CN113527877A - 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 high CTI value black red phosphorus flame-retardant reinforced nylon 66 which is prepared from the following raw materials, by weight, 33.5-55.3% of nylon 66 resin, 14-17% of a red phosphorus flame-retardant master batch, 1-4% of a high heat conductor metal hydroxide, 1-4% of an organic black master batch, 3-5% of a lubricant, 0.5-1.0% of an antioxidant, 0.2-0.5% of a glass fiber. The prepared black red phosphorus flame-retardant reinforced nylon 66 compound can meet the requirement that the CTI value in the fields of electronics and electricity and the like can reach 550V and above, and the other properties of the product are good.
Description
Technical Field
The invention relates to the technical field of flame-retardant high polymer materials, and particularly relates to black red phosphorus flame-retardant reinforced nylon 66 with a high CTI value and a preparation method thereof.
Background
Nylon (PA) is a versatile engineering plastic with the highest yield, the largest variety, and the widest range of applications, and is widely used in the fields of electronics, electrical, automobiles, home appliances, machinery, and the like because of its excellent comprehensive properties. When the nylon is applied to the industries of electronics, electricity, household appliances, electromechanics and the like, the fire hazard of materials is inevitably considered, so that the flame-retardant and flame-retardant reinforced nylon is produced. The flame-retardant reinforced nylon is mainly applied to coil frameworks, low-voltage electrical apparatus switches, low-voltage electrical casings, relays, temperature controllers, circuit breakers, motor accessories, thin-wall electronic and electrical elements and the like because of excellent mechanical properties, good flame retardance and good insulativity.
The red phosphorus is used as a halogen-free environment-friendly flame retardant, has high flame retardant efficiency, low density, small influence on the mechanical properties of materials, high Comparative Tracking Index (CTI) and excellent processability, and is widely applied to flame-retardant reinforced nylon, but the red phosphorus is brownish red, so the red phosphorus flame-retardant reinforced nylon can only be made into brownish red or black products of the red phosphorus. Compared with black red phosphorus flame-retardant reinforced nylon, the brownish red phosphorus flame-retardant reinforced nylon has better mechanical property and electrical property, particularly, the CTI value of the brownish red phosphorus flame-retardant reinforced nylon can generally reach more than 500V on the electrical property CTI value, while the CTI value of the black red phosphorus flame-retardant reinforced nylon adopting common carbon black masterbatch is only about 350V generally, and the requirements of certain low-voltage electrical elements on the electrical property CTI value are difficult to meet. However, red phosphorus flame retardant reinforced nylons A3X2G5, A3X2G7 and A3X2G10 from BASF of Germany have CTI values of 550V or more regardless of red or black products. In order to improve the CTI value of red phosphorus flame-retardant reinforced nylon, the prior art generally adds metal oxide into red brown phosphorus flame-retardant reinforced nylon to enable the CTI value to reach about 600V, and adopts organic black masterbatch and metal oxide to improve the CTI value of black red phosphorus flame-retardant reinforced nylon to reach more than 550V. For example, chinese patent CN 103304997a discloses an acid corrosion-free, high-electrical insulation red phosphorus flame-retardant reinforced nylon and a preparation method thereof, wherein the red phosphorus flame-retardant reinforced nylon comprises the following components in parts by weight: PA 6650-60 parts, microcapsule red phosphorus master batch 10-18 parts, red phosphorus stabilizer 1-4 parts, acid absorbent 2-5 parts, nylon heat stabilizer 0.5-1 part, nylon antioxidant 0.2-0.5 part, silicone lubricant 0.5-1 part, black powder 0.5-2 parts, glass fiber 20-30 parts, wherein the red phosphorus stabilizer is metal zinc oxide, the acid absorbent is metal magnesium aluminum compound, the nylon heat stabilizer is a mixture of metal iodide compounds, and black powder is organic black pigment.
