CN112898662B - Teflon modified polyethylene sheath material and preparation method thereof - Google Patents
Teflon modified polyethylene sheath material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a Teflon modified polyethylene sheath material and a preparation method thereof, which belong to the technical field of cable materials and are prepared from the following raw materials in parts by weight: 100-200 parts of polyethylene resin, 120-170 parts of ethylene-tetrafluoroethylene copolymer, 15-30 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 1-3 parts of antioxidant, 1-4 parts of plasticizer, 2-4 parts of flame retardant, 1-2 parts of toughening agent and 0.5-1 part of stabilizer. The Teflon modified polyethylene sheath material prepared by the invention has the advantages of simple preparation method, good mechanical property, chemical corrosion resistance, high temperature resistance, ageing resistance, good comprehensive performance and wide application prospect.
Description
Technical Field
The invention relates to the technical field of cable materials, in particular to a Teflon modified polyethylene sheath material and a preparation method thereof.
Background
Teflon is a generic name of Polytetrafluoroethylene (PTFE), which is abbreviated as PTFE (commonly known as "Plastic King, hara") and has the chemical formula- (CF) 2 -CF 2 ) n -. Trade nameIn China, the trademark "Teflon" is also called "Teflon", etc. for sound production, and is transliterated as "Teflon".
Products of this material are generally referred to collectively as "non-stick coatings"; is an artificial synthetic polymer material using fluorine to replace all hydrogen atoms in polyethylene. The material has the characteristics of acid resistance, alkali resistance and resistance to various organic solvents, and is almost insoluble in all solvents. Meanwhile, polytetrafluoroethylene has the characteristic of high temperature resistance, and has extremely low friction coefficient, so the polytetrafluoroethylene can be used as a lubricating effect and also is an ideal paint which is not sticky to the inner layers of a pot and a water pipe.
The high temperature resistance and chemical stability of the composite material can be widely applied to special fields of optical cables, acid resistance, alkali resistance and various organic solvents are generally realized by firstly compressing and then sintering a Teflon material at high temperature, mixing Teflon powder with processing auxiliary materials to form paste, then extruding the paste into a thin-wall material at high pressure, heating to remove volatile processing auxiliary materials and finally sintering the thin-wall material, however, in the actual preparation process, the condition of uneven quality often occurs, so that the performance of the sheath material is influenced.
Disclosure of Invention
The invention aims to provide a Teflon modified polyethylene sheath material and a preparation method thereof, which have good anti-aging effect.
The technical scheme of the invention is realized as follows:
the invention provides a Teflon modified polyethylene sheath material which is prepared from the following raw materials in parts by weight: 100-200 parts of polyethylene resin, 120-170 parts of ethylene-tetrafluoroethylene copolymer, 15-30 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 1-3 parts of antioxidant, 1-4 parts of plasticizer, 2-4 parts of flame retardant, 1-2 parts of toughening agent and 0.5-1 part of stabilizer;
the porous polyethylene-tetrafluoroethylene copolymer microsphere is prepared by the following method:
s1, preparing reaction gas: ethylene and tetrafluoroethylene are mixed to obtain reaction gas;
s2, preparing polyethylene-tetrafluoroethylene copolymer microspheres: the method comprises the steps of 1, replacing a dried reactor with high-purity nitrogen for 2-3 times, taking liquid alkane as a solvent, introducing reaction gas, obtaining a saturated solution after the solvent is saturated in gas absorption, adding a catalyst, reacting at 40-50 ℃ while stirring at a high speed, adding sulfuric acid/diethyl ether mixed solution after 3-7 hours to terminate the reaction, washing the obtained copolymer with diethyl ether, filtering, and drying to obtain polyethylene-tetrafluoroethylene copolymer microspheres;
s3, preparing porous polyethylene-tetrafluoroethylene copolymer microspheres: dispersing the polyethylene-tetrafluoroethylene copolymer microsphere in water, adding a pore-forming agent and a dispersing agent, emulsifying, filtering and drying to obtain the porous polyethylene-tetrafluoroethylene copolymer microsphere.
As a further improvement of the invention, the invention is prepared from the following raw materials in parts by weight: 120-180 parts of polyethylene resin, 140-150 parts of ethylene-tetrafluoroethylene copolymer, 19-25 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 1.5-2.5 parts of antioxidant, 2-3 parts of plasticizer, 2.5-3.5 parts of flame retardant, 1.2-1.8 parts of toughening agent and 0.6-0.8 part of stabilizer.
