CN112111149A - High-strength flame-retardant cable material and preparation method thereof - Google Patents

High-strength flame-retardant cable material and preparation method thereof Download PDF

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CN112111149A
CN112111149A CN202010993078.3A CN202010993078A CN112111149A CN 112111149 A CN112111149 A CN 112111149A CN 202010993078 A CN202010993078 A CN 202010993078A CN 112111149 A CN112111149 A CN 112111149A
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cable material
retardant cable
strength flame
boron fiber
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2201/02—Flame or fire retardant/resistant
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    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2312/00—Crosslinking

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Abstract

The invention discloses a preparation method of a high-strength flame-retardant cable material, which is characterized by comprising the following steps of: step S1, preparing a fluorine-containing polycondensate based on calixarene crown ether, step S2, modifying nano boron fibers by phenyl hydroxyl phosphinyl groups, and step S3, and forming a cable material. The invention also provides the high-strength flame-retardant cable material prepared by the preparation method of the high-strength flame-retardant cable material. The high-strength flame-retardant cable material provided by the invention has the advantages of better comprehensive performance, better mechanical property, more excellent weather resistance, flame retardance, high-temperature resistance and environmental protection performance and longer service life.

Description

High-strength flame-retardant cable material and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-strength flame-retardant cable material and a preparation method thereof.
Background
With the rapid development of economic construction, the living standard of people is continuously improved, and the demand of various cables is more and more increased due to the rapid development of various infrastructures in cities and countryside. The cable is a carrier of power transmission, is the basis of guaranteeing the normal work of electric products, plays the effect of transmission electric power, transmission information and realization electromagnetic energy conversion in electric products. The cable material is a necessary material for preparing the cable, and the performance of the cable material directly influences the transmission quality of various energies and signals and the service life of the cable. The cable material with excellent performance can effectively restrain the occurrence of safety accidents, is the technical core and key for forming high-voltage and extra-high-voltage power transmission and transformation equipment and networks, and the level and stability of the electrical performance of the cable material are directly related to the voltage level and safety of the whole power transmission network.
The common cable material in the prior art has poor weather resistance, when equipment works outdoors or is always placed in the atmosphere and is irradiated by solar ultraviolet rays for a long time, the surface of the cable material is cracked, and connecting wires of some equipment or automobiles are in direct contact with mineral oil such as gasoline, engine oil and the like, so that the surface swelling phenomenon is easy to occur, and the physical and mechanical properties of the product are greatly reduced. The cable materials have more potential dangers in the using process, and directly influence the property safety and the personal safety of electronic and electric equipment, automobiles and the like. In particular, the short circuit of the cable in some large-scale electronic and electric equipment is easy to burn out the electric equipment, and a fire disaster can happen in serious conditions. When the working environment is high, the phenomena of melting, dry cracking and the like can occur, the insulating function is lost, the cable becomes soft under the long-time high-power use state, and the mechanical property is poor. In addition, in the practical application process, the electric wire and the electric cable can be bent along with the movement of the electric wire and the electric cable, the electric wire and the electric cable are frequently inserted and pulled out, the electric wire and the electric cable are not good in flexibility and can be broken when being used for a long time, and the phenomenon is more obvious particularly in a high-temperature working occasion.
The Chinese patent with the application number of 201310652136.6 discloses an environment-friendly filling cable material which is prepared from the following raw materials in parts by weight: 90-110 parts of PVC resin powder, 5-8 parts of CPE (chlorinated polyethylene), 5-7 parts of antimony trioxide, 2-3 parts of barium stearate, 2.3-3.5 parts of dioctyl phthalate, 0.1-0.3 part of dysprosium oxide, 2-3 parts of boron nitride, 3000.3-0.5 part of antioxidant, 6260.1-0.2 part of antioxidant, 1.4-2.4 parts of magnesium silicate, 0.2-0.4 part of propylene oxide glycerol polyether, 10-18 parts of modified nano kaolin powder, 30-40 parts of composite filler and 0.2-0.4 part of trioctyl trimellitate. The cable material takes PVC resin powder as a base material, wherein the chlorine content is increased, a large amount of smoke and toxic and corrosive gas are released during combustion, and are dangerous factors in fire, so that the safe evacuation and fire extinguishing work of people is prevented in the fire, and the life and property are seriously lost, wherein more additives are added, so that the processing flow property is required to be further improved, and the leakage is caused by phase separation in the long-term use process, so that the performance stability is influenced; the added dioctyl phthalate plasticizer is toxic, and the use safety needs to be further improved.