Cti (comparative Tracking index), also known as the comparative Tracking index (or relative Tracking index), refers to the highest voltage value at which a material surface can withstand 50 drops of electrolyte without developing Tracking failure and sustaining flame, which reflects the phenomenon that the insulation material surface undergoes Tracking degradation and leads to Tracking failure under certain conditions. The generation of the tracking of the polymer insulation material depends on the production and accumulation of free carbon on the surface of the material, and the spark discharge has the function of removing the free carbon, so that the tracking formation process is actually a dynamic balance process of generating, accumulating 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 material 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 carbon particle substances formed on the surface of the material in the flame-retardant reinforced nylon material, a new way is opened for meeting the requirement of the red phosphorus flame-retardant reinforced nylon on the CTI value of the electrical property, and the method has the needs of research and development and application.
Disclosure of Invention
The invention aims to provide the black red phosphorus flame-retardant reinforced nylon 66 with the high CTI value, and the high heat-conducting substance, the metal hydroxide containing crystal water and the organic black master are added into the nylon 66 resin, so that the CTI value of the black red phosphorus flame-retardant reinforced nylon 66 material can reach more than 550V, and the mechanical property of the material can be better maintained.
The invention also aims to provide a preparation method of the high CTI value black red phosphorus flame-retardant reinforced nylon 66. The prepared black red phosphorus flame-retardant reinforced nylon 66 compound can meet the requirement that the CTI value in the fields of electronics and electricity and the like can reach 550V and above, and the other properties of the product are good.
The purpose of the invention is realized by the following technical scheme: the high CTI value black red phosphorus flame-retardant reinforced nylon 66 is prepared from the following raw materials in percentage by weight:
33.5 to 55.3 percent of nylon 66 resin
14-17% of red phosphorus flame-retardant master batch
1 to 4 percent of high heat-conducting material
1 to 4% of a metal hydroxide
3-5% of organic black master batch
0.5 to 1.0 percent of lubricant
0.2 to 0.5 percent of antioxidant
25-35% of glass fiber
The nylon 66 resin is a PA66 resin with a relative viscosity of 2.7.
The red phosphorus flame-retardant master batch is a microcapsule-coated red phosphorus flame-retardant master batch.
Furthermore, 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 not less than 320 ℃, and the master batch has the characteristics of good flame-retardant effect, high CTI value of the prepared product and the like.
The high thermal conductor is Boron Nitride (BN).
The metal hydroxide is magnesium hydroxide.
The organic black master batch is aniline black organic black master batch.
The lubricant is any one of silicone powder and pentaerythritol stearate (PETS) or a mixture of the two.
The antioxidant is a mixture of an antioxidant 1098 and an antioxidant 168 according to the 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: putting 33.5-55.3% of dried nylon 66 resin, 14-17% of red phosphorus flame-retardant master batch, 1-4% of high thermal conductivity, 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, uniformly mixing, putting into a hopper of a double-screw extruder, adding 25-35% of glass fiber from a glass fiber opening of the extruder, and performing melt extrusion granulation by the double-screw extruder to obtain the 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 area of the double-screw extruder is controlled to be 255-280 ℃, and the rotating speed of the screw is controlled to be 200-220 rpm.
The invention has the beneficial effects that:
(1) boron nitride BN is a high heat-conducting substance, and the heat conductivity coefficient of the boron nitride BN is 40-120W/m.K; magnesium hydroxide is a metal hydroxide containing water of crystallization and is also a commonly used inorganic flame retardant. According to the invention, boron nitride and magnesium hydroxide are added to improve the CTI value of the red phosphorus flame-retardant reinforced nylon 66, so that the black red phosphorus flame-retardant reinforced nylon 66 can meet the requirement that the CTI value reaches 550V or more in the fields of electronics and electricity and the like, other properties of the product are good, and a new way for improving the CTI value of the flame-retardant material is opened up. The adding proportion of the boron nitride and the magnesium hydroxide is 1-4%, so that the requirement for improving the CTI value is met, and the mechanical property of the flame-retardant material cannot be greatly influenced by excessive addition.
(2) The nigrosine organic black master batch 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 master batch has good electrical insulation performance and small influence on the CTI value of the material. In 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 heat-resistant aging performance of the flame-retardant reinforced nylon 66 material is improved by adding the antioxidant.