As a further improvement of the invention, the invention is prepared from the following raw materials in parts by weight: 150 parts of polyethylene resin, 145 parts of ethylene-tetrafluoroethylene copolymer, 22 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 2 parts of antioxidant, 2.5 parts of plasticizer, 3 parts of flame retardant, 1.6 parts of toughening agent and 0.7 part of stabilizer.
As a further improvement of the present invention, the volume ratio of ethylene to tetrafluoroethylene in step S1 is 1: (0.2-0.5).
As a further improvement of the invention, the liquid alkane in the step S2 is selected from one or a combination of a plurality of cyclohexane, n-hexane, n-heptane, cycloheptane, n-octane, cyclooctane and n-undecane; the catalyst is triethylaluminum and dicumyl peroxide, and the mass ratio is 2: (1-3) the addition amount is 2-4wt% of the saturated solution; the rotating speed of the high-speed stirring is 1500-2500r/min, the content of sulfuric acid in the sulfuric acid/diethyl ether mixed solution is 2-5wt%, and the rest is diethyl ether; the drying temperature is 50-90 ℃.
As a further improvement of the present invention, the porogen in step S3 includes a macroporous porogen and a microporous porogen, and the mass ratio is 3: (2-5) the macroporous pore-forming agent is selected from one of polyoxyethylene sorbitan fatty acid ester, polyethylene glycol octyl phenyl ether and sorbitan fatty acid ester; the micropore pore-forming agent is selected from one or a combination of a plurality of cetyl alcohol, stearic acid, povidone, urea and polyvinylpyrrolidone; the dispersing agent is one or a combination of several of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 and polyvinyl alcohol; the mass ratio of the polyethylene-tetrafluoroethylene copolymer microsphere to the pore-foaming agent to the dispersing agent is 100: (1-3): (2-7); the emulsifying condition is 10000-12000r/min for 2-4min.
As a further improvement of the present invention, the antioxidant is selected from one or a combination of several of tris (2, 4-di-t-butylphenyl) phosphite, diphenylamine, p-phenylenediamine and dihydroquinoline, 2, 6-t-butyl-4-methylphenol, bis (3, 5-t-butyl-4-hydroxyphenyl) sulfide, tetrakis [ beta- (3, 5-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol, trioctyl ester, tridecyl ester, triodes and tricetyl alcohol ester; the flame retardant is one or a combination of more of magnesium hydroxide, aluminum hydroxide, TDCPP, ammonium polyphosphate, octabromoether, triphenyl phosphate, hexabromocyclododecane, MPP, zinc borate, decabromodiphenylethane, coated red phosphorus and TBC; the plasticizer is selected from one or a combination of a plurality of di (2-ethylhexyl) phthalate, diisononyl phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate and dibutyl phthalate.
As a further improvement of the invention, the toughening agent is a mixture of polyphenyl ether ketone and polyvinyl alcohol, and the mass ratio is 1: (2-3); the stabilizer is a mixture of magnesium stearate and dibasic lead stearate, and the mass ratio is (1-4): 1.
the invention further protects the Teflon modified polyethylene sheath material, which comprises the following steps:
s1, mixing an ethylene-tetrafluoroethylene copolymer, porous polyethylene-tetrafluoroethylene copolymer microspheres, an antioxidant, a plasticizer, a flame retardant, a toughening agent and a stabilizer, and then adding the mixture into an internal mixer for mixing to obtain a mixed material;
s2, mixing the mixed materials and the polyethylene resin, extruding the mixture into a molten state by a double-screw extruder, extruding the mixture into an injection molding machine after the mixed materials are completely molten, and performing injection molding to obtain the high-temperature-resistant polyethylene resin.
As a further improvement of the invention, the mixing temperature is 95-105 ℃ and the mixing time is 5-10min.
The invention has the following beneficial effects: the porous polyethylene-tetrafluoroethylene copolymer microsphere with high specific surface area is prepared, macropores and mesopores are formed through the pore-forming agent, polytetrafluoroethylene micropowder is adsorbed in pore channels of the porous polyethylene-tetrafluoroethylene copolymer microsphere, and the porous polyethylene-tetrafluoroethylene copolymer microsphere is added into a polyethylene sheath material, has good compatibility with polyethylene and can be well dispersed in the polyethylene material, so that polytetrafluoroethylene has good modification effect on the polyethylene sheath material, and the acid resistance, alkali resistance, chemical solvent resistance, high-temperature resistance, flame retardance and the like of the polyethylene material are improved.
