CN110066450B - Low-smoke halogen-free flame-retardant material and preparation method thereof - Google Patents
Low-smoke halogen-free flame-retardant material and preparation method thereof Download PDFInfo
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Abstract
The technical scheme of the invention provides a low-smoke halogen-free flame-retardant material and a preparation method thereof. The low-smoke halogen-free flame-retardant material contains ethylene-vinyl acetate rubber, magnesium hydroxide, aluminum hydroxide, carbon black and the like, all properties of the material can reach or even exceed the national standard requirements, and the material is superior to the existing similar materials, so that the problems that the existing flame-retardant wire and cable material is not high-temperature resistant, has poor physical properties, has large smoke generation amount during combustion, and generates a large amount of toxic and harmful gas during combustion are solved. The preparation method of the low-smoke halogen-free flame-retardant material provided by the technical scheme of the invention has the advantages of simple process, uncomplicated required equipment and easiness in manufacturing and popularization.
Description
Technical Field
The invention belongs to the technical field of flame retardant materials, and particularly relates to a low-smoke halogen-free flame retardant material and a preparation method thereof.
Background
The electric wire and the electric cable are linear objects and are also linear as ignition sources, flame spreads along with the trend of the electric wire and the electric cable, the fire burning rate of the horizontal electric cable is 3.5m/min, and the vertical burning rate of the electric wire and the electric cable of the vertical frame (well) reaches 8-9 m/min. The wire and cable burn quickly and are difficult to control once ignited. The reasons for fire of the electric wire and the cable include: (1) the electric wire and the cable are used for transferring energy, and have certain temperature, and if the temperature exceeds the tolerable range, the electric wire and the cable are burnt; (2) under the condition of long-term on-load operation of the electric wire and the electric cable, the insulating layer and the sheath layer are locally aged; (3) because the electric wire and the cable have certain temperature under the condition of carrying operation, a common object has a preheating process before combustion, the object with high temperature does not need the preheating process, and the common electric wire and the cable do not have flame retardance, once an external fire source exists, the carried electric wire and the cable are easy to ignite; (4) because the wires and cables laid in the electric well or the wire slot are often laid in bundles, once a fire disaster occurs, heat radiation during combustion is mutually transmitted to generate a gathering effect, so that the fire disaster is spread continuously and floods to cause a disaster; (5) the electric wire and the cable can generate rolling dense smoke and a large amount of toxic gas after being ignited, so that in the conventional fire disaster, delayed diffusion enables escape personnel to distinguish the two alarming measures in the unclear direction, and the time of staying in the fire scene is prolonged. For the above reasons, the wire and cable material is required to have flame retardancy.
The flame-retardant wire and cable material generally refers to a wire and cable material having flame-retardant properties when laid in a bundle. The flame-retardant electric wire and cable are commonly used in places with high cable laying density, such as subway tunnels, power stations, important high-rise buildings, nuclear power stations and the like. The flame retardant wire and cable can be generally classified into general flame retardant wire and cable, low smoke low halogen flame retardant wire and cable and low smoke halogen-free flame retardant wire and cable. The general flame-retardant electric wire and cable release a large amount of dense smoke and corrosive halide during combustion, which easily causes casualties and corrodes various devices. The low-smoke low-halogen flame-retardant wire cable is mainly a PVC wire cable, and the cable has the special functions of low price, good flame-retardant effect, oil resistance, corrosion resistance and the like, is developed earlier, and has more varieties and models at present. The PVC molecular structure contains chlorine atoms, so that the PVC has better flame retardant property, however, the common PVC electric wire and cable still can release more smoke and toxic hydrogen chloride gas when burning, so the smoke abatement flame retardant is added in the PVC formula to inhibit the generation of smoke, and the addition of the smoke abatement flame retardant can influence the mechanical property of the electric wire and cable. The matrix resin of the low-smoke halogen-free flame-retardant wire and cable material is generally halogen-free polyolefin, water and carbon dioxide are decomposed during combustion, obvious smoke and toxic gas are not generated, and the polyolefin mainly comprises PE, PP, EVA, ethylene propylene rubber and the like. Inorganic flame retardant is generally added to the low-smoke halogen-free flame-retardant polyolefin wire and cable material, and the flame-retardant mechanism is as follows: the cable is heated to decompose the intermetallic compound in fire, releases crystal water and absorbs a large amount of heat, thereby inhibiting the temperature rise of polyolefin, delaying the thermal decomposition of the polyolefin, reducing the combustion rate, and generating water vapor which can dilute combustible gas and play a role in flame retardance. However, the inorganic flame retardant has poor compatibility with resin and is added in a relatively large amount, which often causes the mechanical properties of the wire and cable material to be reduced.