(3) The preparation process is simple and easy to control, the prepared black red phosphorus flame-retardant reinforced nylon 66 with the high CTI value can meet the use requirement that the CTI value reaches 550V or more in the fields of electronics and electricity and the like, the production equipment is conventional equipment, the production period is short, no three wastes are generated in the production process, and the method is environment-friendly and suitable for industrial production.
Detailed Description
The present invention will be further described in detail with reference to examples in order to better explain the present invention, but the embodiments of the present invention are not limited thereto.
The following are commercially available or commercially available materials specifically employed in the examples and comparative examples of the present invention, but are not limited to the following:
1) PA66 EP158 Zhejiang Huafeng group;
2) red phosphorus flame retardant masterbatch RPM440T, blue-morning light in RPM 440;
3) boron nitride 15 μm commercially available;
4) magnesium hydroxide is available on the market with 1250 meshes;
5) black masterbatch: organic black masterbatch N54/1033 British Gaolai,
carbon black masterbatch 2772 cabot corporation;
6) lubricant: silicone powder GM-100 blue-morning light,
PETS American Longsha;
7) antioxidant: a mixture of antioxidant 1098 and antioxidant 168 in a weight ratio of 1: 1;
8) glass fiber ER 13-2000-.
The black red phosphorus flame-retardant reinforced nylon 66 with high CTI value is prepared by the following steps of examples 1-6 and comparative examples 1-4, and the weight percentage of the raw materials is shown in the following table 1:
respectively putting the nylon 66 resin, the red phosphorus flame-retardant master batch, the high-heat-conductivity material, the metal hydroxide, the black master batch, the lubricant and the antioxidant in the corresponding weight percentages in the embodiments 1-6 and the comparative examples 1-4 into a high-speed mixer, mixing for 3-5 min, uniformly mixing, putting into a hopper of a double-screw extruder, adding glass fiber from a glass fiber port of the extruder, and performing melt extrusion granulation by the double-screw extruder to obtain the red phosphorus flame-retardant reinforced nylon 66, wherein the temperature of each zone of the double-screw extruder is controlled to be 255-280 ℃, and the rotating speed of the screw is controlled to be 200-220 rpm.
TABLE 1 weight percent usage of examples 1-6 and comparative examples 1-4
And (3) product performance testing: the black red phosphorus flame-retardant reinforced nylon 66 compound with the 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 h at the temperature of 100-120 ℃, and is subjected to injection molding by an injection molding machine to form a mechanical test sample strip, a flame-retardant sample strip and a CTI test sample piece, and the tensile strength, the bending strength, the cantilever beam notch impact strength, the vertical burning and the CTI value are respectively tested according to relevant standards of GB/T1040-2006, GB/T9341-2008, GB/T1843-2008, UL94 and GB/T4207-2003. The performance test data is shown in table 2.
Table 2 results of performance testing
From the performance test results in table 2, it can be seen that, in combination with the formulation in table 1: the CTI value of the black red phosphorus flame-retardant reinforced nylon 66 material can meet the requirement of 550V only by adopting 1-4% of high-heat-conductivity substance boron nitride, 1-4% of magnesium hydroxide, 3-5% of organic black master batch and 14-17% of red phosphorus flame-retardant master batch RPM 440T. Compared with comparative example 1 and comparative example 3 of example 2, although boron nitride and magnesium hydroxide are added to the maximum amount of 4% of the invention, the final CTI value of the flame-retardant reinforced nylon material added with the common carbon black cannot reach 550V by replacing the red phosphorus flame-retardant master batch RPM440T with RPM440 and replacing the organic black master batch N54/1033 with the common carbon black master batch 2772. Compared with the comparative example 2 of the embodiment 4, 4 percent of boron nitride and 1 percent of magnesium hydroxide in the embodiment are changed into only 4 percent of boron nitride, the rest mixture ratio is basically unchanged, and the CTI value of the final flame-retardant reinforced nylon material does not reach 550V; compared with the comparative example 4 of the example 6, the 1% boron nitride and the 4% magnesium hydroxide in the example are changed into only 4% magnesium hydroxide, and the rest mixture ratio is basically unchanged, so that the CTI value of the final flame-retardant reinforced nylon material does not reach 550V.