According to the invention, by adjusting the proportion of the macroporous pore-forming agent and the microporous pore-forming agent, macropores and mesopores with different proportions are formed on the surface of the porous polyethylene-tetrafluoroethylene copolymer microsphere, polytetrafluoroethylene micropowder with larger particle size is adsorbed in the macropores, and other modifiers with smaller particle size, such as an antioxidant, a plasticizer and the like, are adsorbed in the mesopores, so that various materials incompatible with polyethylene materials are adsorbed into the pore channels of the microsphere, the incompatible reaction is reduced, and the mechanical property and the processing property of the Teflon modified polyethylene material are improved.
The Teflon modified polyethylene sheath material prepared by the invention has the advantages of simple preparation method, good mechanical property, chemical corrosion resistance, high temperature resistance, ageing resistance, good comprehensive performance and wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1 porous polyethylene-tetrafluoroethylene copolymer microsphere
The preparation method comprises the following steps:
s1, preparing reaction gas: ethylene and tetrafluoroethylene were mixed in a volume ratio of 1:0.2, obtaining reaction gas;
s2, preparing polyethylene-tetrafluoroethylene copolymer microspheres: the method comprises the steps of 1, replacing a dried reactor with high-purity nitrogen for 2 times, taking n-hexane as a solvent, introducing reaction gas, obtaining a saturated solution after the solvent is saturated in gas absorption, adding a catalyst, reacting at 40 ℃ while stirring at a rotating speed of 1500r/min, adding a sulfuric acid/diethyl ether mixed solution (the content of sulfuric acid is 2wt%, and the rest is diethyl ether) after 3 hours, terminating the reaction, washing the obtained copolymer with diethyl ether, filtering, and drying at 50 ℃ to obtain polyethylene-tetrafluoroethylene copolymer microspheres; the catalyst is triethylaluminum and dicumyl peroxide, and the mass ratio is 2:1, the addition amount is 2wt% of the saturated solution;
s3, preparing porous polyethylene-tetrafluoroethylene copolymer microspheres: dispersing 100g of polyethylene-tetrafluoroethylene copolymer microsphere in water, adding 1g of pore-forming agent and 2g of polyethylene glycol 200, emulsifying for 2min at 10000r/min, filtering, and drying to obtain the porous polyethylene-tetrafluoroethylene copolymer microsphere. The pore-forming agent comprises macroporous pore-forming agent polyethylene glycol octyl phenyl ether and microporous pore-forming agent Kong Jiju ketone, and the mass ratio is 3:2.
preparation example 2 porous polyethylene-tetrafluoroethylene copolymer microsphere
The preparation method comprises the following steps:
s1, preparing reaction gas: ethylene and tetrafluoroethylene were mixed in a volume ratio of 1:0.5, obtaining reaction gas;
s2, preparing polyethylene-tetrafluoroethylene copolymer microspheres: 3 times of replacement of the dried reactor with high-purity nitrogen, taking n-undecane as a solvent, introducing reaction gas, after the solvent is saturated in gas absorption, obtaining a saturated solution, adding a catalyst, reacting at 50 ℃ while stirring at 2500r/min, adding sulfuric acid/diethyl ether mixed solution (the content of sulfuric acid is 5wt%, and the rest is diethyl ether) after 7 hours, terminating the reaction, washing the obtained copolymer with diethyl ether, filtering, and drying at 90 ℃ to obtain the polyethylene-tetrafluoroethylene copolymer microsphere;
s3, preparing porous polyethylene-tetrafluoroethylene copolymer microspheres: dispersing 100g of polyethylene-tetrafluoroethylene copolymer microsphere in water, adding 3g of pore-forming agent and 7g of polyvinyl alcohol, emulsifying for 4min at 12000r/min, filtering and drying to obtain the porous polyethylene-tetrafluoroethylene copolymer microsphere. The pore-forming agent comprises macroporous pore-forming agent polyoxyethylene sorbitan fatty acid ester and microporous pore-forming agent polyvinylpyrrolidone, and the mass ratio is 3:5.
