CN114854115A - Flame-retardant sheath rubber material for salt mist-resistant offshore wind power cable and preparation method thereof - Google Patents
Flame-retardant sheath rubber material for salt mist-resistant offshore wind power cable and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant sheath rubber material for a salt mist resistant offshore wind power cable and a preparation method thereof, and belongs to the technical field of protective materials. According to the invention, vinyl trimethoxy silane is polymerized into polyhedral organic siloxane under the catalysis of hydrochloric acid, n-butyl lithium reacts with polystyrene according to a mass ratio, then reacts with poly-1, 3-butadiene to prepare a macromolecular active chain, the polyhedral organic siloxane reacts with the macromolecular active chain to prepare a polyhedral copolymer, and the hydrolyzed polyhedral copolymer is modified by trifluoromethyl (1, 10-phenanthroline) copper and then is mixed with polyethylene to prepare the flame-retardant sheath rubber material for the salt-resistant fog type offshore wind power cable. The flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable prepared by the invention has excellent corrosion resistance and flame retardance.
Description
Technical Field
The invention relates to the technical field of protective materials, in particular to a flame-retardant sheath rubber material for a salt mist resistant offshore wind power cable and a preparation method thereof.
Background
Wind power generation is the fastest-developing green energy technology in the world, and people have noticed some limitations on land wind energy utilization, such as large occupied area, noise pollution and the like, while land wind power plant construction is rapidly developed. Due to the abundant wind energy resources at sea and the feasibility of the current technology, the sea becomes a rapidly-developing wind power market. The wind farm is already in the fore of large-scale development in europe and the united states. The sea area of the east coastal water depth of China within 50m is vast and is very close to a power load center (a coastal economically developed power shortage area), and with the mature development of offshore wind farm technology, wind power can certainly become an important energy source for sustainable development of the east coastal area of China.
Offshore wind power generation needs a corresponding power cable to transmit high-power electric energy, and the effect of the power cable is equal to that of an underground power cable. Submarine cable engineering is recognized as a complex and difficult large-scale project by countries all over the world due to different application occasions and laying modes, and complex technologies are applied to environment detection, marine physics investigation, and design, manufacture and installation of cables. The offshore wind power cable is in a severe environment, so that a good salt mist resistant flame retardant sheath rubber material is required.
Disclosure of Invention
The invention aims to provide a flame-retardant sheath rubber material for a salt mist resistant offshore wind power cable and a preparation method thereof, and aims to solve the problems in the prior art.
The flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable is characterized by being prepared by reacting polyhedral organic siloxane with a macromolecular active chain, reacting with trifluoromethyl (1, 10-phenanthroline) copper, and finally mixing with polyethylene.
Preferably, the polyhedral organosiloxane is prepared by polymerizing vinyl trimethoxy silane under the catalysis of hydrochloric acid.
Preferably, the macromolecular active chain is prepared by reacting n-butyllithium with polystyrene and then reacting with poly-1, 3-butadiene.
Optimally, the trifluoromethyl (1, 10-phenanthroline) copper is prepared by adding 1, 10-phenanthroline to react after tert-butyl copper reacts with trifluoromethyl trimethyl alkane
A preparation method of a flame-retardant sheath rubber material for a salt mist resistant offshore wind power cable is characterized by mainly comprising the following preparation steps:
(1) preparing polyhedral organic siloxane;
(2) preparing a macromolecular active chain;
(3) preparing a polyhedral copolymer;
(4) modification of the polyhedral copolymer;
(5) and (4) mixing.
