CN115926298B - Fire-retardant cable material for fire protection and preparation method thereof - Google Patents
Fire-retardant cable material for fire protection and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of cable materials, in particular to a fire-retardant cable material for fire protection and a preparation method thereof. The fire-retardant cable material for fire control consists of the following materials: polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, a compatilizer, an anti-aging agent, a zinc-barium stabilizer and a flame retardant; the flame retardant consists of a nitrogen-phosphorus flame retardant and modified magnesium hydroxide. The fire-retardant cable material for fire control prepared by the method has good flame retardant property and mechanical property, can meet the use requirement of the fire-retardant material for fire control, has simple preparation process and low cost, and is suitable for wide popularization.
Description
Technical Field
The invention relates to the technical field of cable materials, in particular to a fire-retardant cable material for fire protection and a preparation method thereof.
Background
With the acceleration of the urban process, the urban scale and the urban population number are rapidly increased, and the rapid development of urban high-rise buildings and rail transit is promoted. Once the fire disaster occurs in the places, the personnel evacuation and rescue work is difficult due to the factors of dense personnel, complex building construction and the like, so that the facilities can be designed and built by adopting flame retardant materials as much as possible, and the potential safety hazard of the fire disaster is reduced. The electric wires and cables play an important role in the construction and use processes of high-rise buildings and rail transit infrastructures, and the flame-retardant cable becomes the primary choice of the matched cable in the places.
In the early days, people achieve the aim of flame retardance by adding a certain amount of halogen-containing flame retardant or using polyvinyl chloride and antimony flame retardant in the wire and cable manufacturing process, but because the halogen flame retardant can generate a large amount of harmful gases in the combustion process, the harmful gases can cause secondary injury in the processes of escaping and rescuing, and the choking death of people can be caused when serious. With the increase of environmental awareness and the release of related laws, the use of halogen-containing flame-retardant cables has been greatly reduced, and the use of halogen-containing cables has been prohibited in buildings of important infrastructure. The great number of applications of low-smoke halogen-free flame-retardant cables are gradually becoming trend, and related research is becoming a research hotspot in the cable field and the composite material field.
The Chinese patent (application number: 202111481966.8) discloses a green flame-retardant high-temperature-resistant oil-resistant special flexible cable material and a production method thereof, wherein the material comprises the following raw materials in parts by weight: 40-60 parts of crosslinked polyethylene, 20-30 parts of polydimethyl vinyl siloxane, 10-20 parts of polyurethane resin, 10-30 parts of aniline formaldehyde resin, 5-15 parts of nano calcium carbonate, 2-6 parts of zinc stannate, 5-10 parts of kaolin, 15-25 parts of flame retardant, 3-5 parts of vulcanizing agent, 1-3 parts of lubricant, 2-3 parts of anti-aging agent, 2-6 parts of plasticizer and 3-5 parts of stabilizer. The green flame-retardant high-temperature-resistant oil-resistant special flexible cable material prepared by the method has higher flame retardant property, and then the flame retardant added in the preparation method is any one of zinc borate, aluminum hydroxide, magnesium hydroxide and antimony trioxide, and the added flame retardant can seriously cause the reduction of the mechanical property of the green flame-retardant high-temperature-resistant oil-resistant special flexible cable material, and various problems such as breakage, tearing and the like can easily occur after long-term use, so that the service life in the use process is influenced. Therefore, it is necessary to provide a flame-retardant cable material having both good flame-retardant properties and good mechanical properties, so as to widen the application occasions.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a fire-retardant cable material for fire protection and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the fire-retardant cable material for fire control consists of the following materials in parts by weight: 60-100 parts of polyethylene, 10-25 parts of ethylene propylene diene monomer, 5-15 parts of kaolin, 5-15 parts of calcium carbonate, 3-8 parts of compatilizer, 0.5-2 parts of anti-aging agent, 2-6 parts of zinc-barium stabilizer and 10-30 parts of flame retardant.
The polyethylene material has better processability and mechanical properties, has higher hardness, poorer bending resistance and poorer flame retardant property because of high crystallinity, and cannot meet the direct use requirement of a low-smoke halogen-free flame-retardant cable, so that a flame retardant is required to be added into the polyethylene flame-retardant material to improve the flame-retardant practical use value of the polyethylene flame-retardant material.