Disclosure of Invention
In order to solve the problems of flame-retardant wire and cable materials in the prior art, one of the embodiments of the present invention is to provide a low-smoke halogen-free flame-retardant material.
Another objective of an embodiment of the present invention is to provide a preparation method of the low-smoke halogen-free flame retardant material.
In order to achieve the above purpose, one of the embodiments of the present invention adopts the following technical solutions:
the low-smoke halogen-free flame-retardant material comprises the following components in parts by weight:
ethylene-vinyl acetate rubber: 80-120 parts of (by weight),
magnesium hydroxide: 40-60 parts of (A) a water-soluble polymer,
aluminum hydroxide: 50-80 parts of a water-soluble polymer,
carbon black: 2 to 10 parts by weight of a stabilizer,
dioctyl sebacate: 5 to 10 parts by weight of a surfactant,
zinc oxide: 4 to 10 parts of (A) a water-soluble polymer,
stearic acid: 0.5 to 1.5 parts by weight,
an anti-aging agent: 2 to 4 parts of (A) a water-soluble polymer,
flame retardant: 10-20 parts of (A) a water-soluble polymer,
vinyltris (2-methoxyethoxy) silane: 1 to 3 parts of (A) a water-soluble polymer,
processing aid: 4 to 6 parts of (A) a water-soluble polymer,
sensitizer: 2-5 parts.
Preferably, the ethylene-vinyl acetate rubber has a mooney viscosity of ML 1+ 4100 ℃: 23-31, the VAC content is as follows: 48.5 to 51.5 percent.
The Mooney viscosity is too low, and the rubber material is easy to stick to a roller in the mixing process; mooney viscosity is too high, rubber flowability is poor, rubber extrusion is difficult, and the product appearance is rough. The Mooney viscosity ranges described above are most effective.
The ethylene-vinyl acetate rubber is formed by copolymerizing ethylene and vinyl acetate, and has excellent heat resistance, ozone resistance and weather resistance.
Preferably, the carbon black has an iodine absorption value of more than 82 +/-6 g/kg and a DBP oil absorption value of more than 102 +/-6 cm3/100g。
The carbon black conforming to the condition has good reinforcing performance, is easy to disperse in the rubber compound, and is beneficial to improving the physical and mechanical properties and the flame retardant property of the rubber compound.
Carbon black, also known as carbon black, is an amorphous carbon, a light, loose and extremely fine black powder with a very large surface area ranging from 10 to 3000m2The carbon-containing substance is a product obtained by incomplete combustion or thermal decomposition of a carbon-containing substance (coal, natural gas, heavy oil, fuel oil, etc.) under the condition of insufficient air. In one embodiment of the invention, the carbon black is used, so that the degradation of the base material and the flame retardant can be further accelerated, a carbon layer with a protection effect can be formed more quickly, and the flame retardant property of the polymer can be improved.
Preferably, the ignition weight loss of the magnesium hydroxide is more than or equal to 30 percent, and the particle size D50 is less than or equal to 2.0 mu m.
The magnesium hydroxide meeting the conditions has high purity and small particle size, has small influence on the mechanical property of the sizing material when being added in a large amount, and can better play the flame-retardant and smoke-eliminating effects when being used together with aluminum hydroxide.