As optimization, the preparation method of the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable mainly comprises the following preparation steps:
(1) mixing vinyl trimethoxy silane, hydrochloric acid with the mass fraction of 25-30% and absolute ethyl alcohol according to the mass ratio of 1: 1: 10-1: 2: 15, uniformly mixing, stirring and reacting at the temperature of 20-30 ℃ at 1500-2000 r/min for 4-6 h, cooling to 1-5 ℃, filtering, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying at the temperature of 60-70 ℃ under the pressure of 5-10 Pa for 6-8 h to obtain polyhedral organic siloxane;
(2) under the anhydrous and oxygen-free conditions, mixing n-butyl lithium and polystyrene according to the mass ratio of 1: 7-1: 9, mixing, stirring and reacting at 20-30 ℃ for 10-12 h at 1500-2000 r/min, adding poly 1, 3-butadiene of which the amount is 2-3 times that of polystyrene, and stirring and reacting at 20-30 ℃ for 10-12 h at 1500-2000 r/min to prepare a macromolecular active chain;
(3) mixing polyhedral organic siloxane and a macromolecular active chain according to a mass ratio of 1: 15-1: 20, uniformly mixing, stirring and reacting at the temperature of 20-30 ℃ at 1500-2000 r/min for 60-80 min, filtering, washing with absolute methanol at the temperature of-5-1 ℃ for 3-5 times, and drying at the temperature of 30-40 ℃ for 4-6 h under 5-10 Pa to obtain a polyhedral copolymer;
(4) hydrolyzing the polyhedral copolymer, and mixing the hydrolyzed polyhedral copolymer with an acetone solution with the mass fraction of 30% according to the mass ratio of 1: 10-1: 15, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.5-0.6 time that of the polyhedral copolymer, stirring at the rotation speed of 2000-3000 r/min for 8-12 h under the conditions of 30 ℃ and ultraviolet irradiation with 60W power and 365nm wavelength, filtering, washing with absolute ethyl alcohol for 3-5 times, and carrying out vacuum freeze drying at-10-5 ℃ and 10Pa for 5-6 h to prepare the modified polyhedral copolymer;
(5) mixing the modified polyhedral copolymer and polyethylene according to a mass ratio of 1: 1, performing mixed smelting at the smelting temperature of 180-200 ℃, at the stirring speed of 2500-3000 r/min and for 30-40 min, and cooling and shaping to obtain the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable.
Preferably, the gas atmosphere of the anhydrous and anaerobic condition in the step (2) is one of nitrogen and argon.
Preferably, the polymerization degree of the polystyrene and the polymerization degree of the poly-1, 3-butadiene in the step (2) are both less than 100.
As an optimization, the hydrolysis method in the step (4) comprises the following steps: immersing the polyhedral copolymer in hydrochloric acid with the mass fraction of 5-8%, carrying out ultrasonic treatment at 30-40 kHz for 20-30 min, filtering, washing with pure water for 3-5 times, and drying at 1-5 ℃ under 5-10 Pa for 4-6 h.
Preferably, the trifluoromethyl (1, 10-phenanthroline) copper in the step (4) is prepared by mixing tert-butyl copper, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of 2: 1: 10-1: 1: 15, stirring and reacting at 50-60 ℃ at 800-1000 r/min for 1-2 h, adding 1, 10-phenanthroline in an amount which is 2 times of the mass of fluoromethyl trimethyl alkane, and stirring at the rotation speed of 100-200 r/min for 5-8 min at 70-80 ℃ to prepare the composite material.
Compared with the prior art, the invention has the following beneficial effects:
when the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable is prepared, vinyl trimethoxy silane is polymerized into polyhedral organic siloxane under the catalysis of hydrochloric acid, n-butyl lithium and polystyrene react according to the mass ratio, then the polyhedral organic siloxane reacts with poly (1, 3-butadiene) to prepare a macromolecular active chain, the polyhedral organic siloxane reacts with the macromolecular active chain to prepare a polyhedral copolymer, and the hydrolyzed polyhedral copolymer is modified by trifluoromethyl (1, 10-phenanthroline) copper and then is mixed with polyethylene to prepare the flame-retardant sheath rubber material.
Firstly, vinyl trimethoxy silane is polymerized into polyhedral organic siloxane under the catalysis of hydrochloric acid, n-butyl lithium and polystyrene react according to the mass ratio, then the polyhedral organic siloxane reacts with the macromolecular active chain to prepare a macromolecular active chain, the polyhedral organic siloxane reacts with the macromolecular active chain to prepare a polyhedral copolymer, vinyl on the polyhedral organic siloxane can be crosslinked with the macromolecular active chain to obtain the polyhedral copolymer with a sea urchin-like structure, macromolecular chains on the polyhedral copolymer can be intertwined with each other to be used as a linking center, the polyhedral organic siloxane has good elasticity and toughness, phenyl can absorb ultraviolet rays, thereby achieving the anti-aging effect, the polyhedral organosiloxane in the polyhedral copolymer forms a silicon dioxide crystal layer at high temperature and is attached on the main body material for protection, thereby achieving the flame retardant effect, and simultaneously improving the corrosion resistance of the material by doping the silicon element.