The compatilizer is at least one of maleic anhydride grafted polyethylene, ethylene ethyl acrylate copolymer, ethylene-octene copolymer grafted maleic anhydride and ethylene-vinyl acetate copolymer grafted maleic anhydride.
The anti-aging agent is at least one of anti-aging agent 4020, anti-aging agent RD and anti-aging agent ODA.
The preparation method of the flame retardant comprises the following steps:
s1, mixing hydrochloric acid and (p-methylphenyl ethyl) methyldimethoxy silane for reaction, and cooling to room temperature to obtain a reaction solution A; adding the trimellitic anhydride chloride and stirring to obtain a reaction solution B; adding melamine and 2-hydroxyphosphonoacetic acid, stirring, filtering, and drying to obtain nitrogen-phosphorus flame retardant;
s2, mixing and stirring the magnesium hydroxide and water, adding an ethanol solution of a coupling agent, continuously stirring, centrifuging, washing and drying to obtain modified magnesium hydroxide;
s3, mixing the modified magnesium hydroxide with an ethanol water solution, and adding a pentabromoethyl benzene ethanol solution for ultrasonic treatment; and adding the nitrogen-phosphorus flame retardant, stirring, filtering and drying to obtain the flame retardant.
Magnesium hydroxide is a highly effective inorganic flame retardant filler that can be used in flame retardant cable materials. However, compared with halogen-free organic flame retardants, the filling amount is generally more than 50% to achieve a comparable flame retardant effect, which not only wastes resources, but also seriously affects the mechanical properties of the flame retardant cable material by adding excessive inorganic filler. The reason is that because magnesium hydroxide is an inorganic substance, the compatibility of the surface and the high molecular compound is poor, and if the magnesium hydroxide is not subjected to surface modification treatment, the high filling amount is filled into the flame-retardant cable material, so that the mechanical properties of the high molecular material are reduced. Therefore, it is necessary to perform a surface modification treatment to improve its compatibility with the polymer material.
The phosphorus-nitrogen flame retardant, namely the halogen-free flame retardant, has good flame retardant effect by adding a small amount of halogen-free flame retardant into the high polymer composite material, and has less toxic and harmful substances generated in the combustion process, and the phosphorus-nitrogen flame retardant is compounded with the inorganic flame retardant for use, so that the use amount of the flame retardant is greatly reduced, the flame retardant performance of the material is synergistically improved, better flame retardant effect is exerted, and the problems of mechanical property reduction and the like of the flame retardant cable material caused by the added inorganic flame retardant can be solved. The nitrogen-phosphorus flame retardant prepared by the invention contains an acid source, a phosphorus source and a nitrogen source, can simultaneously play roles in a gas phase and a condensed phase, is heated and expanded at high temperature, generates an acid catalyst after the acid source is decomposed, promotes the polymer to be dehydrogenated into carbon, and can play a role in preventing heat transfer and mass transfer by covering the surface of the condensed phase by acidic viscous substances, so that an effective carbon layer can be formed on the surface of a material to protect an internal substrate from being damaged, and simultaneously, nonflammable gas is released to dilute oxygen to generate a blowing-out effect, thereby effectively preventing the continuous combustion of the material, and overcoming the defects of large combustion smoke, toxic and corrosive gas and the like of a halogen flame retardant technology; meanwhile, the adverse effect of large addition amount of the inorganic flame retardant technology on the mechanical property of the material is avoided.
Preferably, the preparation method of the flame retardant comprises the following steps:
s1, mixing 10-30 parts by weight of 0.5-2mol/L hydrochloric acid and 5-15 parts by weight of (p-methylphenyl ethyl) methyldimethoxy silane, reacting for 1-3 hours at 60-80 ℃ and 300-500rpm, and cooling to room temperature to obtain a reaction solution A; adding 10-20 parts by weight of chlorinated trimellitic anhydride, and stirring at 500-700rpm for 0.5-2h to obtain a reaction solution B; adding 15-25 parts by weight of melamine and 20-30 parts by weight of 2-hydroxyphosphonoacetic acid, stirring for 1-3 hours at 500-700rpm, filtering, and drying to obtain a nitrogen-phosphorus flame retardant;
s2, mixing 15-30 parts by weight of magnesium hydroxide and 60-120 parts by weight of water, stirring for 25-50min at 400-800rpm, adding 15-300 parts by weight of 5-15wt% of coupling agent ethanol solution, continuously stirring for 1-3h at 60-80 ℃ and 300-500rpm, centrifuging, washing and drying to obtain modified magnesium hydroxide;
s3, mixing 5-12 parts by weight of the modified magnesium hydroxide with 80-140 parts by weight of 50-70wt% ethanol water solution, adding 7-13 parts by weight of 5-10wt% pentabromoethyl benzene ethanol solution, and performing ultrasonic treatment for 0.5-2 hours under the conditions of ultrasonic power of 100-300W and ultrasonic frequency of 30-60 kHz; adding 10-30 parts by weight of the nitrogen-phosphorus flame retardant, stirring for 2-5 hours at 25-35 ℃ and 400-800rpm, filtering, and drying to obtain the flame retardant.