example 1
The raw materials comprise the following components in parts by weight: 100 parts of polyethylene resin, 120 parts of ethylene-tetrafluoroethylene copolymer, 15 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 1 part of tricetyl (cetyl alcohol) ester, 1 part of dicyclohexyl phthalate, 2 parts of octabromoether, 1 part of toughening agent and 0.5 part of stabilizer. The toughening agent is a mixture of polyphenyl ether ketone and polyvinyl alcohol, and the mass ratio is 1:2; the stabilizer is a mixture of magnesium stearate and dibasic lead stearate, and the mass ratio is 1:1.
the preparation method comprises the following steps:
s1, mixing an ethylene-tetrafluoroethylene copolymer, porous polyethylene-tetrafluoroethylene copolymer microspheres, tricetyl alcohol ester, dicyclohexyl phthalate, octabromoether, a toughening agent and a stabilizer, and then adding the mixture into an internal mixer for mixing at the temperature of 95 ℃ for 5min to obtain a mixed material;
s2, mixing the mixed materials and the polyethylene resin, extruding the mixture into a molten state by a double-screw extruder, extruding the mixture into an injection molding machine after the mixed materials are completely molten, and performing injection molding to obtain the high-temperature-resistant polyethylene resin.
Example 2
The raw materials comprise the following components in parts by weight: 200 parts of polyethylene resin, 170 parts of ethylene-tetrafluoroethylene copolymer, 30 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 3 parts of tri (dodecanol) ester, 4 parts of di (2-ethylhexyl) phthalate, 4 parts of hexabromocyclododecane, 2 parts of toughening agent and 1 part of stabilizer. The toughening agent is a mixture of polyphenyl ether ketone and polyvinyl alcohol, and the mass ratio is 1:3, a step of; the stabilizer is a mixture of magnesium stearate and dibasic lead stearate, and the mass ratio is 4:1.
the preparation method comprises the following steps:
s1, mixing an ethylene-tetrafluoroethylene copolymer, porous polyethylene-tetrafluoroethylene copolymer microspheres, tri (dodecanol) ester, di (2-ethylhexyl) phthalate, hexabromocyclododecane, a toughening agent and a stabilizer, and then adding the mixture into an internal mixer for mixing at 105 ℃ for 10min to obtain a mixed material;
s2, mixing the mixed materials and the polyethylene resin, extruding the mixture into a molten state by a double-screw extruder, extruding the mixture into an injection molding machine after the mixed materials are completely molten, and performing injection molding to obtain the high-temperature-resistant polyethylene resin.
Example 3
The raw materials comprise the following components in parts by weight: 120 parts of polyethylene resin, 140 parts of ethylene-tetrafluoroethylene copolymer, 19 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 1.5 parts of tricetyl (cetyl alcohol) ester, 2 parts of dioctyl phthalate, 2.5 parts of flame retardant MPP, 1.2 parts of toughening agent and 0.6 part of stabilizer. The toughening agent is a mixture of polyphenyl ether ketone and polyvinyl alcohol, and the mass ratio is 1:2.2; the stabilizer is a mixture of magnesium stearate and dibasic lead stearate, and the mass ratio is 2:1.
the preparation method comprises the following steps:
s1, mixing an ethylene-tetrafluoroethylene copolymer, porous polyethylene-tetrafluoroethylene copolymer microspheres, tricetyl (cetyl alcohol) ester, dioctyl phthalate, a flame retardant MPP, a toughening agent and a stabilizer, and then adding the mixture into an internal mixer for mixing at the temperature of 97 ℃ for 6min to obtain a mixed material;
s2, mixing the mixed materials and the polyethylene resin, extruding the mixture into a molten state by a double-screw extruder, extruding the mixture into an injection molding machine after the mixed materials are completely molten, and performing injection molding to obtain the high-temperature-resistant polyethylene resin.