Magnesium hydroxide is a novel filling type flame retardant, releases bound water when being heated and decomposed, absorbs a large amount of latent heat to reduce the surface temperature of a synthetic material filled with the magnesium hydroxide in flame, and has the effects of inhibiting the decomposition of a polymer and cooling generated combustible gas. The magnesium oxide generated by decomposition is a good refractory material, and can also help to improve the fire resistance of the synthetic material, and the water vapor emitted by the magnesium oxide can also be used as a smoke suppressant. The magnesium hydroxide has triple functions of flame retardance, smoke suppression and filling.
Preferably, the ignition weight loss of the aluminum hydroxide is more than or equal to 34%, the particle size D50 is less than or equal to 2.0um, and the content of aluminum oxide in the aluminum hydroxide is more than or equal to 64.5%.
The aluminum hydroxide serving as a flame retardant can not only resist flame, but also prevent fuming, does not produce drippings and does not produce toxic gas.
The aluminum hydroxide meeting the conditions has high purity and small particle size, has small influence on the mechanical property of the rubber material when being added in a large amount, and can better play the flame-retardant and smoke-eliminating functions when being used together with the magnesium hydroxide.
Preferably, the anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole in a mass ratio of 1: (1-2).
The 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer has excellent protection effect on aging caused by thermal oxidation aging, also has extremely strong inhibition effect on metal catalytic oxidation, and has no influence on the processability, vulcanization characteristic and physical properties of vulcanized rubber.
2-mercaptobenzimidazole is a main non-polluting antioxidant in the rubber industry and reduces discoloration during rubber vulcanization.
Preferably, the flame retardant is a mixture of melamine polyphosphate and pentaerythritol caged phosphate.
The mass ratio of the melamine polyphosphate to the pentaerythritol caged phosphate is (2-3): (1-2).
The melamine polyphosphate contains rich acid sources and gas sources, and can form a flame-retardant and non-dripping carbonized coke-forming material when being compounded with carbon source pentaerythritol caged phosphate to be used as a flame retardant.
Preferably, the processing aid is polyethylene wax and microcrystalline wax according to the mass ratio of (2-1): 1.
Preferably, the sensitizer is triallyl isocyanurate and trimethylolpropane trimethacrylate according to the mass ratio of (1-2): (2-3).
The preparation method of the low-smoke halogen-free flame-retardant material comprises the following steps:
(1) weighing the components according to the proportion, and sequentially adding ethylene-vinyl acetate rubber, carbon black, stearic acid, an anti-aging agent, a processing aid, magnesium hydroxide, a flame retardant, a sensitizer and vinyltris (2-methoxyethoxy) silane into an internal mixer for primary internal mixing;
(2) sequentially adding zinc oxide, aluminum hydroxide and dioctyl sebacate into the product obtained in the step (1) for secondary banburying;
(3) and (3) cleaning and turning the product obtained in the step (2), carrying out third banburying, and then unloading, filtering and mixing to obtain the low-smoke halogen-free flame retardant material.
Preferably, the preparation method of the low-smoke halogen-free flame retardant material comprises the following steps:
(1) weighing the components according to the ratio, and sequentially adding ethylene-vinyl acetate rubber, carbon black, stearic acid, an anti-aging agent, a processing aid, magnesium hydroxide, a sensitizer and vinyltris (2-methoxyethoxy) silane into an internal mixer for first internal mixing, wherein the time for the first internal mixing is 160-200 s;
(2) sequentially adding zinc oxide, aluminum hydroxide and dioctyl sebacate into the product obtained in the step (1), and carrying out secondary banburying for 140-160 s;
(3) and (3) cleaning and turning the product obtained in the step (2), carrying out third banburying for 100-140 s, carrying out the second banburying for 60s, unloading, controlling the unloading temperature at 125 +/-5 ℃, then filtering, preferably selecting 60 meshes for the number of the filtered rubber materials, mixing the filtered rubber materials on an open mill, and guiding the rubber materials to an automatic turner for turning for 300s to obtain the low-smoke halogen-free flame retardant material.
After the step (3), the obtained low-smoke halogen-free flame retardant material can be rolled into a film by a three-roll calender.