Therefore, the development of the high-strength flame-retardant cable material with better comprehensive performance, better mechanical property, better weather resistance, flame retardance, high-temperature resistance and environmental protection performance and longer service life meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the electrical transmission technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-strength flame-retardant cable material which has better comprehensive performance, better mechanical property, better weather resistance, flame retardance, high temperature resistance and environmental protection performance and longer service life; meanwhile, the invention also provides a preparation method of the high-strength flame-retardant cable material, which is simple and easy to implement, has low requirements on equipment and reaction conditions, high preparation efficiency and low labor environment and labor intensity, is suitable for industrial production, and has higher economic value, social value and ecological value.
In order to achieve the purpose, the invention adopts the technical scheme that the preparation method of the high-strength flame-retardant cable material is characterized by comprising the following steps of:
step S1, preparation of the fluorine-containing polycondensate based on the calixarene crown ether: adding 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6 and a catalyst into a high-boiling-point solvent to form a solution, dropwise adding an N, N-dimethylformamide solution of 25-35% by mass of hexafluoroglutaryl chloride in an inert gas atmosphere in an ice-water bath while stirring, continuously stirring for reacting for 6-8 hours after completing dropwise addition, then precipitating in water, washing the precipitated polymer for 3-7 times by using ethanol, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain a condensation polymer containing fluorine based on calixarene crown ether;
step S2, modifying the nano boron fiber by the phenyl hydroxyl phosphinyl group: dispersing the nano boron fiber in an organic solvent, then adding 2- (diphenyl hydroxyl phosphinylene) ethyl triethoxysilane into the organic solvent, refluxing and stirring for 4-6 hours at the temperature of 60-80 ℃, and then removing the solvent by rotary evaporation to obtain the phenyl hydroxyl phosphinylene modified nano boron fiber;
step S3, cable material molding: and (2) uniformly mixing the fluorine-containing polycondensate based on the calixarene crown ether prepared in the step S1, the phenylphosphine based modified nano boron fiber prepared in the step S2, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber to form a mixed material, and then adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-strength flame-retardant cable material finished product.
Preferably, the molar ratio of the 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6, the hexafluoroglutaryl chloride, the catalyst and the high boiling point solvent in the step S1 is 1.05:1 (0.8-1.2): 7-12.
Preferably, the preparation method of the 11, 23-di (amino) -25, 27-di (2-propoxy) -calix [4] arene-crown-6 is described in the first embodiment of the Chinese patent with the application number of 201510593363.5.
Preferably, the catalyst is any one of triethanolamine and anhydrous pyridine.
Preferably, the high boiling point solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the mass ratio of the nano boron fiber, the organic solvent and the 2- (diphenyl hydroxyl phosphinyl) ethyl triethoxysilane in the step S2 is 1 (3-5) to (0.1-0.2).
Preferably, the diameter of the nano boron fiber is 200-400nm, and the length-diameter ratio is (13-15): 1.
Preferably, the organic solvent is any one of ethanol, isopropyl ketone, acetone and dichloromethane.
Preferably, the mass ratio of the fluorine-containing polycondensate based on the calixarene crown ether, the modified nano boron fiber based on the phenylphosphine group, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber in the step S3 is (80-100): (10-20): (5-10): (1-2): (25-35).
Preferably, the number average molecular weight M of the poly-2-acrylamide-2-methylpropanesulfonic acidnIs 5200g/mol, Mn/MwIs 1.33.