Secondly, the hydrolyzed polyhedral copolymer is modified by trifluoromethyl (1, 10-phenanthroline) copper, chlorine on the hydrolyzed polyhedral copolymer is substituted by the trifluoromethyl (1, 10-phenanthroline) copper, and trifluoromethyl is introduced, so that the effect of shielding and protecting a carbon chain is achieved, the damage of the external environment to an internal chemical bond is isolated, the corrosion resistance of the material is improved, and meanwhile, halogen has a flame retardant effect and improves the flame retardance of the material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the invention, the method is illustrated in detail by the following examples, and the method for testing each index of the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable manufactured in the following examples is as follows:
corrosion resistance: the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable obtained in each embodiment and a comparative material are made into the same size and shape to test the breaking strength, then the flame-retardant sheath rubber material and the comparative material are placed in the same seawater environment to be corroded for the same time, the breaking strength is measured again, and the retention rate is calculated as the post-corrosion breaking strength/initial breaking strength.
Flame retardancy: the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable obtained in each embodiment and a comparative example material are in the same mass shape, and the limit oxygen index is tested according to GB/T2046.
Example 1
A preparation method of a flame-retardant sheath rubber material for a salt mist-resistant offshore wind power cable mainly comprises the following preparation steps:
(1) mixing vinyl trimethoxy silane, hydrochloric acid with the mass fraction of 30% and absolute ethyl alcohol according to the mass ratio of 1: 1: 10, uniformly mixing, stirring and reacting at 20 ℃ and 1500r/min for 6 hours, cooling to 1 ℃, filtering, washing with pure water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ and under the pressure of 5Pa for 8 hours to obtain polyhedral organic siloxane;
(2) under the anhydrous and oxygen-free conditions, mixing n-butyl lithium and polystyrene according to the mass ratio of 1: 7, mixing, stirring and reacting for 10 hours at the temperature of 20-30 ℃ at 1500r/min, adding poly 1, 3-butadiene 2 times of polystyrene, stirring and reacting for 12 hours at the temperature of 20 ℃ at 1500r/min to prepare a macromolecular active chain;
(3) mixing polyhedral organic siloxane and macromolecular active chain according to the mass ratio of 1: 15, uniformly mixing, stirring and reacting at 20 ℃ and 1500r/min for 80min, filtering, washing with absolute methanol at the temperature of-5 ℃ for 3 times, and drying at 30 ℃ and 5Pa for 6h to obtain a polyhedral copolymer;
(4) copper tert-butoxide, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of 2: 1: 10, mixing, stirring and reacting for 2 hours at 50 ℃ and 800r/min, adding 1, 10-phenanthroline with the mass being 2 times that of fluoromethyl trimethyl alkane, stirring for 8 minutes at 70 ℃ and the rotating speed of 100r/min to prepare trifluoromethyl (1, 10-phenanthroline), immersing a polyhedral copolymer in hydrochloric acid with the mass fraction being 5%, carrying out ultrasonic treatment for 30 minutes at 30kHz, filtering and washing for 3 times by using pure water, drying for 6 hours at 1 ℃ and 5Pa, and mixing the copper with an acetone solution with the mass fraction being 30% according to the mass ratio of 1: 10, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.5 time of that of the polyhedral copolymer, stirring at the condition of ultraviolet irradiation with the power of 30 ℃ and the wavelength of 365nm at 60W and the rotating speed of 2000r/min for 12 hours, filtering, washing for 3 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying at the temperature of-10 ℃ and the pressure of 10Pa for 6 hours to prepare the modified polyhedral copolymer;
(5) mixing the modified polyhedral copolymer and polyethylene according to a mass ratio of 1: 1, performing mixed smelting at the smelting temperature of 180 ℃, at the stirring speed of 2500r/min for 40min, and cooling and shaping to obtain the salt mist resistant flame-retardant sheath rubber material for the offshore wind power cable.