In order to prevent the surface of the film from being adhered and prolong the storage time of the film, a release agent can be coated on the surface of the film.
The release agent may be an aqueous solution of zinc stearate.
The embodiment of the invention has the beneficial effects
The low-smoke halogen-free flame-retardant material provided by one of the embodiments of the invention has various performances which can reach or even exceed national standard requirements, is superior to the existing similar materials, and solves the problems that the existing flame-retardant wire and cable material is not high temperature resistant, has poor physical properties, has large smoke generation amount during combustion, and generates a large amount of toxic and harmful gas during combustion.
The preparation method of the low-smoke halogen-free flame-retardant material provided by the embodiment of the invention has the advantages of simple process, uncomplicated equipment and easiness in manufacturing and popularization.
The low-smoke halogen-free flame-retardant material provided by one embodiment of the invention is used for preparing a rubber sheath material, and all properties of the prepared rubber sheath can reach or even exceed the national standard requirements and are superior to those of the existing similar rubber sheaths.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment provides a low-smoke halogen-free flame-retardant material which comprises the following components in parts by weight:
ethylene-vinyl acetate rubber: 80 parts, magnesium hydroxide: 40 parts, aluminum hydroxide: 50 parts of carbon black: 2 parts, dioctyl sebacate: 5 parts, zinc oxide: 4 parts, stearic acid: 0.5 part of anti-aging agent: 2 parts, flame retardant: 10 parts of vinyltris (2-methoxyethoxy) silane: 1 part, processing aid: 4 parts, sensitizer: and 2 parts.
Wherein the Mooney viscosity of the ethylene-vinyl acetate rubber is ML 1+ 4100 ℃: 23, the VAC content is: 48.5 percent.
The carbon black has iodine absorption value of more than 82 +/-6 g/kg and DBP oil absorption value of more than 102 +/-6 cm3/100g。
The ignition weight loss of the magnesium hydroxide is more than or equal to 30 percent, and the particle size D50 is less than or equal to 2.0 mu m.
The ignition weight loss of the aluminum hydroxide is more than or equal to 34 percent, the particle size D50 is less than or equal to 2.0um, and the content of aluminum oxide in the aluminum hydroxide is more than or equal to 64.5 percent.
The anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole in a mass ratio of 1: 1.
The 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer has excellent protection effect on aging caused by thermal oxidation aging, also has extremely strong inhibition effect on metal catalytic oxidation, and has no influence on the processability, vulcanization characteristic and physical properties of vulcanized rubber.
The flame retardant is melamine polyphosphate and pentaerythritol caged phosphate according to the mass ratio of 1: 1.
The processing aid is polyethylene wax and microcrystalline wax according to a mass ratio of 2: 1.
The sensitizer is triallyl isocyanurate and trimethylolpropane trimethacrylate according to the mass ratio of 1: 2, or a mixture thereof.
Example 2
The embodiment provides a low-smoke halogen-free flame-retardant material which comprises the following components in parts by weight:
ethylene-vinyl acetate rubber: 120 parts, magnesium hydroxide: 60 parts, aluminum hydroxide: 80 parts, carbon black: 10 parts, dioctyl sebacate: 10 parts, zinc oxide: 10 parts, stearic acid: 1.5 parts of an anti-aging agent: 4 parts, flame retardant: 20 parts of vinyl tri (2-methoxyethoxy) silane: 3 parts of processing aid: 6 parts, sensitizer: 5 parts of the raw materials.
Wherein the Mooney viscosity of the ethylene-vinyl acetate rubber is ML 1+ 4100 ℃: 31, the VAC content is: 51.5 percent.
The carbon black has iodine absorption value of more than 82 +/-6 g/kg and DBP oil absorption value of more than 102 +/-6 cm3/100g。
The ignition weight loss of the magnesium hydroxide is more than or equal to 30 percent, and the particle size D50 is less than or equal to 2.0 mu m.
