CN113527877B - High CTI value black red phosphorus flame-retardant reinforced nylon 66 and preparation method thereof - Google Patents
High CTI value black red phosphorus flame-retardant reinforced nylon 66 and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a black red phosphorus flame-retardant reinforced nylon 66 with a high CTI value, which is prepared from the following raw materials, by weight, 33.5-55.3% of nylon 66 resin, 14-17% of red phosphorus flame-retardant master batch, 1-4% of high heat-conductive material, 3-5% of organic black master batch, 0.5-1.0% of lubricant, 0.2-0.5% of antioxidant and 25-35% of glass fiber. The dry nylon 66 resin raw materials and other component raw materials are weighed and added into a high-speed mixer to be mixed uniformly, the mixed materials are melted, extruded and granulated by a double-screw extruder, the preparation process is simple and easy to control, the preparation process is suitable for industrial production, the prepared black red phosphorus flame-retardant reinforced nylon 66 compound can meet the requirements of 550V and above in the fields of electronics, electrics and the like, and other performances of the product are good.
Description
Technical Field
The invention relates to the technical field of flame-retardant high polymer materials, in particular to a black red phosphorus flame-retardant reinforced nylon 66 with a high CTI value and a preparation method thereof.
Background
Nylon (PA), which is a general-purpose engineering plastic with the greatest yield, the greatest variety and the greatest use, is widely used in the fields of electronics, electricity, automobiles, home appliances, machinery, etc. because of its excellent combination properties. When nylon is used in electronic, electric, household electrical appliances, electromechanical and other industries, the fire hazard of materials is inevitably considered, so that flame retardant and flame retardant reinforced nylon is produced. The flame-retardant reinforced nylon has excellent mechanical properties, good flame retardance and insulativity, and is mainly applied to the aspects of coil frameworks, piezoelectric switches, low-voltage electric housings, relays, temperature controllers, circuit breakers, motor accessories, thin-wall electronic and electric elements and the like.
As a halogen-free environment-friendly flame retardant, the red phosphorus has high flame retardant efficiency, low density, small influence on mechanical properties of materials, high tracking index (CTI) resistance and excellent processability, and is widely applied to flame-retardant reinforced nylon, but the red phosphorus is brownish red in color, so that the red phosphorus flame-retardant reinforced nylon can only be generally made into brownish red or black products of the red phosphorus. The red phosphorus flame-retardant reinforced nylon with brownish red color is more excellent in mechanical performance and electrical performance than black red phosphorus flame-retardant reinforced nylon, particularly in electrical performance CTI value, the CTI value of the red phosphorus flame-retardant reinforced nylon with brownish red color can generally reach more than 500V, and the CTI value of the black red phosphorus flame-retardant reinforced nylon adopting general carbon black matrix is generally only about 350V, so that the requirements of certain electrical elements on electrical performance CTI value are difficult to meet. However, red phosphorus flame retardant reinforced nylon A3X2G5, A3X2G7, A3X2G10, of Germany BASF corporation, has CTI values of 550V or more, regardless of whether it is a red or black product. In order to improve the CTI value of red phosphorus flame-retardant reinforced nylon, in the prior art, metal oxide is added into red phosphorus flame-retardant reinforced nylon with brownish red color to enable the CTI value to reach about 600V, and organic black matrix and metal oxide are adopted in black red phosphorus flame-retardant reinforced nylon to improve the CTI value to be more than 550V. As chinese patent CN 103304997a discloses a red phosphorus flame-retardant reinforced nylon with no acid corrosion and high electrical insulation and a preparation method thereof, the red phosphorus flame-retardant reinforced nylon comprises the following components in parts by weight: 50-60 parts of PA66, 10-18 parts of microcapsule red phosphorus master batch, 1-4 parts of red phosphorus stabilizer, 2-5 parts of acid absorber, 0.5-1 part of nylon heat stabilizer, 0.2-0.5 part of nylon antioxidant, 0.5-1 part of silicone lubricant, 0.5-2 parts of black powder and 20-30 parts of glass fiber, wherein the red phosphorus stabilizer is metal zinc oxide, the acid absorber is metal magnesium aluminum compound, the nylon heat stabilizer is a mixture of metal iodine compound, the black powder is organic black pigment, and the final CTI value of the black red phosphorus flame-retardant reinforced nylon can reach 600V, but the rigidity of the material is poor.