Example 2
A preparation method of a flame-retardant sheath rubber material for a salt mist-resistant offshore wind power cable mainly comprises the following preparation steps:
(1) mixing vinyl trimethoxy silane, hydrochloric acid with the mass fraction of 28% and absolute ethyl alcohol according to the mass ratio of 1: 1: 12, uniformly mixing, stirring and reacting at 25 ℃ and 1800r/min for 5 hours, cooling to 3 ℃, filtering, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying at 65 ℃ and under the pressure of 8Pa for 7 hours to obtain polyhedral organic siloxane;
(2) under the anhydrous and oxygen-free conditions, mixing n-butyl lithium and polystyrene according to the mass ratio of 1: 8, mixing, stirring and reacting for 11 hours at 25 ℃ and 1800r/min, adding poly 1, 3-butadiene 2.5 times of polystyrene, stirring and reacting for 11 hours at 25 ℃ and 1800r/min to prepare a macromolecular active chain;
(3) mixing polyhedral organic siloxane and a macromolecular active chain according to a mass ratio of 1: 18, uniformly mixing, stirring and reacting at 25 ℃ and 1800r/min for 70min, filtering, washing with absolute methanol at-3 ℃ for 4 times, and drying at 35 ℃ and 8Pa for 5h to obtain a polyhedral copolymer;
(4) copper tert-butoxide, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of 2: 1: 12, mixing, stirring and reacting at 55 ℃ and 900r/min for 1.5h, adding 1, 10-phenanthroline with the mass being 2 times that of fluoromethyl trimethyl alkane, stirring at 75 ℃ and the rotating speed of 150r/min for 7min to prepare trifluoromethyl (1, 10-phenanthroline) copper, immersing the polyhedral copolymer in hydrochloric acid with the mass fraction of 7%, performing ultrasonic treatment at 35kHz for 25min, filtering and washing with pure water for 4 times, drying at 3 ℃ and 8Pa for 5h, and mixing with an acetone solution with the mass fraction of 30% according to the mass ratio of 1: 12, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.55 time of that of the polyhedral copolymer, stirring at the rotating speed of 2500r/min for 10 hours under the conditions of 30 ℃ and 60W power and ultraviolet irradiation with the wavelength of 365nm, filtering, washing for 4 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 5.5 hours at the temperature of-8 ℃ and under the pressure of 10Pa to prepare the modified polyhedral copolymer;
(5) mixing the modified polyhedral copolymer and polyethylene according to a mass ratio of 1: 1, performing mixed smelting at the smelting temperature of 190 ℃, at the stirring speed of 2800r/min and for 35min, and cooling and shaping to obtain the salt mist resistant flame-retardant sheath rubber material for the offshore wind power cable.
Example 3
A preparation method of a flame-retardant sheath rubber material for a salt mist-resistant offshore wind power cable mainly comprises the following preparation steps:
(1) mixing vinyl trimethoxy silane, hydrochloric acid with the mass fraction of 28% and absolute ethyl alcohol according to the mass ratio of 1: 2: 15, uniformly mixing, stirring and reacting at 30 ℃ and 2000r/min for 4 hours, cooling to 5 ℃, filtering, washing with pure water and absolute ethyl alcohol for 5 times respectively, and drying at 70 ℃ and under the pressure of 10Pa for 6 hours to obtain polyhedral organic siloxane;
(2) under the anhydrous and oxygen-free conditions, mixing n-butyl lithium and polystyrene according to the mass ratio of 1: 9, mixing, stirring and reacting for 10 hours at 30 ℃ and 2000r/min, adding poly 1, 3-butadiene with 3 times of polystyrene, stirring and reacting for 10 hours at 30 ℃ and 2000r/min to prepare a macromolecular active chain;
(3) mixing polyhedral organic siloxane and a macromolecular active chain according to a mass ratio of 1: 20, uniformly mixing, stirring and reacting at 30 ℃ and 2000r/min for 60min, filtering, washing with absolute methanol at the temperature of-1 ℃ for 5 times, and drying at 40 ℃ and 10Pa for 4h to obtain a polyhedral copolymer;
(4) copper tert-butoxide, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of 1: 1: 15, stirring and reacting at 60 ℃ and 1000r/min for 1h, adding 1, 10-phenanthroline with the mass being 2 times that of fluoromethyl trimethyl alkane, stirring at 80 ℃ and the rotating speed of 200r/min for 5min to prepare trifluoromethyl (1, 10-phenanthroline) copper, immersing the polyhedral copolymer in hydrochloric acid with the mass fraction of 8%, performing ultrasonic treatment at 40kHz for 20min, filtering and washing with pure water for 5 times, drying at 5 ℃ and 10Pa for 4h, and mixing with an acetone solution with the mass fraction of 30% according to the mass ratio of 1: 15, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.6 time that of the polyhedral copolymer, stirring at the condition of ultraviolet irradiation with the power of 30 ℃ and the wavelength of 365nm at 60W and the rotating speed of 3000r/min for 12 hours, filtering, washing for 5 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 5 hours at the temperature of-5 ℃ and the pressure of 10Pa to prepare the modified polyhedral copolymer;
(5) mixing the modified polyhedral copolymer and polyethylene according to the mass ratio of 1: 1, performing mixed smelting at the smelting temperature of 200 ℃, at the stirring speed of 3000r/min and for 30min, and cooling and shaping to obtain the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable.