The mechanism for preparing the flame retardant is as follows: (1) Firstly, hydrolyzing (p-methyl phenyl ethyl) methyl dimethoxy silane under an acidic condition to obtain a hydroxylated crude product, then carrying out a grafting reaction with chlorinated trimellitic anhydride to generate carboxylated silane ester, and finally carrying out a reaction with melamine and 2-hydroxyphosphonoacetic acid to generate an organosilicon flame retardant containing nitrogen and phosphorus; (2) The magnesium hydroxide generates modified magnesium hydroxide under the action of a coupling agent; (3) And reacting the modified magnesium hydroxide with an organosilicon flame retardant containing nitrogen and phosphorus through amide to obtain the flame retardant.
In the invention, if 2-hydroxyphosphonoacetic acid is not added, the reaction of modified magnesium hydroxide and nitrogen-phosphorus flame retardant can not be carried out as no carboxyl groups exist, so that the amide or esterification reaction can not be carried out by the reaction of the carboxyl groups in the nitrogen-phosphorus flame retardant and the amino groups or hydroxyl groups in the modified magnesium hydroxide to generate the amide or esterification reaction, and finally the content of the nitrogen-phosphorus flame retardant in the obtained flame retardant is reduced, so that the flame retardant performance and mechanical performance of the flame-retardant cable are affected.
The coupling agent is at least one of gamma-aminopropyl triethoxysilane, 3- [2- (2-amino ethylamino) ethylamino ] propyl-trimethoxysilane and 3- [2- (2-amino ethylamino) ethylamino ] propyl-trimethoxysilane.
The preparation method of the fire-retardant cable material for fire control comprises the following steps:
(1) Adding polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, compatilizer and flame retardant into a reaction kettle, stirring for 20-50min at 800-1200rpm, mixing for 10-25min at 120-140 ℃, and cooling to room temperature to obtain a mixture A;
(2) Adding an anti-aging agent and a zinc-barium stabilizer into the mixture A, stirring for 20-40min at 1200-2000rpm, and mixing for 1-4min at 120-140 ℃ to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 140-160 ℃, and the screw rotation speed is 150-250rpm, so that the fire-fighting flame-retardant cable material is obtained.
The invention has the beneficial effects that: according to the invention, the halogen-free nitrogen-phosphorus flame retardant and the inorganic flame retardant are compounded for use, so that the use amount of the flame retardant is greatly reduced, the flame retardant property of the material is synergistically improved, a better flame retardant effect is achieved, and the problems of mechanical property reduction and the like of the flame retardant cable material caused by the added inorganic flame retardant can be solved. The flame-retardant cable material for fire control prepared by the method has the advantages that the problem of poor compatibility of magnesium hydroxide in the flame-retardant cable material for fire control is effectively solved, meanwhile, the flame-retardant effect of magnesium hydroxide is improved, the cable material has higher flame retardant property, substances harmful to human bodies can not be generated during combustion, and the flame-retardant cable material for fire control is more environment-friendly and has flame retardant effect and mechanical property.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Introduction of some of the raw materials in this application:
polyethylene was purchased from Kaiki pigeon plasticization Co., yuyao, trade name: DMDA-8008.
Ethylene propylene diene monomer is purchased from Guangzhou market force big rubber raw materials trade limited company, model: NBR-35LM.
Maleic anhydride grafted polyethylene is provided by Dongguan plastic big plastic raw material Co., ltd., model: 1052H.
The zinc barium stabilizer was purchased from plastic chemical engineering sales company, model R218, of the rui county.