Example 4
The raw materials comprise the following components in parts by weight: 180 parts of polyethylene resin, 150 parts of ethylene-tetrafluoroethylene copolymer, 25 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 2.5 parts of pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], 3 parts of di Zhong Xin phthalate, 3.5 parts of flame retardant MPP, 1.8 parts of toughening agent and 0.8 part of stabilizer. The toughening agent is a mixture of polyphenyl ether ketone and polyvinyl alcohol, and the mass ratio is 1:2.8; the stabilizer is a mixture of magnesium stearate and dibasic lead stearate, and the mass ratio is 3:1.
the preparation method comprises the following steps:
s1, mixing an ethylene-tetrafluoroethylene copolymer, porous polyethylene-tetrafluoroethylene copolymer microspheres, pentaerythritol tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], di-sec-octyl phthalate, a flame retardant MPP, a toughening agent and a stabilizer, and then adding the mixture into an internal mixer for mixing at the temperature of 102 ℃ for 9min to obtain a mixed material;
s2, mixing the mixed materials and the polyethylene resin, extruding the mixture into a molten state by a double-screw extruder, extruding the mixture into an injection molding machine after the mixed materials are completely molten, and performing injection molding to obtain the high-temperature-resistant polyethylene resin.
Example 5
The raw materials comprise the following components in parts by weight: 150 parts of polyethylene resin, 145 parts of ethylene-tetrafluoroethylene copolymer, 22 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 2 parts of pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], 2.5 parts of dioctyl phthalate, 3 parts of flame retardant TDCPP, 1.6 parts of toughening agent and 0.7 part of stabilizer. The toughening agent is a mixture of polyphenyl ether ketone and polyvinyl alcohol, and the mass ratio is 1:2.5; the stabilizer is a mixture of magnesium stearate and dibasic lead stearate, and the mass ratio is 2.5:1.
the preparation method comprises the following steps:
s1, mixing an ethylene-tetrafluoroethylene copolymer, porous polyethylene-tetrafluoroethylene copolymer microspheres, pentaerythritol tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], dioctyl phthalate, a flame retardant TDCPP, a toughening agent and a stabilizer, and then adding the mixture into an internal mixer for mixing at the temperature of 100 ℃ for 7min to obtain a mixed material;
s2, mixing the mixed materials and the polyethylene resin, extruding the mixture into a molten state by a double-screw extruder, extruding the mixture into an injection molding machine after the mixed materials are completely molten, and performing injection molding to obtain the high-temperature-resistant polyethylene resin.
Example 6
In comparison with example 5, the toughening agent was polyvinyl alcohol, and the other conditions were not changed.
Example 7
Compared with example 5, the toughening agent is polyphenyl ether ketone, and other conditions are not changed.
Example 8
In comparison with example 5, the stabilizer was magnesium stearate, and the other conditions were not changed.
Example 9
In comparison with example 5, the stabilizer was dibasic lead stearate, and the other conditions were unchanged.
Comparative example 1
In comparison with example 5, no porous polyethylene-tetrafluoroethylene copolymer microsphere was added, and the other conditions were not changed.
The raw materials comprise the following components in parts by weight: 150 parts of polyethylene resin, 167 parts of ethylene-tetrafluoroethylene copolymer, 2 parts of pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], 2.5 parts of dioctyl phthalate, 3 parts of flame retardant TDCPP, 1.6 parts of toughening agent and 0.7 part of stabilizer.
Comparative example 2
In comparison with example 5, no toughening agent was added and the other conditions were not changed.
The raw materials comprise the following components in parts by weight: 150 parts of polyethylene resin, 145 parts of ethylene-tetrafluoroethylene copolymer, 22 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 2 parts of pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], 4.1 parts of dioctyl phthalate, 3 parts of flame retardant TDCPP and 0.7 part of stabilizer.
Comparative example 3
In comparison with example 5, no dioctyl phthalate was added and the other conditions were unchanged.
The raw materials comprise the following components in parts by weight: 150 parts of polyethylene resin, 145 parts of ethylene-tetrafluoroethylene copolymer, 22 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 2 parts of pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], 3 parts of flame retardant TDCPP, 4.1 parts of toughening agent and 0.7 part of stabilizer.
Comparative example 4
In comparison with example 5, no stabilizer was added and the other conditions were not changed.
The raw materials comprise the following components in parts by weight: 150 parts of polyethylene resin, 145 parts of ethylene-tetrafluoroethylene copolymer, 22 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 2 parts of pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], 2.5 parts of dioctyl phthalate, 3.7 parts of flame retardant TDCPP and 1.6 parts of toughening agent.
Comparative example 5
In comparison with example 5, no flame retardant TDCPP was added and the other conditions were unchanged.