Comparative example 1
A preparation method of a flame-retardant sheath rubber material for a salt mist-resistant offshore wind power cable mainly comprises the following preparation steps:
(1) under the anhydrous and anaerobic conditions, mixing n-butyl lithium and polystyrene according to the mass ratio of 1: 8, mixing, stirring and reacting for 11 hours at 25 ℃ and 1800r/min, adding poly 1, 3-butadiene 2.5 times of polystyrene, stirring and reacting for 11 hours at 25 ℃ and 1800r/min to prepare a macromolecular active chain;
(2) mixing vinyl trimethoxy silane and a macromolecular active chain according to a mass ratio of 1: 18, uniformly mixing, stirring and reacting at 25 ℃ and 1800r/min for 70min, filtering, washing with absolute methanol at-3 ℃ for 4 times, and drying at 35 ℃ and 8Pa for 5h to obtain a polyhedral copolymer;
(3) copper tert-butoxide, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of 2: 1: 12, mixing, stirring and reacting at 55 ℃ and 900r/min for 1.5h, adding 1, 10-phenanthroline with the mass being 2 times that of fluoromethyl trimethyl alkane, stirring at 75 ℃ and the rotating speed of 150r/min for 7min to prepare trifluoromethyl (1, 10-phenanthroline) copper, immersing the polyhedral copolymer in hydrochloric acid with the mass fraction of 7%, performing ultrasonic treatment at 35kHz for 25min, filtering and washing with pure water for 4 times, drying at 3 ℃ and 8Pa for 5h, and mixing with an acetone solution with the mass fraction of 30% according to the mass ratio of 1: 12, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.55 time of that of the polyhedral copolymer, stirring at the rotating speed of 2500r/min for 10 hours under the conditions of 30 ℃ and 60W power and ultraviolet irradiation with the wavelength of 365nm, filtering, washing for 4 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 5.5 hours at the temperature of-8 ℃ and under the pressure of 10Pa to prepare the modified polyhedral copolymer;
(4) mixing the modified polyhedral copolymer and polyethylene according to a mass ratio of 1: 1, performing mixed smelting at the smelting temperature of 190 ℃, at the stirring speed of 2800r/min and for 35min, and cooling and shaping to obtain the salt mist resistant flame-retardant sheath rubber material for the offshore wind power cable.