Example 1
The fire-retardant cable material for fire control consists of the following materials in parts by weight: 80 parts of polyethylene, 16 parts of ethylene propylene diene monomer, 10 parts of kaolin, 10 parts of calcium carbonate, 5 parts of maleic anhydride grafted polyethylene, 1 part of anti-aging agent 4020, 4 parts of zinc-barium stabilizer and 20 parts of flame retardant.
The flame retardant is magnesium hydroxide.
The preparation method of the fire-retardant cable material for fire control comprises the following steps:
(1) Adding polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, maleic anhydride grafted polyethylene and a flame retardant into a reaction kettle, stirring for 30min at 1000rpm, mixing for 15min at 130 ℃, and cooling to room temperature to obtain a mixture A;
(2) Adding an anti-aging agent 4020 and a zinc-barium stabilizer into the mixture A, stirring at 1600rpm for 30min, and mixing at 140 ℃ for 2min to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 150 ℃, and the screw rotating speed is 200rpm, so that the fire-fighting flame-retardant cable material is obtained.
Example 2
The fire-retardant cable material for fire control consists of the following materials in parts by weight: 80 parts of polyethylene, 16 parts of ethylene propylene diene monomer, 10 parts of kaolin, 10 parts of calcium carbonate, 5 parts of maleic anhydride grafted polyethylene, 1 part of anti-aging agent 4020, 4 parts of zinc-barium stabilizer and 20 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps: mixing 20 parts by weight of magnesium hydroxide and 80 parts by weight of water, stirring for 30min at 600rpm, adding 20 parts by weight of 10wt%3- [2- (2-amino ethylamino) ethylamino ] propyl-trimethoxy silane ethanol solution, continuously stirring for 2h at 70 ℃ and 400rpm, centrifuging, washing and drying to obtain a flame retardant;
the preparation method of the fire-retardant cable material for fire control comprises the following steps:
(1) Adding polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, maleic anhydride grafted polyethylene and a flame retardant into a reaction kettle, stirring for 30min at 1000rpm, mixing for 15min at 130 ℃, and cooling to room temperature to obtain a mixture A;
(2) Adding an anti-aging agent 4020 and a zinc-barium stabilizer into the mixture A, stirring at 1600rpm for 30min, and mixing at 140 ℃ for 2min to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 150 ℃, and the screw rotating speed is 200rpm, so that the fire-fighting flame-retardant cable material is obtained.
Example 3
The fire-retardant cable material for fire control consists of the following materials in parts by weight: 80 parts of polyethylene, 16 parts of ethylene propylene diene monomer, 10 parts of kaolin, 10 parts of calcium carbonate, 5 parts of maleic anhydride grafted polyethylene, 1 part of anti-aging agent 4020, 4 parts of zinc-barium stabilizer and 20 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps: mixing 20 parts by weight of 1mol/L hydrochloric acid and 10 parts by weight of (p-methylphenyl ethyl) methyldimethoxy silane, reacting at 70 ℃ and 400rpm for 2 hours, and cooling to room temperature to obtain a reaction solution A; then 15 parts by weight of chlorinated trimellitic anhydride is added and stirred for 1 hour at 600rpm to obtain a reaction solution B; then adding 20 parts by weight of melamine and 25 parts by weight of 2-hydroxyphosphonoacetic acid, stirring for 1.5 hours at 600rpm, carrying out suction filtration, and drying to obtain the flame retardant.
The preparation method of the fire-retardant cable material for fire control comprises the following steps:
(1) Adding polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, maleic anhydride grafted polyethylene and a flame retardant into a reaction kettle, stirring for 30min at 1000rpm, mixing for 15min at 130 ℃, and cooling to room temperature to obtain a mixture A;
(2) Adding an anti-aging agent 4020 and a zinc-barium stabilizer into the mixture A, stirring at 1600rpm for 30min, and mixing at 140 ℃ for 2min to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 150 ℃, and the screw rotating speed is 200rpm, so that the fire-fighting flame-retardant cable material is obtained.