The ignition weight loss of the aluminum hydroxide is more than or equal to 34 percent, the particle size D50 is less than or equal to 2.0um, and the content of aluminum oxide in the aluminum hydroxide is more than or equal to 64.5 percent.
The anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole in a mass ratio of 1: 2, or a mixture thereof.
The 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer has excellent protection effect on aging caused by thermal oxidation aging, also has extremely strong inhibition effect on metal catalytic oxidation, and has no influence on the processability, vulcanization characteristic and physical properties of vulcanized rubber.
The flame retardant is melamine polyphosphate and pentaerythritol caged phosphate in a mass ratio of 3: 1.
The processing aid is polyethylene wax and microcrystalline wax according to a mass ratio of 2: 1.
The sensitizer is triallyl isocyanurate and trimethylolpropane trimethacrylate according to the mass ratio of 1: 3 in a mixture of two or more.
Example 3
The embodiment provides a low-smoke halogen-free flame-retardant material which comprises the following components in parts by weight:
ethylene-vinyl acetate rubber: 100 parts, magnesium hydroxide: 50 parts, aluminum hydroxide: 65 parts, carbon black: 6 parts, dioctyl sebacate: 7.5 parts, zinc oxide: 7 parts, stearic acid: 1 part of an anti-aging agent: 3 parts of flame retardant: 15 parts of vinyltris (2-methoxyethoxy) silane: 2 parts, processing aid: 5 parts, sensitizer: and 3 parts.
Wherein the Mooney viscosity of the ethylene-vinyl acetate rubber is ML 1+ 4100 ℃: 27, the VAC content is: 50 percent.
The iodine absorption value of the carbon black is more than 82 +/-6 g/kg, and the DBP oil absorption value is more than 102 +/-6 cm3/100g。
The ignition weight loss of the magnesium hydroxide is more than or equal to 30 percent, and the particle size D50 is less than or equal to 2.0 mu m.
The ignition weight loss of the aluminum hydroxide is more than or equal to 34 percent, the particle size D50 is less than or equal to 2.0um, and the content of aluminum oxide in the aluminum hydroxide is more than or equal to 64.5 percent.
The anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole in a mass ratio of 1: 1.5.
The 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer has excellent protection effect on aging caused by thermal oxidation aging, also has extremely strong inhibition effect on metal catalytic oxidation, and has no influence on the processability, vulcanization characteristic and physical properties of vulcanized rubber.
The flame retardant is a mixture of melamine polyphosphate and pentaerythritol caged phosphate according to the mass ratio of 2: 1.
The processing aid is polyethylene wax and microcrystalline wax according to a mass ratio of 1.5: 1.
The sensitizer is triallyl isocyanurate and trimethylolpropane trimethacrylate according to the mass ratio of 1: 1.
Example 4
The embodiment provides a low-smoke halogen-free flame-retardant material which comprises the following components in parts by weight:
ethylene-vinyl acetate rubber: 100 parts, magnesium hydroxide: 40 parts, aluminum hydroxide: 70 parts of carbon black: 5 parts, dioctyl sebacate: 5 parts, zinc oxide: 8 parts, stearic acid: 1 part of an anti-aging agent: 2.5 parts, flame retardant: 10 parts of vinyltris (2-methoxyethoxy) silane: 1.5 parts, processing aid: 4.5 parts, sensitizer: 4.5 parts.
Wherein the ethylene-vinyl acetate rubber is LEVAPREN 500, and the Mooney viscosity thereof is ML 1+ 4100 ℃: 27, the VAC content is: 50 percent.
The carbon black is N330, the iodine absorption value is more than 82 +/-6 g/kg, and the DBP oil absorption value is more than 102 +/-6 cm3/100g。
The ignition weight loss of the magnesium hydroxide is more than or equal to 30 percent, and the particle size D50 is less than or equal to 2.0 mu m.
The ignition weight loss of the aluminum hydroxide is more than or equal to 34 percent, the particle size D50 is less than or equal to 2.0um, and the content of aluminum oxide in the aluminum hydroxide is more than or equal to 64.5 percent.
The anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole in a mass ratio of 1.5: 1.