Preferably, the styrene-butadiene rubber is at least one of SBR1502, SBR-1712 and SBR 1500.
The invention also aims to provide the high-strength flame-retardant cable material prepared by the preparation method of the high-strength flame-retardant cable material.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the preparation method of the high-strength flame-retardant cable material provided by the invention is simple and feasible, has low requirements on equipment and reaction conditions, is high in preparation efficiency, low in labor environment and labor intensity, suitable for industrial production, and has higher economic value, social value and ecological value.
(2) The high-strength flame-retardant cable material provided by the invention overcomes the defects that the common cable material is poor in weather resistance, low in physical and mechanical properties and low in flame resistance and high temperature resistance, and the flame resistance and the high temperature resistance need to be further improved.
(3) According to the high-strength flame-retardant cable material, when the cable material is formed, under the condition that phosphorus pentoxide is used as a catalyst, sulfonic groups on poly (2-acrylamide-2-methylpropanesulfonic acid) can perform a cross-linking reaction with a fluorine-containing condensation polymer based on calixarene crown ether, phenyl hydroxyl phosphinyl modified nano boron fibers and benzene rings on styrene butadiene rubber to form a three-dimensional network structure, so that the comprehensive performance of the cable material is effectively improved; the elasticity and toughness of the cable material can be improved by adding the styrene butadiene rubber, so that the cable material has better mechanical property, is not easy to move, bend, frequently plug and pull in the actual use process, and is not easy to break after long-term use.
(4) According to the high-strength flame-retardant cable material provided by the invention, the nano boron fiber is added, the mechanical property of the cable material can be effectively improved, and the chemical resistance and the flame retardance can be effectively improved by introducing the phenylphosphine oxide structure through surface modification, so that the service life is longer; on the other hand, the compatibility and the dispersion uniformity between the nano boron fiber and the polymer base material can be improved.
(5) The high-strength flame-retardant cable material provided by the invention is based on the introduction of the fluorine-containing condensation polymer of the calixarene crown ether, the comprehensive performance of the cable material is better due to the introduction of fluorine, amide groups and benzene ring groups on a molecular chain, and the flame-retardant performance can be effectively improved due to the introduction of the calixarene crown ether, so that the comprehensive performance is better under the multiple actions of the electronic effect, the steric effect and the conjugate effect of each component structure.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto; the preparation method of the 11, 23-di (amino) -25, 27-di (2-propoxy) -calix [4] arene-crown-6 is described in the first embodiment of the Chinese patent with the application number of 201510593363.5; all other materials involved were purchased commercially.
Example 1
Embodiment 1 provides a preparation method of a high-strength flame-retardant cable material, which is characterized by comprising the following steps:
step S1, preparation of the fluorine-containing polycondensate based on the calixarene crown ether: adding 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6 and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding a N, N-dimethylformamide solution of 25% by mass of hexafluoroglutaryl chloride in an inert gas atmosphere in an ice-water bath while stirring, continuously stirring and reacting for 6 hours after completing dropwise adding, then precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and finally drying in a vacuum drying oven at 85 ℃ to constant weight to obtain the calixarene-based crown ether fluorine-containing polycondensate;
step S2, modifying the nano boron fiber by the phenyl hydroxyl phosphinyl group: dispersing the nano boron fiber in an organic solvent, then adding 2- (diphenyl hydroxyl phosphinylene) ethyl triethoxysilane into the organic solvent, refluxing and stirring for 4 hours at 60 ℃, and then removing the solvent by rotary evaporation to obtain the phenyl hydroxyl phosphinylene modified nano boron fiber;
step S3, cable material molding: and (2) uniformly mixing the fluorine-containing polycondensate based on the calixarene crown ether prepared in the step S1, the phenylphosphine based modified nano boron fiber prepared in the step S2, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber to form a mixed material, and then adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-strength flame-retardant cable material finished product.