The raw materials comprise the following components in parts by weight: 150 parts of polyethylene resin, 145 parts of ethylene-tetrafluoroethylene copolymer, 22 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 2 parts of pentaerythritol tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ], 2.5 parts of dioctyl phthalate, 4.1 parts of toughening agent and 3.7 parts of stabilizer.
Test example 1 mechanical test
The mechanical properties of the sheath materials and commercially available sheath materials obtained in examples 1 to 9 and comparative examples 1 to 5 of the present invention were tested, and the tensile strength and elongation at break were measured according to JISK6251, and the results are shown in Table 1.
TABLE 1
As shown in the table above, the Teflon modified polyethylene sheath material prepared by the embodiment of the invention has good mechanical properties.
Test example 2 volume resistivity test
The jacket materials and commercial jacket materials prepared in examples 1 to 9 and comparative examples 1 to 5 of the present invention were subjected to insulation property test, and the volume resistivity was measured at 20℃according to GB/15662-1995 standard, and the results are shown in Table 2.
TABLE 2
Group of | Volume resistivity (10) 16 Ω﹒m) |
Example 1 | 57.2 |
Example 2 | 59.1 |
Example 3 | 60.5 |
Example 4 | 59.7 |
Example 5 | 61.5 |
Example 6 | 56.4 |
Example 7 | 57.2 |
Example 8 | 55.7 |
Example 9 | 56.0 |
Comparative example 1 | 22.4 |
Comparative example 2 | 32.5 |
Comparative example 3 | 35.7 |
Comparative example 4 | 50.2 |
Comparative example 5 | 55.6 |
Commercially available | 43.5 |
As shown in the table above, the Teflon modified polyethylene sheath material prepared by the embodiment of the invention has good insulativity.
Test example 3 flame retardancy test
The jacket materials and commercial jacket materials prepared in examples 1 to 9 and comparative examples 1 to 5 of the present invention were subjected to flame retardant property test, oxygen index test according to GB/T2406-1993, and the results are shown in Table 3.
TABLE 3 Table 3
Group of | Flame retardant oxygen index |
Example 1 | 46.0 |
Example 2 | 46.2 |
Example 3 | 46.9 |
Example 4 | 46.7 |
Example 5 | 47.5 |
Example 6 | 45.7 |
Example 7 | 45.2 |
Example 8 | 31.2 |
Example 9 | 32.5 |
Comparative example 1 | 29.4 |
Comparative example 2 | 42.5 |
Comparative example 3 | 43.1 |
Comparative example 4 | 31.0 |
Comparative example 5 | 30.2 |
Commercially available | 20.3 |
As shown in the table above, the Teflon modified polyethylene sheath material prepared by the embodiment of the invention has good flame retardant property.
Compared with example 5, the toughening agents in examples 6 and 7 are respectively polyphenyl ether ketone or polyvinyl alcohol, and compared with example 5, the toughening agent in comparative example 2 is not added, so that the mechanical properties of the toughening agent are obviously reduced, and the addition of polyphenyl ether ketone and polyvinyl alcohol has a synergistic effect.
Examples 8 and 9 are respectively magnesium stearate or dibasic lead stearate, and comparative example 4 is lower in flame retardant property and volume resistivity than example 5 without adding a stabilizer, and thus the addition of magnesium stearate and dibasic lead stearate has a synergistic effect.
Compared with the example 5, the comparative example 1 is not added with the porous polyethylene-tetrafluoroethylene copolymer microsphere, the mechanical property, the flame retardant property and the volume resistivity of the porous polyethylene-tetrafluoroethylene copolymer microsphere are obviously reduced, and the porous polyethylene-tetrafluoroethylene copolymer microsphere can adsorb the modifier, so that the compatibility of the modifier in a polyethylene material system is improved, and the mechanical property and the comprehensive property are improved.
Compared with the example 5, the comparative examples 2 and 3 are respectively free from adding the toughening agent and the plasticizer, the mechanical property is reduced, and the addition of the toughening agent and the plasticizer has a synergistic effect.
In comparative examples 4 and 5, compared with example 5, the flame retardant performance was lowered without adding the stabilizer and the flame retardant, respectively, and it was found that the addition of the stabilizer and the flame retardant had a synergistic effect.