Comparative example 2
A preparation method of a flame-retardant sheath rubber material for a salt mist-resistant offshore wind power cable mainly comprises the following preparation steps:
(1) mixing vinyl trimethoxy silane, hydrochloric acid with the mass fraction of 28% and absolute ethyl alcohol according to the mass ratio of 1: 1: 12, uniformly mixing, stirring and reacting at 25 ℃ and 1800r/min for 5 hours, cooling to 3 ℃, filtering, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying at 65 ℃ and under the pressure of 8Pa for 7 hours to obtain polyhedral organic siloxane;
(2) under the anhydrous and oxygen-free conditions, mixing n-butyl lithium and polystyrene according to the mass ratio of 1: 8, mixing, stirring and reacting for 11 hours at the temperature of 25 ℃ and 1800r/min to prepare a macromolecular active chain;
(3) mixing polyhedral organic siloxane and a macromolecular active chain according to a mass ratio of 1: 18, uniformly mixing, stirring and reacting at 25 ℃ and 1800r/min for 70min, filtering, washing with absolute methanol at-3 ℃ for 4 times, and drying at 35 ℃ and 8Pa for 5h to obtain a polyhedral copolymer;
(4) copper tert-butoxide, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of 2: 1: 12, mixing, stirring and reacting at 55 ℃ and 900r/min for 1.5h, adding 1, 10-phenanthroline with the mass being 2 times that of fluoromethyl trimethyl alkane, stirring at 75 ℃ and the rotating speed of 150r/min for 7min to prepare trifluoromethyl (1, 10-phenanthroline) copper, immersing the polyhedral copolymer in hydrochloric acid with the mass fraction of 7%, performing ultrasonic treatment at 35kHz for 25min, filtering and washing with pure water for 4 times, drying at 3 ℃ and 8Pa for 5h, and mixing with an acetone solution with the mass fraction of 30% according to the mass ratio of 1: 12, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.55 time of that of the polyhedral copolymer, stirring at the rotating speed of 2500r/min for 10 hours under the conditions of 30 ℃ and 60W power and ultraviolet irradiation with the wavelength of 365nm, filtering, washing for 4 times by using absolute ethyl alcohol, and carrying out vacuum freeze drying for 5.5 hours at the temperature of-8 ℃ and under the pressure of 10Pa to prepare the modified polyhedral copolymer;
(5) mixing the modified polyhedral copolymer and polyethylene according to a mass ratio of 1: 1, performing mixed smelting at the smelting temperature of 190 ℃, at the stirring speed of 2800r/min and for 35min, and cooling and shaping to obtain the salt mist resistant flame-retardant sheath rubber material for the offshore wind power cable.
Comparative example 3
A preparation method of a flame-retardant sheath rubber material for a salt mist-resistant offshore wind power cable mainly comprises the following preparation steps:
(1) mixing vinyl trimethoxy silane, hydrochloric acid with the mass fraction of 28% and absolute ethyl alcohol according to the mass ratio of 1: 1: 12, uniformly mixing, stirring and reacting at 25 ℃ and 1800r/min for 5 hours, cooling to 3 ℃, filtering, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying at 65 ℃ and under the pressure of 8Pa for 7 hours to obtain polyhedral organic siloxane;
(2) under the anhydrous and oxygen-free conditions, mixing n-butyl lithium and polystyrene according to the mass ratio of 1: 8, mixing, stirring and reacting for 11 hours at 25 ℃ and 1800r/min, adding poly 1, 3-butadiene 2.5 times of polystyrene, stirring and reacting for 11 hours at 25 ℃ and 1800r/min to prepare a macromolecular active chain;
(3) mixing polyhedral organic siloxane and a macromolecular active chain according to a mass ratio of 1: 18, uniformly mixing, stirring and reacting at 25 ℃ and 1800r/min for 70min, filtering, washing with absolute methanol at-3 ℃ for 4 times, and drying at 35 ℃ and 8Pa for 5h to obtain a polyhedral copolymer;
(4) mixing the polyhedral copolymer and polyethylene according to a mass ratio of 1: 1, performing mixed smelting at the smelting temperature of 190 ℃, at the stirring speed of 2800r/min and for 35min, and cooling and shaping to obtain the salt mist resistant flame-retardant sheath rubber material for the offshore wind power cable.
Examples of effects
The following table 1 shows the results of performance analysis of corrosion resistance and flame retardancy using examples 1 to 3 of the present invention and comparative examples 1 to 3.
TABLE 1
As can be seen from the comparison of the experimental data of examples 1-3 and comparative columns 1-3 in Table 1, the flame-retardant sheath rubber material for the salt mist-resistant offshore wind power cable prepared by the invention has excellent corrosion resistance and flame retardance.