Therefore, the raw materials and the proportion for preparing the black red phosphorus flame-retardant reinforced nylon 66 with the high CTI value are complementary to each other, the raw materials in the proportion are interactive, the CTI value of the red phosphorus flame-retardant reinforced nylon 66 can be influenced by the change of any raw material and the adjustment of the proportion, and the requirements that the CTI value reaches 550V or more in the fields of electronics and electricity and the like and other performances of products cannot be met.
The above-described embodiments are merely intended to better illustrate the present invention and should not be construed as limiting the scope of the present invention, and any modifications, equivalents, improvements, etc. based on the above-described embodiments of the present invention are intended to fall within the scope of the present invention.
Claims (11)
1. The high CTI value black red phosphorus flame-retardant reinforced nylon 66 is characterized in that: the material is prepared from the following raw materials in percentage by weight:
33.5 to 55.3 percent of nylon 66 resin
14-17% of red phosphorus flame-retardant master batch
1 to 4 percent of high heat-conducting material
1 to 4% of a metal hydroxide
3-5% of organic black master batch
0.5 to 1.0 percent of lubricant
0.2 to 0.5 percent of antioxidant
25-35% of glass fiber.
2. The high CTI value black red phosphorus flame retardant reinforced nylon 66 according to claim 1, wherein: the nylon 66 resin is a PA66 resin with a relative viscosity of 2.7.
3. The high CTI value black red phosphorus flame retardant reinforced nylon 66 according to claim 1, wherein: the red phosphorus flame-retardant master batch is a microcapsule-coated red phosphorus flame-retardant master batch.
4. The high CTI value black red phosphorus flame retardant reinforced nylon 66 according to claim 1, wherein: the red phosphorus flame-retardant master batch is selected from medium-blue-morning light RPM 440T.
5. The high CTI value black red phosphorus flame retardant reinforced nylon 66 according to claim 1, wherein: the high thermal conductor is boron nitride.
6. The high CTI value black red phosphorus flame retardant reinforced nylon 66 according to claim 1, wherein: the metal hydroxide is magnesium hydroxide.
7. The high CTI value black red phosphorus flame retardant reinforced nylon 66 according to claim 1, wherein: the organic black master batch is aniline black organic black master batch.
8. The high CTI value black red phosphorus flame retardant reinforced nylon 66 according to claim 1, wherein: the lubricant is any one of or a mixture of silicone powder and pentaerythritol stearate.
9. The high CTI value black red phosphorus flame retardant reinforced nylon 66 according to claim 1, wherein: the antioxidant is a mixture of an antioxidant 1098 and an antioxidant 168 according to the weight ratio of 1: 1.
10. 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.
11. A method for preparing the high CTI value black red phosphorus flame retardant reinforced nylon 66 as claimed in claim 1, wherein the method comprises the following steps: putting 33.5-55.3% of dried nylon 66 resin, 14-17% of red phosphorus flame-retardant master batch, 1-4% of high thermal conductivity, 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, uniformly mixing, putting into a hopper of a double-screw extruder, adding 25-35% of glass fiber from a glass fiber opening of the extruder, and performing melt extrusion granulation by the double-screw extruder to obtain the 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 area of the double-screw extruder is controlled to be 255-280 ℃, and the rotating speed of the screw is controlled to be 200-220 rpm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN116041871A (en) * | 2023-02-21 | 2023-05-02 | 万华化学（宁波）有限公司 | Flame-retardant master batch and high CTI flame-retardant PC product |
| CN116640440A (en) * | 2023-04-03 | 2023-08-25 | 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN116041871A (en) * | 2023-02-21 | 2023-05-02 | 万华化学（宁波）有限公司 | Flame-retardant master batch and high CTI flame-retardant PC product |
| CN116640440A (en) * | 2023-04-03 | 2023-08-25 | 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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| CN113527877B (en) | 2023-05-02 |
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