The molar ratio of the 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6, the hexafluoroglutaryl chloride, the catalyst and the high boiling point solvent in step S1 is 1.05:1:0.8: 7; the catalyst is triethanolamine; the high boiling point solvent is N, N-dimethylformamide; the inert gas is nitrogen.
In the step S2, the mass ratio of the nano boron fiber to the organic solvent to the 2- (diphenylphosphinyl) ethyltriethoxysilane is 1:3: 0.1; the diameter of the nano boron fiber is 200nm, and the length-diameter ratio is 13: 1; the organic solvent is ethanol.
In the step S3, the mass ratio of the fluorine-containing polycondensate based on the calixarene crown ether, the phenyl hydroxyl phosphinyl modified nano boron fiber, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber is 80:10:5:1: 25; the number average molecular weight M of the poly 2-acrylamide-2-methylpropanesulfonic acidnIs 5200g/mol, Mn/MwIs 1.33; the styrene butadiene rubber is of the SBR 1502.
The high-strength flame-retardant cable material is prepared according to the preparation method of the high-strength flame-retardant cable material.
Example 2
Embodiment 2 provides a preparation method of a high-strength flame-retardant cable material, which is characterized by comprising the following steps:
step S1, preparation of the fluorine-containing polycondensate based on the calixarene crown ether: adding 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6 and a catalyst into a high boiling point solvent to form a solution, then dropwise adding an N, N-dimethylformamide solution of 27% by mass of hexafluoroglutaryl chloride in an inert gas atmosphere in an ice-water bath while stirring, continuously stirring and reacting for 6.5 hours after the dropwise adding, then precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and finally drying in a vacuum drying oven at 87 ℃ to constant weight to obtain the fluorinated polycondensate based on the calixarene crown ether;
step S2, modifying the nano boron fiber by the phenyl hydroxyl phosphinyl group: dispersing the nano boron fiber in an organic solvent, then adding 2- (diphenyl hydroxyl phosphinylene) ethyl triethoxysilane into the organic solvent, refluxing and stirring for 4.5 hours at 65 ℃, and then removing the solvent by rotary evaporation to obtain the phenyl hydroxyl phosphinylene modified nano boron fiber;
step S3, cable material molding: and (2) uniformly mixing the fluorine-containing polycondensate based on the calixarene crown ether prepared in the step S1, the phenylphosphine based modified nano boron fiber prepared in the step S2, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber to form a mixed material, and then adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-strength flame-retardant cable material finished product.
The molar ratio of the 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6, the hexafluoroglutaryl chloride, the catalyst and the high boiling point solvent in the step S1 is 1.05:1:0.9: 8; the catalyst is anhydrous pyridine; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is helium.
In the step S2, the mass ratio of the nano boron fiber to the organic solvent to the 2- (diphenylphosphinyl) ethyltriethoxysilane is 1:3.5: 0.13; the diameter of the nano boron fiber is 250nm, and the length-diameter ratio is 13.5: 1; the organic solvent is isopropyl ketone.
The calixarene crown ether-based fluorine-containing polycondensate, the phenylphosphine-based modified nano boron fiber and the poly-2-acrylamide-2-methyl in the step S3The mass ratio of the propyl sulfonic acid to the phosphorus pentoxide to the styrene butadiene rubber is 85:12:6:1.2: 27; the number average molecular weight M of the poly 2-acrylamide-2-methylpropanesulfonic acidnIs 5200g/mol, Mn/MwIs 1.33; the styrene butadiene rubber is of the brand SBR-1712.
The high-strength flame-retardant cable material is prepared according to the preparation method of the high-strength flame-retardant cable material.