Example 4
The fire-retardant cable material for fire control consists of the following materials in parts by weight: 80 parts of polyethylene, 16 parts of ethylene propylene diene monomer, 10 parts of kaolin, 10 parts of calcium carbonate, 5 parts of maleic anhydride grafted polyethylene, 1 part of anti-aging agent 4020, 4 parts of zinc-barium stabilizer and 20 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps:
s1, mixing 20 parts by weight of 1mol/L hydrochloric acid and 10 parts by weight of (p-methylphenyl ethyl) methyldimethoxy silane, reacting for 2 hours at 70 ℃ and 400rpm, and cooling to room temperature to obtain a reaction solution A; then 15 parts by weight of chlorinated trimellitic anhydride is added and stirred for 1 hour at 600rpm to obtain a reaction solution B; adding 20 parts by weight of melamine and 25 parts by weight of 2-hydroxyphosphonoacetic acid, stirring at 600rpm for 1.5 hours, filtering, and drying to obtain a nitrogen-phosphorus flame retardant;
s2, mixing 20 parts by weight of magnesium hydroxide and 80 parts by weight of water, stirring for 30min at 600rpm, adding 20 parts by weight of 10wt%3- [2- (2-amino ethylamino) ethylamino ] propyl-trimethoxy silane ethanol solution, continuously stirring for 2h at 70 ℃ and 400rpm, centrifuging, washing and drying to obtain modified magnesium hydroxide;
s3, mixing 8 parts by weight of the modified magnesium hydroxide with 100 parts by weight of 60wt% ethanol water solution, adding 10 parts by weight of 7.5wt% pentabromoethyl phenethyl alcohol solution, and performing ultrasonic treatment for 1h at ultrasonic power of 200W and ultrasonic frequency of 45 kHz; then 15 parts by weight of the nitrogen-phosphorus flame retardant is added, and the mixture is stirred for 3 hours at 30 ℃ and 600rpm, filtered and dried to obtain the flame retardant.
The preparation method of the fire-retardant cable material for fire control comprises the following steps:
(1) Adding polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, maleic anhydride grafted polyethylene and a flame retardant into a reaction kettle, stirring for 30min at 1000rpm, mixing for 15min at 130 ℃, and cooling to room temperature to obtain a mixture A;
(2) Adding an anti-aging agent 4020 and a zinc-barium stabilizer into the mixture A, stirring at 1600rpm for 30min, and mixing at 140 ℃ for 2min to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 150 ℃, and the screw rotating speed is 200rpm, so that the fire-fighting flame-retardant cable material is obtained.
Example 5
The fire-retardant cable material for fire control consists of the following materials in parts by weight: 80 parts of polyethylene, 16 parts of ethylene propylene diene monomer, 10 parts of kaolin, 10 parts of calcium carbonate, 5 parts of maleic anhydride grafted polyethylene, 1 part of anti-aging agent 4020, 4 parts of zinc-barium stabilizer and 20 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps:
s1, mixing 20 parts by weight of 1mol/L hydrochloric acid and 10 parts by weight of (p-methylphenyl ethyl) methyldimethoxy silane, reacting for 2 hours at 70 ℃ and 400rpm, and cooling to room temperature to obtain a reaction solution A; then 15 parts by weight of chlorinated trimellitic anhydride is added and stirred for 1 hour at 600rpm to obtain a reaction solution B; adding 20 parts by weight of melamine and 25 parts by weight of 2-hydroxyphosphonoacetic acid, stirring at 600rpm for 1.5 hours, filtering, and drying to obtain a nitrogen-phosphorus flame retardant;
s2, 8 parts by weight of magnesium hydroxide and 100 parts by weight of 60wt% ethanol aqueous solution are mixed, 10 parts by weight of 7.5wt% pentabromoethyl phenethyl alcohol solution is added, and ultrasonic is carried out for 1h under the conditions of ultrasonic power of 200W and ultrasonic frequency of 45 kHz; then 15 parts by weight of the nitrogen-phosphorus flame retardant is added, and the mixture is stirred for 3 hours at 30 ℃ and 600rpm, filtered and dried to obtain the flame retardant.
The preparation method of the fire-retardant cable material for fire control comprises the following steps:
(1) Adding polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, maleic anhydride grafted polyethylene and a flame retardant into a reaction kettle, stirring for 30min at 1000rpm, mixing for 15min at 130 ℃, and cooling to room temperature to obtain a mixture A;
(2) Adding an anti-aging agent 4020 and a zinc-barium stabilizer into the mixture A, stirring at 1600rpm for 30min, and mixing at 140 ℃ for 2min to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 150 ℃, and the screw rotating speed is 200rpm, so that the fire-fighting flame-retardant cable material is obtained.