CTI (Comparative Tracking Index) is also referred to as comparative tracking index (or relative tracking index), which refers to the highest voltage value at which the surface of a material can withstand 50 drops of electrolyte without developing tracking failure and sustaining flame, and is a phenomenon in which the surface of an insulating material undergoes tracking degradation under specific conditions and causes tracking failure. The occurrence of the tracking of the polymer insulating material depends on the production and accumulation of free carbon on the surface of the material, and the spark discharge has the effect of removing the free carbon, so that the tracking formation process is actually a dynamic balance process of generating, gathering and removing the carbon on the surface of the material, and the CTI value of the polymer material is improved when the heat on the surface of the polymer material is easily taken away and is not easily carbonized into carbon or the carbon formed on the surface of the polymer is easily removed. Based on the principle, the CTI value of the flame-retardant material is improved by adding carbon particle substances which can conduct away heat or release crystal water to wash away the surface of the material into the flame-retardant reinforced nylon material, so that a new way is opened for meeting the requirement of red phosphorus flame-retardant reinforced nylon on the electrical property CTI value, and the flame-retardant reinforced nylon material has the requirements of research, development and application.
Disclosure of Invention
The invention aims to provide the black red phosphorus flame-retardant reinforced nylon 66 with a high CTI value, and by adding the high heat-conducting substance, the metal hydroxide containing crystal water and the organic black matrix into the nylon 66 resin, the CTI value of the black red phosphorus flame-retardant reinforced nylon 66 material can reach more than 550V, and meanwhile, the mechanical property of the material can be better maintained.
The invention further aims to provide a preparation method of the black red phosphorus flame-retardant reinforced nylon 66 with a high CTI value. The dry nylon 66 resin raw materials and other component raw materials are weighed and added into a high-speed mixer to be mixed uniformly, the mixed materials are melted, extruded and granulated by a double-screw extruder, the preparation process is simple and easy to control, the preparation process is suitable for industrial production, the prepared black red phosphorus flame-retardant reinforced nylon 66 compound can meet the requirements of 550V and above in the fields of electronics, electrics and the like, and other performances of the product are good.
The aim of the invention is achieved by the following technical scheme: the black red phosphorus flame-retardant reinforced nylon 66 with the high CTI value is prepared from the following raw materials in percentage by weight:
33.5 to 55.3 percent of nylon 66 resin
14 to 17 percent of red phosphorus flame-retardant master batch
1 to 4 percent of high heat conductive material
1 to 4 percent of metal hydroxide
3 to 5 percent of organic black matrix
0.5 to 1.0 percent of lubricant
Antioxidant 0.2-0.5%
25 to 35 percent of glass fiber
The nylon 66 resin is PA66 resin with relative viscosity of 2.7.
The red phosphorus flame-retardant master batch is a microcapsule coated red phosphorus flame-retardant master batch.
Further, the red phosphorus flame-retardant master batch is selected from medium blue morning light RPM440T, the red phosphorus content of the master batch is 40%, the ignition point is more than or equal to 320 ℃, and the flame-retardant master batch has the characteristics of good flame-retardant effect, higher CTI value of the manufactured product and the like.
The high thermal conductivity material is Boron Nitride (BN).
The metal hydroxide is magnesium hydroxide.
The organic black matrix is aniline black organic black matrix.
The lubricant is any one or a mixture of two of silicone powder and pentaerythritol stearate (PETS).
The antioxidant is a mixture of antioxidant 1098 and antioxidant 168 in a weight ratio of 1:1.
The glass fiber is alkali-free continuous long glass fiber with the surface treated.
A preparation method of black red phosphorus flame-retardant reinforced nylon 66 with a high CTI value comprises the following steps: the method comprises the steps of (by weight) placing 33.5-55.3% of nylon 66 resin, 14-17% of red phosphorus flame-retardant master batch, 1-4% of high heat conduction material, 1-4% of metal hydroxide, 3-5% of organic black master batch, 0.5-1.0% of lubricant and 0.2-0.5% of antioxidant into a high-speed mixer, mixing for 3-5 min, placing into a hopper of a double-screw extruder after mixing uniformly, adding 25-35% of glass fiber from a glass fiber port of the extruder, and carrying out melt extrusion granulation by the double-screw extruder to obtain black red phosphorus flame-retardant reinforced nylon 66; the CTI value of the black red phosphorus flame-retardant reinforced nylon 66 is more than or equal to 550V, the tensile strength is more than or equal to 120 MPa, and the bending strength is more than or equal to 190 MPa.
The temperature of each region of the double-screw extruder is controlled between 255 and 280 ℃, and the screw rotating speed is controlled between 200 and 220rpm.