Example 3
Embodiment 3 provides a preparation method of a high-strength flame-retardant cable material, which is characterized by comprising the following steps:
step S1, preparation of the fluorine-containing polycondensate based on the calixarene crown ether: adding 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6 and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding a solution of N, N-dimethylformamide of hexafluoroglutaryl chloride with the mass percentage concentration of 30% in an ice-water bath under the condition of stirring in an inert gas atmosphere, continuously stirring for reacting for 7 hours after the completion of dropwise adding, then precipitating in water, washing the precipitated polymer for 5 times by using ethanol, and finally drying the polymer in a vacuum drying oven at 90 ℃ to constant weight to obtain the calixarene-based crown ether fluorine-containing polycondensate;
step S2, modifying the nano boron fiber by the phenyl hydroxyl phosphinyl group: dispersing the nano boron fiber in an organic solvent, then adding 2- (diphenyl hydroxyl phosphinylene) ethyl triethoxysilane into the organic solvent, refluxing and stirring the mixture for 5 hours at 70 ℃, and then removing the solvent by rotary evaporation to obtain the phenyl hydroxyl phosphinylene modified nano boron fiber;
step S3, cable material molding: and (2) uniformly mixing the fluorine-containing polycondensate based on the calixarene crown ether prepared in the step S1, the phenylphosphine based modified nano boron fiber prepared in the step S2, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber to form a mixed material, and then adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-strength flame-retardant cable material finished product.
The molar ratio of the 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6, the hexafluoroglutaryl chloride, the catalyst and the high boiling point solvent in the step S1 is 1.05:1:1: 9; the catalyst is triethanolamine; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is neon.
In the step S2, the mass ratio of the nano boron fiber to the organic solvent to the 2- (diphenylphosphinyl) ethyltriethoxysilane is 1:4: 0.15; the diameter of the nano boron fiber is 300nm, and the length-diameter ratio is 14: 1; the organic solvent is acetone.
In the step S3, the mass ratio of the fluorine-containing polycondensate based on the calixarene crown ether, the phenyl hydroxyl phosphinyl modified nano boron fiber, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber is 90:15:8:1.5: 30; the number average molecular weight M of the poly 2-acrylamide-2-methylpropanesulfonic acidnIs 5200g/mol, Mn/MwIs 1.33; the styrene butadiene rubber is SBR 1500.
The high-strength flame-retardant cable material is prepared according to the preparation method of the high-strength flame-retardant cable material.
Example 4
Embodiment 4 provides a preparation method of a high-strength flame-retardant cable material, which is characterized by comprising the following steps:
step S1, preparation of the fluorine-containing polycondensate based on the calixarene crown ether: adding 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6 and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding a 33 mass percent N, N-dimethylformamide solution into an ice-water bath under the condition of stirring in an inert gas atmosphere, continuously stirring and reacting for 7.8 hours after the dropwise adding, then precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying the polymer in a vacuum drying oven at 93 ℃ to constant weight to obtain the calixarene-based crown ether fluorine-containing polycondensate;
step S2, modifying the nano boron fiber by the phenyl hydroxyl phosphinyl group: dispersing the nano boron fiber in an organic solvent, then adding 2- (diphenyl hydroxyl phosphinylene) ethyl triethoxysilane into the organic solvent, refluxing and stirring the mixture for 5.5 hours at 78 ℃, and then removing the solvent by rotary evaporation to obtain the phenyl hydroxyl phosphinylene modified nano boron fiber;
step S3, cable material molding: and (2) uniformly mixing the fluorine-containing polycondensate based on the calixarene crown ether prepared in the step S1, the phenylphosphine based modified nano boron fiber prepared in the step S2, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber to form a mixed material, and then adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-strength flame-retardant cable material finished product.
The molar ratio of the 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6, the hexafluoroglutaryl chloride, the catalyst and the high boiling point solvent in the step S1 is 1.05:1:1.1: 11; the catalyst is triethanolamine; the high-boiling-point solvent is formed by mixing N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:3: 4; the inert gas is argon.
In the step S2, the mass ratio of the nano boron fiber to the organic solvent to the 2- (diphenylphosphinyl) ethyltriethoxysilane is 1:4.5: 0.18; the diameter of the nano boron fiber is 380nm, and the length-diameter ratio is 14.5: 1; the organic solvent is dichloromethane.