Example 6
The fire-retardant cable material for fire control consists of the following materials in parts by weight: 80 parts of polyethylene, 16 parts of ethylene propylene diene monomer, 10 parts of kaolin, 10 parts of calcium carbonate, 5 parts of maleic anhydride grafted polyethylene, 1 part of anti-aging agent 4020, 4 parts of zinc-barium stabilizer and 20 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps:
s1, mixing 20 parts by weight of 1mol/L hydrochloric acid and 10 parts by weight of (p-methylphenyl ethyl) methyldimethoxy silane, reacting for 2 hours at 70 ℃ and 400rpm, and cooling to room temperature to obtain a reaction solution A; then 15 parts by weight of chlorinated trimellitic anhydride is added and stirred for 1 hour at 600rpm to obtain a reaction solution B; adding 20 parts by weight of melamine, stirring for 1.5 hours at 600rpm, carrying out suction filtration and drying to obtain a nitrogen-phosphorus flame retardant;
s2, mixing 20 parts by weight of magnesium hydroxide and 80 parts by weight of water, stirring for 30min at 600rpm, adding 20 parts by weight of 10wt%3- [2- (2-amino ethylamino) ethylamino ] propyl-trimethoxy silane ethanol solution, continuously stirring for 2h at 70 ℃ and 400rpm, centrifuging, washing and drying to obtain modified magnesium hydroxide;
s3, mixing 8 parts by weight of the modified magnesium hydroxide with 100 parts by weight of 60wt% ethanol water solution, adding 10 parts by weight of 7.5wt% pentabromoethyl phenethyl alcohol solution, and performing ultrasonic treatment for 1h at ultrasonic power of 200W and ultrasonic frequency of 45 kHz; then 15 parts by weight of the nitrogen-phosphorus flame retardant is added, and the mixture is stirred for 3 hours at 30 ℃ and 600rpm, filtered and dried to obtain the flame retardant.
The preparation method of the fire-retardant cable material for fire control comprises the following steps:
(1) Adding polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, maleic anhydride grafted polyethylene and a flame retardant into a reaction kettle, stirring for 30min at 1000rpm, mixing for 15min at 130 ℃, and cooling to room temperature to obtain a mixture A;
(2) Adding an anti-aging agent 4020 and a zinc-barium stabilizer into the mixture A, stirring at 1600rpm for 30min, and mixing at 140 ℃ for 2min to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 150 ℃, and the screw rotating speed is 200rpm, so that the fire-fighting flame-retardant cable material is obtained.
Test example 1
Flame retardant performance test: determination of the Combustion behavior by the oxygen index method for plastics, part 2, with reference to the national Standard GB/T2406.2-2009: and (3) performing injection molding on the fire-fighting flame-retardant cable material prepared in the embodiment by using an injection molding machine, and then performing oxygen index measurement. Sample size: the test specimen was 100mm in length, 10mm in width and 4mm in thickness, adjusted at 23℃and 50% humidity for 90 hours, and a scribe line was marked at 50mm of the specimen. Parallel to the 5 groups, the average was taken and the results are shown in Table 1.
Vertical burn (UL-94) test: the fire-retardant cable material for fire protection prepared in the examples was injection molded with an injection molding machine with reference to GB/T2408-2008 "determination of the combustion performance of plastics horizontal method and vertical method", and then vertical combustion determination was performed, using test method B therein: vertical combustion (V). Sample size: 125mm in length, 13mm in width and 3mm in thickness. Each group of samples was tested in parallel five times and the results averaged and are shown in table 1.