The invention has the beneficial effects that:
(1) Boron nitride BN is a high heat conduction substance, and the heat conduction coefficient is 40-120W/m.K; magnesium hydroxide is a metal hydroxide containing crystal water and is also a commonly used inorganic flame retardant. According to the invention, the CTI value of the red phosphorus flame-retardant reinforced nylon 66 is improved by adding boron nitride and magnesium hydroxide, so that the black red phosphorus flame-retardant reinforced nylon 66 can meet the requirements of 550V and above in the fields of electronics and electrics, and other properties of the product are good, and a new way is opened up for improving the CTI value of the flame-retardant material. The adding proportion of the boron nitride and the magnesium hydroxide in the invention is 1-4%, which not only meets the requirement of improving CTI value, but also does not greatly influence the mechanical property of the flame retardant material due to excessive addition.
(2) The nigrosine black organic black matrix used in the invention has little influence on the mechanical property and appearance of the flame-retardant reinforced nylon 66 material; meanwhile, the organic black matrix has good electrical insulation performance, and has little influence on CTI value of the material. According to the invention, any one of silicone powder and pentaerythritol stearate (PETS) is used as a lubricant, so that the appearance of the glass fiber reinforced flame-retardant nylon 66 material is improved to a certain extent, and the addition of the antioxidant improves the heat aging resistance of the flame-retardant reinforced nylon 66 material.
(3) The preparation process is simple and easy to control, the prepared black red phosphorus flame-retardant reinforced nylon 66 with high CTI value can meet the use requirement that CTI value reaches 550V or above in the fields of electronics and electrics, production equipment is conventional equipment, production period is short, no three wastes are generated in the production process, and the preparation process is environment-friendly and suitable for industrial production.
Detailed Description
The present invention will be further described in detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The following are the raw materials provided by the relevant commercial or commercial suppliers specifically employed in the examples and comparative examples of the present invention, but are not limited to the following:
1) PA66 EP158 Zhejiang peak group;
2) Red phosphorus flame retardant master RPM440T, blue morning light in RPM 440;
3) Boron nitride 15 μm is commercially available;
4) Magnesium hydroxide 1250 mesh is commercially available;
5) Black matrix: organic black matrix N54/1033 uk Gao Lai,
black carbon master 2772 cabot corporation;
6) And (3) a lubricant: blue morning light in the silicone powder GM-100,
PETS us longsha;
7) An antioxidant: a mixture of antioxidant 1098 and antioxidant 168 in a weight ratio of 1:1;
8) Glass fiber ER13-2000-940 type boulder group.
Examples 1-6 and comparative examples 1-4 a high CTI black red phosphorus flame retardant reinforced nylon 66 was prepared as follows, the weight percentages of the raw materials being shown in Table 1:
respectively placing nylon 66 resin, red phosphorus flame-retardant master batch, high heat-conducting material, metal hydroxide, black master batch, lubricant and antioxidant which are in the embodiments 1-6 and the comparative examples 1-4 in the high-speed mixer in percentage by weight, mixing for 3-5 min, placing the mixture into a hopper of a double-screw extruder after uniformly mixing, adding glass fibers from a glass fiber port of the extruder, and carrying out melt extrusion granulation by the double-screw extruder to obtain the red phosphorus flame-retardant reinforced nylon 66, wherein the temperature of each region of the double-screw extruder is controlled at 255-280 ℃, and the screw rotating speed is controlled at 200-220 rpm.
TABLE 1 weight percent amounts of examples 1-6 and comparative examples 1-4
Product performance test: the black red phosphorus flame-retardant reinforced nylon 66 compound with high CTI value obtained in the examples 1-6 and the comparative examples 1-4 is placed in a blast oven to be dried for 4-6 hours at the temperature of 100-120 ℃, and is subjected to injection molding into mechanical test sample bars, flame-retardant sample bars and CTI test sample pieces by an injection molding machine, and the tensile strength, the bending strength, the cantilever notched impact strength, the vertical combustion and the CTI value of the black red phosphorus flame-retardant reinforced nylon 66 compound are tested according to the relevant standards of GB/T1040-2006, GB/T9341-2008, GB/T1843-2008, UL94 and GB/T4207-2003. The performance test data are shown in Table 2.