Compared with the prior art, the porous polyethylene-tetrafluoroethylene copolymer microsphere with high specific surface area is prepared, macropores and mesopores are formed through the pore-forming agent, polytetrafluoroethylene micropowder is adsorbed in pore channels of the porous polyethylene-tetrafluoroethylene copolymer microsphere, and the porous polyethylene-tetrafluoroethylene copolymer microsphere is added into a polyethylene sheath material, has good compatibility with polyethylene and can be well dispersed in the polyethylene material, so that polytetrafluoroethylene has good modification effect on the polyethylene sheath material, and the acid resistance, alkali resistance, chemical solvent resistance, high-temperature resistance, flame retardance and the like of the polyethylene material are improved.
According to the invention, by adjusting the proportion of the macroporous pore-forming agent and the microporous pore-forming agent, macropores and mesopores with different proportions are formed on the surface of the porous polyethylene-tetrafluoroethylene copolymer microsphere, polytetrafluoroethylene micropowder with larger particle size is adsorbed in the macropores, and other modifiers with smaller particle size, such as an antioxidant, a plasticizer and the like, are adsorbed in the mesopores, so that various materials incompatible with polyethylene materials are adsorbed into the pore channels of the microsphere, the incompatible reaction is reduced, and the mechanical property and the processing property of the Teflon modified polyethylene material are improved.
The Teflon modified polyethylene sheath material prepared by the invention has the advantages of simple preparation method, good mechanical property, chemical corrosion resistance, high temperature resistance, ageing resistance, good comprehensive performance and wide application prospect.
Claims (10)
1. The Teflon modified polyethylene sheath material is characterized by being prepared from the following raw materials in parts by weight: 100-200 parts of polyethylene resin, 120-170 parts of ethylene-tetrafluoroethylene copolymer, 15-30 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 1-3 parts of antioxidant, 1-4 parts of plasticizer, 2-4 parts of flame retardant, 1-2 parts of toughening agent and 0.5-1 part of stabilizer;
the porous polyethylene-tetrafluoroethylene copolymer microsphere is prepared by the following method:
s1, preparing reaction gas: ethylene and tetrafluoroethylene are mixed to obtain reaction gas;
s2, preparing polyethylene-tetrafluoroethylene copolymer microspheres: the method comprises the steps of 1, replacing a dried reactor with high-purity nitrogen for 2-3 times, taking liquid alkane as a solvent, introducing reaction gas, obtaining a saturated solution after the solvent is saturated in gas absorption, adding a catalyst, reacting at 40-50 ℃ while stirring at a high speed, adding sulfuric acid/diethyl ether mixed solution after 3-7 hours to terminate the reaction, washing the obtained copolymer with diethyl ether, filtering, and drying to obtain polyethylene-tetrafluoroethylene copolymer microspheres;
s3, preparing porous polyethylene-tetrafluoroethylene copolymer microspheres: dispersing the polyethylene-tetrafluoroethylene copolymer microsphere in water, adding a pore-forming agent and a dispersing agent, emulsifying, filtering and drying to obtain the porous polyethylene-tetrafluoroethylene copolymer microsphere.
2. The teflon modified polyethylene sheath material according to claim 1, which is prepared from the following raw materials in parts by weight: 120-180 parts of polyethylene resin, 140-150 parts of ethylene-tetrafluoroethylene copolymer, 19-25 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 1.5-2.5 parts of antioxidant, 2-3 parts of plasticizer, 2.5-3.5 parts of flame retardant, 1.2-1.8 parts of toughening agent and 0.6-0.8 part of stabilizer.
3. The teflon modified polyethylene sheath material according to claim 2, which is prepared from the following raw materials in parts by weight: 150 parts of polyethylene resin, 145 parts of ethylene-tetrafluoroethylene copolymer, 22 parts of porous polyethylene-tetrafluoroethylene copolymer microsphere, 2 parts of antioxidant, 2.5 parts of plasticizer, 3 parts of flame retardant, 1.6 parts of toughening agent and 0.7 part of stabilizer.
4. The teflon modified polyethylene sheath material of claim 1, wherein the volume ratio of ethylene to tetrafluoroethylene in step S1 is 1: (0.2-0.5).
5. The teflon-modified polyethylene sheath material according to claim 1, wherein the liquid alkane in step S2 is selected from one or a combination of several of cyclohexane, n-hexane, n-heptane, cycloheptane, n-octane, cyclooctane, n-undecane; the catalyst is triethylaluminum and dicumyl peroxide, and the mass ratio is 2: (1-3) the addition amount is 2-4wt% of the saturated solution; the rotating speed of the high-speed stirring is 1500-2500r/min, the content of sulfuric acid in the sulfuric acid/diethyl ether mixed solution is 2-5wt%, and the rest is diethyl ether; the drying temperature is 50-90 ℃.