TABLE 1 flame retardant Property test results
| LOI(％) | UL-94 rating | |
| Example 1 | 31.5 | V-2 |
| Example 2 | 38.7 | V-2 |
| Example 3 | 41.8 | V-1 |
| Example 4 | 47.2 | V-0 |
| Example 5 | 45.1 | V-1 |
| Example 6 | 43.6 | V-1 |
From the above results, the fire-fighting flame-retardant cable material prepared by the method has good flame-retardant effect, because the fire-fighting flame-retardant cable material is added with the halogen-free flame retardant and the inorganic flame retardant which are synergistic. In the embodiment 2, the modified magnesium hydroxide is adopted, so that the compatibility of the surface and the high molecular compound is effectively improved, and the modified magnesium hydroxide can be effectively and uniformly dispersed and distributed in the fire-retardant cable material for fire protection, so that the fire-retardant performance of the fire-retardant cable material is effectively improved. In the embodiment 3, a phosphorus-nitrogen flame retardant, namely a halogen-free flame retardant is added, a small amount of halogen-free flame retardant is added into a high polymer composite material to play a good flame retardant effect, the nitrogen-phosphorus flame retardant contains an acid source, a phosphorus source and a nitrogen source, can play roles in a gas phase and a condensed phase at the same time, and is heated and expanded at high temperature, an acid catalyst is generated after the acid source is decomposed, so that the polymer is dehydrogenated into carbon, an acidic viscous substance covers the surface of the condensed phase to play a role in preventing heat transfer and mass transfer, an effective carbon layer can be formed on the surface of the material, so that the internal base material is protected from being damaged, meanwhile, nonflammable gas is released to dilute oxygen, a blow-out effect is generated, and the continuous combustion of the material is effectively prevented, so that the defects of large combustion smoke, toxic and corrosive gas and the like of the halogen flame retardant technology are overcome; meanwhile, the adverse effect of large addition amount of the inorganic flame retardant technology on the mechanical property of the material is avoided. In the embodiment 4, the nitrogen-phosphorus flame retardant and the inorganic flame retardant are compounded, so that the use amount of the flame retardant is greatly reduced, and the flame retardant performance of the material can be synergistically improved, and a better flame retardant effect is exerted, so that the flame retardant effect of the fire-retardant cable material for fire protection is effectively improved. In example 6, however, when 2-hydroxyphosphonoacetic acid is not added, the reaction of modified magnesium hydroxide and nitrogen-phosphorus flame retardant cannot proceed with amide or esterification reaction because of no carboxyl group, so that the flame retardant cannot be obtained by reacting carboxyl group in nitrogen-phosphorus flame retardant with amino group or hydroxyl group in modified magnesium hydroxide to generate amide or esterification reaction, and finally the content of nitrogen-phosphorus flame retardant in the obtained flame retardant is reduced, which affects flame retardant performance of flame-retardant cable.
Test example 2
Mechanical property test: determination of Plastic tensile Property Using national Standard GB/T1040.2-2006 section 2: test conditions for molded and extruded plastics. The fire-retardant cable material for fire protection prepared in the example is injection molded by an injection molding machine, and a type II sample is adopted, wherein the test temperature is 25 ℃, and the stretching rate is 250mm/min. Each group was provided with 5 replicates and averaged, the results are shown in table 2.
TABLE 2 mechanical test results
| Tensile strength, MPa | Elongation at break% | |
| Example 1 | 15.3 | 229 |
| Example 2 | 18.1 | 264 |
| Example 3 | 21.5 | 311 |
| Example 4 | 23.8 | 324 |
| Example 5 | 20.9 | 281 |
| Example 6 | 20.2 | 272 |
From the results, the fire-retardant cable material for fire control prepared by the invention has good flame retardant effect and good mechanical property. The flame retardant is prepared by compounding the nitrogen-phosphorus organic flame retardant and the modified magnesium hydroxide, so that not only is the mechanical property of the flame-retardant cable material reduced due to the addition of the magnesium hydroxide effectively improved, but also the problem of poor compatibility of the magnesium hydroxide and a high polymer compound is effectively solved.
Claims (7)
1. The fire-retardant cable material for fire protection is characterized by comprising the following materials: 60-100 parts of polyethylene, 10-25 parts of ethylene propylene diene monomer rubber, 5-15 parts of kaolin, 5-15 parts of calcium carbonate, 3-8 parts of compatilizer, 0.5-2 parts of anti-aging agent, 2-6 parts of zinc-barium stabilizer and 10-30 parts of flame retardant;
the preparation method of the flame retardant comprises the following steps:
s1, mixing 10-30 parts by weight of 0.5-2mol/L hydrochloric acid and 5-15 parts by weight of (p-methylphenyl ethyl) methyldimethoxy silane, reacting for 1-3 hours at 60-80 ℃ and 300-500rpm, and cooling to room temperature to obtain a reaction solution A; adding 10-20 parts by weight of chlorinated trimellitic anhydride, and stirring at 500-700rpm for 0.5-2h to obtain a reaction solution B; adding 15-25 parts by weight of melamine and 20-30 parts by weight of 2-hydroxyphosphonoacetic acid, stirring for 1-3 hours at 500-700rpm, filtering, and drying to obtain a nitrogen-phosphorus flame retardant;
s2, mixing 15-30 parts by weight of magnesium hydroxide and 60-120 parts by weight of water, stirring for 25-50min at 400-800rpm, adding 15-300 parts by weight of 5-15wt% of coupling agent ethanol solution, continuously stirring for 1-3h at 60-80 ℃ and 300-500rpm, centrifuging, washing and drying to obtain modified magnesium hydroxide;
s3, mixing 5-12 parts by weight of the modified magnesium hydroxide with 80-140 parts by weight of 50-70wt% ethanol water solution, adding 7-13 parts by weight of 5-10wt% pentabromoethyl benzene ethanol solution, and performing ultrasonic treatment for 0.5-2 hours under the conditions of ultrasonic power of 100-300W and ultrasonic frequency of 30-60 kHz; adding 10-30 parts by weight of the nitrogen-phosphorus flame retardant, stirring for 2-5 hours at 25-35 ℃ and 400-800rpm, filtering, and drying to obtain the flame retardant.