TABLE 2 Performance test results
From the performance test results of table 2, in combination with the ratios of table 1, it can be seen that: as long as the black red phosphorus flame-retardant reinforced nylon 66 material with high heat conduction material boron nitride of 1-4%, magnesium hydroxide of 1-4%, organic black masterbatch of 3-5% and red phosphorus flame-retardant masterbatch RPM440T of 14-17% is adopted, the CTI value can reach 550V. While both boron nitride and magnesium hydroxide were added to a maximum of 4% of the present invention as compared to comparative examples 1 and 3 of example 2, the final CTI value was not up to 550V by changing the red phosphorus flame retardant masterbatch RPM440T to RPM440 and the organic black masterbatch N54/1033 to the ordinary carbon black masterbatch 2772, and the CTI value of the flame retardant reinforced nylon material to which the ordinary carbon black was added was reduced more. Compared with comparative example 2 of example 4, the comparative example 2 changes 4% boron nitride and 1% magnesium hydroxide into only 4% boron nitride, the rest proportion is basically unchanged, and the CTI value of the final flame-retardant reinforced nylon material does not reach 550V; compared with comparative example 4 of example 6, the comparative example 4 is prepared by changing 1% of boron nitride and 4% of magnesium hydroxide into only 4% of magnesium hydroxide, and the rest of the proportion is basically unchanged, and the CTI value of the final flame-retardant reinforced nylon material does not reach 550V.
Therefore, the preparation of the raw materials and the proportions of the black red phosphorus flame-retardant reinforced nylon 66 with the high CTI value are complementary, the raw materials with the proportions interact, the CTI value of the red phosphorus flame-retardant reinforced nylon 66 is possibly affected by the change of any one of the raw materials and the adjustment of the proportions, and the requirements that the CTI value reaches 550V or above in the fields of electronics and electrics and the like and other performances of products cannot be met.
The above embodiments are only for better illustrating the present invention, but are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements, etc. based on the above description of the present invention fall within the scope of the present invention.
Claims (5)
1. A black red phosphorus flame-retardant reinforced nylon 66 with a high CTI value is characterized in that: comprises the following raw materials in percentage by weight:
33.5 to 55.3 percent of nylon 66 resin
14 to 17 percent of red phosphorus flame-retardant master batch
1 to 4 percent of high heat conductive material
1 to 4 percent of metal hydroxide
3 to 5 percent of organic black matrix
0.5 to 1.0 percent of lubricant
Antioxidant 0.2-0.5%
25 to 35 percent of glass fiber
The nylon 66 resin is PA66 resin with relative viscosity of 2.7;
the red phosphorus flame-retardant master batch is a microcapsule coated red phosphorus flame-retardant master batch, and medium blue morning light RPM440T is selected;
the high heat conduction material is boron nitride;
the metal hydroxide is magnesium hydroxide;
the organic black matrix is aniline black organic black matrix.
2. The high CTI value black red phosphorus flame-retardant reinforced nylon 66 according to claim 1, wherein: the lubricant is any one or a mixture of two of silicone powder and pentaerythritol stearate.
3. The high CTI value black red phosphorus flame-retardant reinforced nylon 66 according to claim 1, wherein: the antioxidant is a mixture of antioxidant 1098 and antioxidant 168 in a weight ratio of 1:1.
4. The high CTI value black red phosphorus flame-retardant reinforced nylon 66 according to claim 1, wherein: the glass fiber is alkali-free continuous long glass fiber with the surface treated.
5. A method for preparing the high CTI black red phosphorus flame-retardant reinforced nylon 66 according to claim 1, which is characterized in that: the method comprises the steps of (by weight) placing 33.5-55.3% of nylon 66 resin, 14-17% of red phosphorus flame-retardant master batch, 1-4% of high heat conduction material, 1-4% of metal hydroxide, 3-5% of organic black master batch, 0.5-1.0% of lubricant and 0.2-0.5% of antioxidant into a high-speed mixer, mixing for 3-5 min, placing into a hopper of a double-screw extruder after mixing uniformly, adding 25-35% of glass fiber from a glass fiber port of the extruder, and carrying out melt extrusion granulation by the double-screw extruder to obtain black red phosphorus flame-retardant reinforced nylon 66; the CTI value of the black red phosphorus flame-retardant reinforced nylon 66 is more than or equal to 550V, the tensile strength is more than or equal to 120 MPa, and the bending strength is more than or equal to 190 MPa; the temperature of each region of the double-screw extruder is controlled between 255 and 280 ℃, and the screw rotating speed is controlled between 200 and 220rpm.
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| CN115710430A (en) * | 2022-11-30 | 2023-02-24 | 广东道生科技股份有限公司 | Nylon material and preparation method and application thereof |
| CN116041871B (en) * | 2023-02-21 | 2024-06-25 | 万华化学（宁波）有限公司 | Flame-retardant master batch and high CTI flame-retardant PC product |
| CN116640440B (en) * | 2023-04-03 | 2024-07-05 | 金旸（厦门）新材料科技有限公司 | Low-precipitation red phosphorus flame-retardant glass fiber reinforced nylon and preparation method and application thereof |
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