The experimental data comparison of examples 1, 2 and 3 and comparative example 1 in table 1 shows that the retention rate of examples 1, 2 and 3 is high compared with comparative example 1, which shows that vinyl trimethoxy silane is polymerized to prepare multi-face organic siloxane, so that a regular and ordered multi-face copolymer similar to a sea urchin shape is obtained in the subsequent reaction with a macromolecular active chain, and the corrosion resistance of the flame-retardant sheath rubber material for the salt mist-resistant offshore wind power cable is improved by better protection effect after subsequent treatment; the embodiment 1, the embodiment 2 and the embodiment 3 have high retention rate and high limit oxygen index compared with the comparative embodiment 2 and the comparative embodiment 3, which shows that the poly-1, 3-butadiene is added in the process of preparing the macromolecular active chain, can be hydrolyzed and reacted with trifluoromethyl (1, 10-phenanthroline) copper in the subsequent process to form trifluoromethyl, plays a role in shielding and protecting a carbon chain, and isolates the damage of the external environment to an internal chemical bond, so that the corrosion resistance of the flame-retardant sheath rubber material for the salt mist-resistant offshore wind power cable is improved, and meanwhile, the halogen has a flame-retardant effect, and the flame retardance of the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable is characterized by being prepared by reacting polyhedral organic siloxane with a macromolecular active chain, reacting with trifluoromethyl (1, 10-phenanthroline) copper, and finally mixing with polyethylene.
2. The flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable according to claim 1, wherein the polyhedral organic siloxane is formed by polymerizing vinyl trimethoxy silane under the catalysis of hydrochloric acid.
3. The flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable according to claim 2, wherein the macromolecular active chain is prepared by reacting n-butyllithium with polystyrene and then reacting with poly-1, 3-butadiene.
4. The flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable according to claim 1, wherein the trifluoromethyl (1, 10-phenanthroline) copper is prepared by reacting tert-butyl copper with trifluoromethyl trimethyl alkane, and then adding 1, 10-phenanthroline for continuous reaction.
5. A preparation method of a flame-retardant sheath rubber material for a salt mist resistant offshore wind power cable is characterized by mainly comprising the following preparation steps:
(1) preparing polyhedral organic siloxane;
(2) preparing a macromolecular active chain;
(3) preparing a polyhedral copolymer;
(4) modification of the polyhedral copolymer;
(5) and (4) mixing.
6. The preparation method of the flame-retardant sheath rubber material for the salt mist-resistant offshore wind power cable according to claim 5, wherein the preparation method of the flame-retardant sheath rubber material for the salt mist-resistant offshore wind power cable mainly comprises the following preparation steps:
(1) mixing vinyl trimethoxy silane, hydrochloric acid with the mass fraction of 25-30% and absolute ethyl alcohol according to the mass ratio of 1: 1: 10-1: 2: 15, uniformly mixing, stirring and reacting at the temperature of 20-30 ℃ at 1500-2000 r/min for 4-6 h, cooling to 1-5 ℃, filtering, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying at the temperature of 60-70 ℃ under the pressure of 5-10 Pa for 6-8 h to obtain polyhedral organic siloxane;
(2) under the anhydrous and oxygen-free conditions, mixing n-butyl lithium and polystyrene according to the mass ratio of 1: 7-1: 9, mixing, stirring and reacting at the temperature of 20-30 ℃ at 1500-2000 r/min for 10-12 h, adding poly 1, 3-butadiene of which the amount is 2-3 times that of polystyrene, stirring and reacting at the temperature of 20-30 ℃ at 1500-2000 r/min for 10-12 h, and preparing a macromolecular active chain;
(3) mixing polyhedral organic siloxane and a macromolecular active chain according to a mass ratio of 1: 15-1: 20, uniformly mixing, stirring and reacting at the temperature of 20-30 ℃ at 1500-2000 r/min for 60-80 min, filtering, washing with absolute methanol at the temperature of-5-1 ℃ for 3-5 times, and drying at the temperature of 30-40 ℃ for 4-6 h under 5-10 Pa to obtain a polyhedral copolymer;
(4) hydrolyzing the polyhedral copolymer, and mixing the hydrolyzed polyhedral copolymer with an acetone solution with the mass fraction of 30% according to the mass ratio of 1: 10-1: 15, adding trifluoromethyl (1, 10-phenanthroline) copper with the mass of 0.5-0.6 time that of the polyhedral copolymer, stirring at the rotation speed of 2000-3000 r/min for 8-12 h under the conditions of 30 ℃ and ultraviolet irradiation with 60W power and 365nm wavelength, filtering, washing with absolute ethyl alcohol for 3-5 times, and carrying out vacuum freeze drying at-10-5 ℃ and 10Pa for 5-6 h to prepare the modified polyhedral copolymer;
(5) mixing the modified polyhedral copolymer and polyethylene according to a mass ratio of 1: 1, performing mixed smelting at the smelting temperature of 180-200 ℃, at the stirring speed of 2500-3000 r/min and for 30-40 min, and cooling and shaping to obtain the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable.