The 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer has excellent protection effect on aging caused by thermal oxidation aging, also has extremely strong inhibition effect on metal catalytic oxidation, and has no influence on the processability, vulcanization characteristic and physical properties of vulcanized rubber.
The flame retardant is a mixture of melamine polyphosphate and pentaerythritol caged phosphate according to the mass ratio of 3: 2.
The processing aid is polyethylene wax and microcrystalline wax according to a mass ratio of 2: 1.
The sensitizer is triallyl isocyanurate and trimethylolpropane trimethacrylate according to the mass ratio of 1: 3.5 of a mixture.
Example 5
The embodiment provides a low-smoke halogen-free flame-retardant material which comprises the following components in parts by weight:
ethylene-vinyl acetate rubber: 100 parts, magnesium hydroxide: 50 parts, aluminum hydroxide: 60 parts, carbon black: 10 parts, dioctyl sebacate: 10 parts, zinc oxide: 6 parts, stearic acid: 1 part of an anti-aging agent: 2.4 parts, flame retardant: 15 parts of vinyltris (2-methoxyethoxy) silane: 2 parts, processing aid: 4.5 parts, sensitizer: 4.5 parts.
Wherein the ethylene-vinyl acetate rubber is LEVAPREN 500, and the Mooney viscosity thereof is ML 1+ 4100 ℃: 27, the VAC content is: 50 percent.
The carbon black is N330, and has iodine absorption value of more than 82 + -6 g/kg and DBP oil absorption value of more than 102 + -6 cm3/100g。
The ignition weight loss of the magnesium hydroxide is more than or equal to 30 percent, and the particle size D50 is less than or equal to 2.0 mu m.
The ignition weight loss of the aluminum hydroxide is more than or equal to 34 percent, the particle size D50 is less than or equal to 2.0um, and the content of aluminum oxide in the aluminum hydroxide is more than or equal to 64.5 percent.
The anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole in a mass ratio of 1: 1.
The 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer has excellent protection effect on aging caused by thermal oxidative aging, has extremely strong inhibition effect on the catalytic oxidation of metal, and has no influence on the processability, vulcanization characteristic and physical properties of vulcanized rubber.
The flame retardant is a mixture of melamine polyphosphate and pentaerythritol caged phosphate according to the mass ratio of 2: 1.
The processing aid is polyethylene wax and microcrystalline wax in a mass ratio of 4: 1.
The sensitizer is triallyl isocyanurate and trimethylolpropane trimethacrylate according to the mass ratio of 1: 2, or a mixture thereof.
Example 6
The embodiment provides a low-smoke halogen-free flame-retardant material which comprises the following components in parts by weight:
ethylene-vinyl acetate rubber: 100 parts, magnesium hydroxide: 40 parts, aluminum hydroxide: 60 parts, carbon black: 6 parts, dioctyl sebacate: 8 parts, zinc oxide: 6 parts, stearic acid: 1.5 parts of an anti-aging agent: 2.3 parts, flame retardant: 20 parts of vinyl tri (2-methoxyethoxy) silane: 2 parts, processing aid: 4.5 parts, sensitizer: 4.5 parts.
Wherein the ethylene-vinyl acetate rubber is LEVAPREN 500, and the Mooney viscosity thereof is ML 1+ 4100 ℃: 27, the VAC content is: 50 percent.
The carbon black is N330, the iodine absorption value is more than 82 +/-6 g/kg, and the DBP oil absorption value is more than 102 +/-6 cm3/100g。
The ignition weight loss of the magnesium hydroxide is more than or equal to 30 percent, and the particle size D50 is less than or equal to 2.0 mu m.
The ignition weight loss of the aluminum hydroxide is more than or equal to 34 percent, the particle size D50 is less than or equal to 2.0um, and the content of aluminum oxide in the aluminum hydroxide is more than or equal to 64.5 percent.
The anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole in a mass ratio of 1.5: 0.8 of the mixture.