In the step S3, the mass ratio of the fluorine-containing polycondensate based on the calixarene crown ether, the phenyl hydroxyl phosphinyl modified nano boron fiber, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber is 95:18:9:1.8: 33; the number average molecular weight M of the poly 2-acrylamide-2-methylpropanesulfonic acidnIs 5200g/mol, Mn/MwIs 1.33; the styrene butadiene rubber is of the SBR 1502.
The high-strength flame-retardant cable material is prepared according to the preparation method of the high-strength flame-retardant cable material.
Example 5
Embodiment 5 provides a preparation method of a high-strength flame-retardant cable material, which is characterized by comprising the following steps:
step S1, preparation of the fluorine-containing polycondensate based on the calixarene crown ether: adding 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6 and a catalyst into a high-boiling-point solvent to form a solution, then dropwise adding a 35 mass percent N, N-dimethylformamide solution into an ice-water bath under the condition of stirring in an inert gas atmosphere, continuously stirring and reacting for 8 hours after the dropwise adding is finished, then precipitating in water, washing the precipitated polymer for 7 times by using ethanol, and finally drying the polymer in a vacuum drying oven at 95 ℃ to constant weight to obtain the calixarene-based crown ether fluorine-containing polycondensate;
step S2, modifying the nano boron fiber by the phenyl hydroxyl phosphinyl group: dispersing the nano boron fiber in an organic solvent, then adding 2- (diphenyl hydroxyl phosphinylene) ethyl triethoxysilane into the organic solvent, refluxing and stirring the mixture for 6 hours at the temperature of 80 ℃, and then removing the solvent by rotary evaporation to obtain the phenyl hydroxyl phosphinylene modified nano boron fiber;
step S3, cable material molding: and (2) uniformly mixing the fluorine-containing polycondensate based on the calixarene crown ether prepared in the step S1, the phenylphosphine based modified nano boron fiber prepared in the step S2, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber to form a mixed material, and then adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-strength flame-retardant cable material finished product.
The molar ratio of the 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6, the hexafluoroglutaryl chloride, the catalyst and the high boiling point solvent in the step S1 is 1.05:1:1.2: 12; the catalyst is anhydrous pyridine; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is argon.
In the step S2, the mass ratio of the nano boron fiber to the organic solvent to the 2- (diphenylphosphinyl) ethyltriethoxysilane is 1:5: 0.2; the diameter of the nano boron fiber is 400nm, and the length-diameter ratio is 15: 1; the organic solvent is ethanol.
In the step S3, the mass ratio of the fluorine-containing polycondensate based on the calixarene crown ether, the phenyl hydroxyl phosphinyl modified nano boron fiber, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber is 100:20:10:2: 35; the number average molecular weight M of the poly 2-acrylamide-2-methylpropanesulfonic acidnIs 5200g/mol, Mn/MwIs 1.33; the styrene butadiene rubber is of the SBR 1502.
The high-strength flame-retardant cable material is prepared according to the preparation method of the high-strength flame-retardant cable material.
Comparative example 1
Comparative example 1 provides a high-strength flame-retardant cable material, the formulation and preparation method of which are substantially the same as those of example 1, except that the phenylethanophosphine-based modified nano boron fiber is not added.
Comparative example 2
Comparative example 2 provides a high strength flame retardant cable material having substantially the same formulation and preparation method as example 1 except that poly 2-acrylamido-2-methylpropanesulfonic acid was not added.
Comparative example 3
Comparative example 3 provides a high-strength flame-retardant cable material, whose formulation and preparation method are substantially the same as those of example 1, except that styrene-butadiene rubber is not added.
In order to further illustrate the beneficial technical effects of the high-strength flame-retardant cable material according to the embodiments of the present invention, the high-strength flame-retardant cable material samples according to the embodiments 1 to 5 and the comparative examples 1 to 3 are subjected to the related performance tests, and the test methods and the test results are shown in table 1; the aging is thermal aging at 70 ℃ for 4 h.