6. The teflon modified polyethylene sheath material according to claim 1, wherein the porogen in step S3 comprises a macroporous porogen and a microporous porogen with a mass ratio of 3: (2-5) the macroporous pore-forming agent is selected from one of polyoxyethylene sorbitan fatty acid ester, polyethylene glycol octyl phenyl ether and sorbitan fatty acid ester; the micropore pore-forming agent is selected from one or a combination of a plurality of cetyl alcohol, stearic acid, povidone, urea and polyvinylpyrrolidone; the dispersing agent is one or a combination of several of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 and polyvinyl alcohol; the mass ratio of the polyethylene-tetrafluoroethylene copolymer microsphere to the pore-foaming agent to the dispersing agent is 100: (1-3): (2-7); the emulsifying condition is 10000-12000r/min for 2-4min.
7. The teflon modified polyethylene sheath material according to claim 1, wherein the antioxidant is selected from one or a combination of several of tris (2, 4-di-tert-butylphenyl) phosphite, diphenylamine, p-phenylenediamine and dihydroquinoline, 2, 6-tert-butyl-4-methylphenol, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, tetrakis [ beta- (3, 5-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol, trioctyl ester, tridecyl ester, tricodecyl alcohol ester and tricetyl alcohol ester; the flame retardant is one or a combination of more of magnesium hydroxide, aluminum hydroxide, TDCPP, ammonium polyphosphate, octabromoether, triphenyl phosphate, hexabromocyclododecane, MPP, zinc borate, decabromodiphenylethane, coated red phosphorus and TBC; the plasticizer is selected from one or a combination of a plurality of di (2-ethylhexyl) phthalate, diisononyl phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate and dibutyl phthalate.
8. The teflon modified polyethylene sheath material according to claim 1, wherein the toughening agent is a mixture of polyphenyl ether ketone and polyvinyl alcohol, and the mass ratio is 1: (2-3); the stabilizer is a mixture of magnesium stearate and dibasic lead stearate, and the mass ratio is (1-4): 1.
9. a process for preparing a teflon modified polyethylene sheath material as claimed in any one of claims 1 to 8, comprising the steps of:
s1, mixing an ethylene-tetrafluoroethylene copolymer, porous polyethylene-tetrafluoroethylene copolymer microspheres, an antioxidant, a plasticizer, a flame retardant, a toughening agent and a stabilizer, and then adding the mixture into an internal mixer for mixing to obtain a mixed material;
s2, mixing the mixed materials and the polyethylene resin, extruding the mixture into a molten state by a double-screw extruder, extruding the mixture into an injection molding machine after the mixed materials are completely molten, and performing injection molding to obtain the high-temperature-resistant polyethylene resin.
10. The method according to claim 9, wherein the kneading temperature is 95 to 105 ℃ for 5 to 10 minutes.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102186909A (en) * | 2008-10-16 | 2011-09-14 | 旭硝子株式会社 | Process for producing porous ethylene/tetrafluoroethylene copolymer and porous ethylene/tetrafluoroethylene copolymer |
CN105924758A (en) * | 2016-06-16 | 2016-09-07 | 中广核三角洲(江苏)塑化有限公司 | Irradiation-crosslinkable low-density modified polyethylene-tetrafluoroethylene copolymer insulating material |
CN107200906A (en) * | 2017-06-07 | 2017-09-26 | 深圳众厉电力科技有限公司 | A kind of CABLE MATERIALS with antimildew and antibacterial function |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN102186909A (en) * | 2008-10-16 | 2011-09-14 | 旭硝子株式会社 | Process for producing porous ethylene/tetrafluoroethylene copolymer and porous ethylene/tetrafluoroethylene copolymer |
CN105924758A (en) * | 2016-06-16 | 2016-09-07 | 中广核三角洲(江苏)塑化有限公司 | Irradiation-crosslinkable low-density modified polyethylene-tetrafluoroethylene copolymer insulating material |
CN107200906A (en) * | 2017-06-07 | 2017-09-26 | 深圳众厉电力科技有限公司 | A kind of CABLE MATERIALS with antimildew and antibacterial function |
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