The 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer has excellent protection effect on aging caused by thermal oxidation aging, also has extremely strong inhibition effect on metal catalytic oxidation, and has no influence on the processability, vulcanization characteristic and physical properties of vulcanized rubber.
The flame retardant is a mixture of melamine polyphosphate and pentaerythritol caged phosphate according to the mass ratio of 1: 1.
The processing aid is polyethylene wax and microcrystalline wax according to the mass ratio of 2.5: 2, or a mixture thereof.
The sensitizer is triallyl isocyanurate and trimethylolpropane trimethacrylate according to the mass ratio of 2: 2.5 of a mixture.
Example 7
The preparation method of the low-smoke halogen-free flame-retardant material comprises the following steps:
(1) weighing the components according to the proportion, and sequentially adding ethylene-vinyl acetate rubber, carbon black, stearic acid, an anti-aging agent, a processing aid, magnesium hydroxide, a flame retardant, a sensitizer and vinyltris (2-methoxyethoxy) silane into an internal mixer for first internal mixing, wherein the time for the first internal mixing is 160-200 s;
(2) sequentially adding zinc oxide, aluminum hydroxide and dioctyl sebacate into the product obtained in the step (1), and carrying out secondary banburying for 140-160 s;
(3) and (3) cleaning and turning the product obtained in the step (2), carrying out third banburying for 100-140 s, carrying out the second banburying for 60s, unloading, controlling the unloading temperature at 125 +/-5 ℃, then filtering, preferably selecting 60 meshes for the number of the filtered rubber materials, mixing the filtered rubber materials on an open mill, and guiding the rubber materials to an automatic turner for turning for 300s to obtain the low-smoke halogen-free flame retardant material.
After the step (3), the obtained low-smoke halogen-free flame retardant material can be rolled into a film by a three-roll calender.
In order to prevent the surface of the film from being adhered and prolong the storage time of the film, a release agent can be coated on the surface of the film.
The release agent may be an aqueous solution of zinc stearate.
Comparative example 1
This example provides a low smoke, halogen-free, flame retardant material which differs from example 3 in that it does not contain aluminum hydroxide.
Comparative example 2
This example provides a low smoke, halogen-free, flame retardant material which differs from example 3 in that the anti-aging agent is a single polymer of 2,2, 4-trimethyl-1, 2-dihydroquinoline.
Comparative example 3
This example provides a low smoke, halogen-free flame retardant material which differs from example 3 in that the flame retardant is a single melamine polyphosphate.
Example of detection
By the preparation method provided in example 7, 4 flame retardant materials corresponding to the numbers are prepared according to the formulas provided in example 4 and comparative examples 1 to 3, the 4 flame retardant materials are prepared into a sheath, and the performance of the sheath is tested, with the results shown in table 1.
TABLE 1 test results of flame retardant jacket performance of examples and comparative examples
In addition, the performance of the commercially available ethylene propylene diene monomer flame retardant sheath material, polyvinyl chloride flame retardant sheath material and chlorinated polyethylene rubber flame retardant sheath material was also tested, and the results are shown in table 2.
Table 2 performance test results of three commercially available flame retardant sheathing materials
As can be seen from the test results in tables 1 and 2, the low-smoke halogen-free flame retardant material of the embodiment of the invention can reach or even exceed the requirements of national standard GB/T32129-2015 (the standard requires that the oxygen index is more than or equal to 30 percent), and is superior to the common flame retardant rubber sheath material sold in the market. The sheath prepared from the low-smoke halogen-free flame-retardant material solves the problems that the common flame-retardant rubber sheath material is not high-temperature resistant, has poor physical properties, has large smoke generation amount during combustion, and generates a large amount of toxic and harmful gas.