Table 1 cable material performance test results of examples and comparative examples
Figure DEST_PATH_IMAGE001
As can be seen from table 1, the high-strength flame-retardant cable material disclosed in the examples of the present invention has higher mechanical properties and flame retardancy and better aging resistance compared to the comparative example product, which is the result of the synergistic effect of the structures.
The above-mentioned embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention. .

Claims (10)

1. The preparation method of the high-strength flame-retardant cable material is characterized by comprising the following steps of:
step S1, preparation of the fluorine-containing polycondensate based on the calixarene crown ether: adding 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6 and a catalyst into a high-boiling-point solvent to form a solution, dropwise adding an N, N-dimethylformamide solution of 25-35% by mass of hexafluoroglutaryl chloride in an inert gas atmosphere in an ice-water bath while stirring, continuously stirring for reacting for 6-8 hours after completing dropwise addition, then precipitating in water, washing the precipitated polymer for 3-7 times by using ethanol, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain a condensation polymer containing fluorine based on calixarene crown ether;
step S2, modifying the nano boron fiber by the phenyl hydroxyl phosphinyl group: dispersing the nano boron fiber in an organic solvent, then adding 2- (diphenyl hydroxyl phosphinylene) ethyl triethoxysilane into the organic solvent, refluxing and stirring for 4-6 hours at the temperature of 60-80 ℃, and then removing the solvent by rotary evaporation to obtain the phenyl hydroxyl phosphinylene modified nano boron fiber;
step S3, cable material molding: and (2) uniformly mixing the fluorine-containing polycondensate based on the calixarene crown ether prepared in the step S1, the phenylphosphine based modified nano boron fiber prepared in the step S2, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber to form a mixed material, and then adding the mixed material into a double-screw extruder for extrusion molding to obtain a high-strength flame-retardant cable material finished product.
2. The method as claimed in claim 1, wherein the molar ratio of 11, 23-bis (amino) -25, 27-bis (2-propoxy) -calix [4] arene-crown-6, hexafluoroglutaryl chloride, catalyst, high boiling point solvent in step S1 is 1.05:1 (0.8-1.2): 7-12.
3. The method for preparing a high-strength flame-retardant cable material according to claim 1, wherein the catalyst is any one of triethanolamine and anhydrous pyridine.
4. The method for preparing a high-strength flame-retardant cable material according to claim 1, wherein the high-boiling solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
5. The method for preparing a high-strength flame-retardant cable material according to claim 1, wherein the inert gas is any one of nitrogen, helium, neon and argon.
6. The method as claimed in claim 1, wherein the mass ratio of the boron nanofibers, the organic solvent, and the 2- (diphenylphosphinyl) ethyltriethoxysilane in step S2 is 1 (3-5) to (0.1-0.2).
7. The method for preparing the high-strength flame-retardant cable material as claimed in claim 1, wherein the nano boron fiber has a diameter of 200-400nm, an aspect ratio (13-15): 1; the organic solvent is any one of ethanol, isopropyl ketone, acetone and dichloromethane.
8. The method as claimed in claim 1, wherein the mass ratio of the fluorine-containing polycondensate based on calixarene crown ether, the modified nano boron fiber based on phenylphosphine, the poly 2-acrylamide-2-methylpropanesulfonic acid, the phosphorus pentoxide and the styrene butadiene rubber in step S3 is (80-100): 10-20): 5-10): 1-2): 25-35.
9. The method for preparing a high-strength flame-retardant cable material as claimed in claim 1, wherein the number average molecular weight M of the poly-2-acrylamido-2-methylpropanesulfonic acidnIs 5200g/mol, Mn/MwIs 1.33; the styrene butadiene rubber is at least one of SBR1502, SBR-1712 and SBR 1500.
10. A high-strength flame-retardant cable material prepared by the preparation method of the high-strength flame-retardant cable material according to any one of claims 1 to 9.
CN202010993078.3A 2020-09-21 2020-09-21 High-strength flame-retardant cable material and preparation method thereof Withdrawn CN112111149A (en)

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