosphorus powder accounts for 60-85% of the content of the in-situ coated red phosphorus flame retardant.
2. An in-situ coated red phosphorus flame retardant according to claim 1, characterized in that: in the activation process, when the heating temperature of caprolactam monomer in a reaction kettle reaches 130-140 ℃, adding an alkaline catalyst; maintaining the vacuum degree at 0.09-0.1 MPa for 15-20 min, and recovering the normal pressure; the dosage of the alkaline catalyst is 0.05 to 0.15 percent of the mass of caprolactam monomer.
3. An in-situ coated red phosphorus flame retardant according to claim 1, characterized in that: adding activated caprolactam, red phosphorus powder and a cocatalyst into an internal mixer, preserving heat for 30-60 min at 160-180 ℃, controlling the rotation speed of the internal mixer to be 10-200 rpm, processing for 5-10 min, and discharging, wherein the consumption of the cocatalyst is 1.5-3.5% of the mass of the caprolactam.
4. A method for preparing a flame retardant polyamide material by adopting the in-situ coated red phosphorus flame retardant of claim 1, which is characterized in that: the polyamide, the stabilizer and the lubricant are mixed and then sent into a double-screw extruder by a main feeder, the in-situ coated red phosphorus flame retardant is added into a third section of the double-screw extruder by a second feeder, glass fiber is added into a fifth section of the double-screw extruder by a third feeder, the extrusion temperature is controlled to be 230-275 ℃, the screw rotation speed is 100-500 rpm, and the weight percentage is calculated,
polyamide: 40-68%;
in-situ coating of red phosphorus flame retardant: 6-12%;
glass fiber: 20-50%;
stabilizing agent: 0.2 to 1.0 percent;
and (3) a lubricant: 0.1 to 0.7 percent.
5. The method according to claim 4, wherein: the polyamide is selected from one or a mixture of nylon 6 and nylon 66, and the relative viscosity index of the polyamide is 2.0-2.9.
6. The method according to claim 4, wherein: the glass fiber is glass fiber treated by at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
7. The method according to claim 4, wherein: the stabilizer is at least one selected from N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, tris [2, 4-di-tert-butylphenyl ] phosphite and bis (2, 4-di-tert-butyl) quaternary tetraol diphosphite.
8. The method according to claim 4, wherein: the lubricant is at least one selected from zinc stearate, calcium stearate, ethylene bis-stearamide, polyethylene wax and oxidized polyethylene wax.
9. A flame retardant polyamide material prepared by the method of claim 4.
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| US3951908A (en) * | 1969-12-31 | 1976-04-20 | Badische Anilin- & Soda Fabrik Aktiengesellschaft | Flame-proofing, high melting point thermoplastic polymers with lactam-impregnated red phosphorus |
| US4584149A (en) * | 1983-07-04 | 1986-04-22 | Consiglio Nazionale Delle Ricerche | Process for preparing self-extinguishing formed thermo-plastic bodies based on polycaprolactam |
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| DE10126760A1 (en) * | 2001-06-01 | 2002-12-05 | Bayer Ag | Microencapsulated red phosphorus |
| CN101503568B (en) * | 2008-02-04 | 2011-07-20 | 金发科技股份有限公司 | Red phosphorus flame-retardant enhanced thermoplastic polyamide composition |
| CN105038211A (en) * | 2015-06-24 | 2015-11-11 | 南京聚隆科技股份有限公司 | Low-corrosion and low-odor glassfiber reinforced red phosphorus flame-retardant nylon 66 composite and preparation method thereof |
| CN106336658B (en) * | 2016-08-29 | 2019-06-28 | 会通新材料股份有限公司 | A kind of red phosphorus flame-retardant reinforced plastic PA66 and POK alloy material and preparation method thereof |
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| US3951908A (en) * | 1969-12-31 | 1976-04-20 | Badische Anilin- & Soda Fabrik Aktiengesellschaft | Flame-proofing, high melting point thermoplastic polymers with lactam-impregnated red phosphorus |
| US4584149A (en) * | 1983-07-04 | 1986-04-22 | Consiglio Nazionale Delle Ricerche | Process for preparing self-extinguishing formed thermo-plastic bodies based on polycaprolactam |
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