2. The fire-retardant cable material for fire protection according to claim 1, wherein the coupling agent is at least one of γ -aminopropyl triethoxysilane, 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane.
3. The fire-retardant cable material for firefighting according to claim 1, wherein the compatibilizer is at least one of maleic anhydride grafted polyethylene, ethylene ethyl acrylate copolymer, ethylene-octene copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride.
4. The fire-retardant cable material for fire protection according to claim 1, wherein the anti-aging agent is at least one of anti-aging agent 4020, anti-aging agent RD, and anti-aging agent ODA.
5. A method for preparing a fire-retardant cable material for fire protection as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Adding polyethylene, ethylene propylene diene monomer, kaolin, calcium carbonate, compatilizer and flame retardant into a reaction kettle, stirring for 20-50min at 800-1200rpm, mixing for 10-25min at 120-140 ℃, and cooling to room temperature to obtain a mixture A;
(2) Adding an anti-aging agent and a zinc-barium stabilizer into the mixture A, stirring for 20-40min at 1200-2000rpm, and mixing for 1-4min at 120-140 ℃ to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is 140-160 ℃, and the screw rotation speed is 150-250rpm, so that the fire-fighting flame-retardant cable material is obtained.
6. The flame retardant is characterized by comprising a nitrogen-phosphorus flame retardant and modified magnesium hydroxide, and the preparation method of the flame retardant comprises the following steps:
s1, mixing 10-30 parts by weight of 0.5-2mol/L hydrochloric acid and 5-15 parts by weight of (p-methylphenyl ethyl) methyldimethoxy silane, reacting for 1-3 hours at 60-80 ℃ and 300-500rpm, and cooling to room temperature to obtain a reaction solution A; adding 10-20 parts by weight of chlorinated trimellitic anhydride, and stirring at 500-700rpm for 0.5-2h to obtain a reaction solution B; adding 15-25 parts by weight of melamine and 20-30 parts by weight of 2-hydroxyphosphonoacetic acid, stirring for 1-3 hours at 500-700rpm, filtering, and drying to obtain a nitrogen-phosphorus flame retardant;
s2, mixing 15-30 parts by weight of magnesium hydroxide and 60-120 parts by weight of water, stirring for 25-50min at 400-800rpm, adding 15-300 parts by weight of 5-15wt% of coupling agent ethanol solution, continuously stirring for 1-3h at 60-80 ℃ and 300-500rpm, centrifuging, washing and drying to obtain modified magnesium hydroxide;
s3, mixing 5-12 parts by weight of the modified magnesium hydroxide with 80-140 parts by weight of 50-70wt% ethanol water solution, adding 7-13 parts by weight of 5-10wt% pentabromoethyl benzene ethanol solution, and performing ultrasonic treatment for 0.5-2 hours under the conditions of ultrasonic power of 100-300W and ultrasonic frequency of 30-60 kHz; adding 10-30 parts by weight of the nitrogen-phosphorus flame retardant, stirring for 2-5 hours at 25-35 ℃ and 400-800rpm, filtering, and drying to obtain the flame retardant.
7. Use of the flame retardant according to claim 6 for the preparation of fire-retardant cable materials for fire protection.
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| CN101531885B (en) * | 2009-04-17 | 2012-02-01 | 清华大学深圳研究生院 | Environment-friendly inflaming retarding smoke-inhibiting shaping phase-changing energy storage material and preparing method thereof |
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