Claims (6)
1. The low-smoke halogen-free flame-retardant material is characterized by being prepared from the following components in parts by weight:
ethylene-vinyl acetate rubber: 80-120 parts of (a) a water-soluble polymer,
magnesium hydroxide: 40-60 parts of (A) a water-soluble polymer,
aluminum hydroxide: 50-80 parts of a water-soluble polymer,
carbon black: 2 to 10 parts by weight of a stabilizer,
dioctyl sebacate: 5 to 10 parts by weight of a surfactant,
zinc oxide: 4 to 10 parts of (a) a water-soluble polymer,
stearic acid: 0.5 to 1.5 parts by weight,
an anti-aging agent: 2 to 4 parts of (a) a water-soluble polymer,
flame retardant: 10-20 parts of (A) a water-soluble polymer,
vinyltris (2-methoxyethoxy) silane: 1 to 3 parts of (A) a water-soluble polymer,
processing aid: 4 to 6 parts of (A) a water-soluble polymer,
sensitizer: 2-5 parts;
the Mooney viscosity of the ethylene-vinyl acetate rubber is ML 1+ 4100 ℃: 23-31, the VAC content is as follows: 48.5 to 51.5 percent,
the anti-aging agent is a mixture of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole in a mass ratio of 1: (1-2) of the mixture of (A),
the flame retardant is a mixture of melamine polyphosphate and pentaerythritol caged phosphate.
2. The low smoke zero halogen flame retardant material in accordance with claim 1, wherein the carbon black has an iodine absorption value of more than 82 ± 6g/kg and a DBP oil absorption value of more than 102 ± 6cm3/100g。
3. The low-smoke zero-halogen flame-retardant material according to claim 1, wherein the weight loss on ignition of magnesium hydroxide is as follows: more than or equal to 30 percent and the particle size D50 is less than or equal to 2.0 mu m.
4. The low-smoke halogen-free flame-retardant material as claimed in claim 1, wherein the ignition weight loss of the aluminum hydroxide is not less than 34%, the particle size D50 is not more than 2.0um, and the content of aluminum oxide in the aluminum hydroxide is not less than 64.5%.
5. The low-smoke halogen-free flame-retardant material as claimed in claim 1, wherein the sensitizer is triallyl isocyanurate and trimethylolpropane trimethacrylate in a mass ratio of (1-2): (2-3).
6. The preparation method of the low-smoke halogen-free flame retardant material according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) weighing the components according to the proportion, and sequentially adding ethylene-vinyl acetate rubber, carbon black, stearic acid, an anti-aging agent, a processing aid, magnesium hydroxide, a flame retardant, a sensitizer and vinyltris (2-methoxyethoxy) silane into an internal mixer for first internal mixing;
(2) sequentially adding zinc oxide, aluminum hydroxide and dioctyl sebacate into the product obtained in the step (1) for secondary banburying;
(3) and (3) cleaning and turning the product obtained in the step (2), carrying out third banburying, and then unloading, filtering and mixing to obtain the low-smoke halogen-free flame retardant material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| KR20180103527A (en) * | 2017-03-10 | 2018-09-19 | 현대자동차주식회사 | Non-halogen flame retardant foam for automobile and manufacturing method thereof |
| CN109575419A (en) * | 2018-12-14 | 2019-04-05 | 潍坊潍星联合橡塑有限公司 | High anti-tear halogen-free flameproof oil resistant low temperature resistant sizing material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101597397A (en) * | 2009-06-03 | 2009-12-09 | 宝胜科技创新股份有限公司 | Cables of nuclear power irradiation resistant non-halogen low smoke flame-retardant sheath material and preparation method |
| KR20180103527A (en) * | 2017-03-10 | 2018-09-19 | 현대자동차주식회사 | Non-halogen flame retardant foam for automobile and manufacturing method thereof |
| CN109575419A (en) * | 2018-12-14 | 2019-04-05 | 潍坊潍星联合橡塑有限公司 | High anti-tear halogen-free flameproof oil resistant low temperature resistant sizing material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 三聚氰胺聚磷酸盐/笼状季戊四醇磷酸酯协效阻燃聚丙烯/稻壳复合材料的研究;徐盼盼等;《化工新型材料》;20180415;第174页左栏第2段、第175页右栏，第176页右栏 * |
| 无卤阻燃剂三聚氰胺多聚磷酸盐的性能及应用;李曙红;《塑料助剂》;20040420;第25-27页 * |
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