7. The preparation method of the flame-retardant sheath rubber compound for the salt mist resistant offshore wind power cable according to claim 6, wherein the gas atmosphere in the water-free and oxygen-free condition in the step (2) is one of nitrogen and argon.
8. The preparation method of the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable according to claim 7, wherein the polymerization degree of the polystyrene and the polymerization degree of the poly-1, 3-butadiene in the step (2) are both less than 100.
9. The preparation method of the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable according to claim 8, wherein the hydrolysis method in the step (4) comprises the following steps: immersing the polyhedral copolymer in hydrochloric acid with the mass fraction of 5-8%, carrying out ultrasonic treatment at 30-40 kHz for 20-30 min, filtering, washing with pure water for 3-5 times, and drying at 1-5 ℃ under 5-10 Pa for 4-6 h.
10. The preparation method of the flame-retardant sheath rubber material for the salt mist resistant offshore wind power cable according to claim 9, wherein the trifluoromethyl (1, 10-phenanthroline) copper prepared in the step (4) is prepared from tert-butyl alcohol copper, trifluoromethyl trimethyl alkane and absolute ethyl alcohol in a mass ratio of (2): 1: 10-1: 1: 15, stirring and reacting at 50-60 ℃ at 800-1000 r/min for 1-2 h, adding 1, 10-phenanthroline in an amount which is 2 times of the mass of fluoromethyl trimethyl alkane, and stirring at the rotation speed of 100-200 r/min for 5-8 min at 70-80 ℃ to prepare the composite material.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746553A (en) * | 2017-11-29 | 2018-03-02 | 陕西高华知本化工科技有限公司 | The preparation method of vinyl silsesquioxane composite |
| CN107936439A (en) * | 2017-10-17 | 2018-04-20 | 国网江苏省电力公司盐城供电公司 | A kind of high tenacity flame retardant cable and its preparation process for power circuit |
| CN110054898A (en) * | 2019-04-22 | 2019-07-26 | 广东省石油与精细化工研究院 | A kind of halogen-free flame-retardant thermoplastic elastomer and its preparation method and application |
| CN113956555A (en) * | 2021-11-17 | 2022-01-21 | 邓世伟 | Low-temperature-resistant, antioxidant and flame-retardant sheath material and preparation method thereof |
| CN113980621A (en) * | 2021-11-05 | 2022-01-28 | 江苏恒达包装股份有限公司 | High-light-transmittance acid-alkali-resistant hot melt adhesive based on organic silicon-based material modification |
-
2022
- 2022-04-08 CN CN202210367225.5A patent/CN114854115B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936439A (en) * | 2017-10-17 | 2018-04-20 | 国网江苏省电力公司盐城供电公司 | A kind of high tenacity flame retardant cable and its preparation process for power circuit |
| CN107746553A (en) * | 2017-11-29 | 2018-03-02 | 陕西高华知本化工科技有限公司 | The preparation method of vinyl silsesquioxane composite |
| CN110054898A (en) * | 2019-04-22 | 2019-07-26 | 广东省石油与精细化工研究院 | A kind of halogen-free flame-retardant thermoplastic elastomer and its preparation method and application |
| CN113980621A (en) * | 2021-11-05 | 2022-01-28 | 江苏恒达包装股份有限公司 | High-light-transmittance acid-alkali-resistant hot melt adhesive based on organic silicon-based material modification |
| CN113956555A (en) * | 2021-11-17 | 2022-01-21 | 邓世伟 | Low-temperature-resistant, antioxidant and flame-retardant sheath material and preparation method thereof |
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