CN115304914A - Environment-friendly anti-aging fiber reinforced composite material and preparation method thereof - Google Patents
Environment-friendly anti-aging fiber reinforced composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an environment-friendly anti-aging fiber reinforced composite material and a preparation method thereof, wherein the environment-friendly anti-aging fiber reinforced composite material is prepared from the following raw materials in parts by weight: 70-80 parts of triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate, 8-10 parts of thermoplastic polyester elastomer TPEE, 15-25 parts of glass fiber, 3-5 parts of nano boron fiber, 1-3 parts of coupling agent, 0.3-1 part of antioxidant, 0.5-1.5 parts of lubricant, 1-3 parts of anhydrous aluminum chloride, 5-8 parts of 4,4' -diacyl diphenyl ether and 90-120 parts of solvent; the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate is prepared by amidation condensation polymerization of 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid and bis (4-carboxyphenyl) phenylphosphine oxide. The environment-friendly anti-aging fiber reinforced composite material disclosed by the invention is excellent in anti-aging performance, mechanical property, environment friendliness, flame retardance and heat resistance, good in performance stability and long in service life.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to an environment-friendly anti-aging fiber reinforced composite material and a preparation method thereof.
Background
The material is an essential part for human survival and life, is a material basis and a precursor of human civilization, and is a motive force for directly promoting social development. The development of materials and their applications are important milestones in human social civilization and progress. Without the development of material science, there is no progress and economic prosperity of human society. The material with excellent performance is the precondition of ensuring engineering quality and use safety. The fiber reinforced composite material is one member of a large family of modern materials, is widely applied to the fields of agriculture, fishery, animal husbandry, electricity, mechanical instruments, automobiles, aerospace, national defense tips, building materials, decoration and fitment, medical appliances and the like because of light weight, corrosion resistance, high specific strength, excellent electrical insulation performance and easy processing and forming, and is an indispensable important component part for the development of the material industry.
The traditional fiber reinforced composite material has the defects of insufficient performance stability and short service life due to the compatibility problem between the fiber material and the resin base material. The fiber reinforced composite materials in the market also have the technical problems of insufficient aging resistance, mechanical property, environmental protection, flame retardance and heat resistance. In order to solve the problems, a large amount of functional additives or fillers are usually added into common fiber reinforced composite materials, but the solution causes the defects of poor processing fluidity, extravasation phenomenon in the long-term use process, poor performance stability and short service life.
For example, patent CN102731907B discloses a glass fiber reinforced PP/PA composite material, which is composed of the following raw materials by mass percent: 25-40 parts of PP, 20-40 parts of PA, 0.2-0.5 part of coupling agent, 5-10 parts of compatilizer, 5-10 parts of toughening agent, 0.2-0.5 part of antioxidant, 0.5-0.7 part of lubricant and 20-30 parts of glass fiber. The glass fiber reinforced PP/PA composite material prepared by the invention has excellent mechanical property and good appearance, meets the use requirements of multiple industries, and can be widely applied to industries such as automobiles, machinery, electric appliances and the like. However, the aging resistance, flame retardancy and heat resistance of the composite material are all to be further improved.
Therefore, the development of the environment-friendly aging-resistant fiber reinforced composite material with excellent aging resistance, mechanical property, environmental protection, flame retardance and heat resistance, good performance stability and long service life and the preparation method thereof meet market demands, have wide market value and application prospect, and have very important significance for promoting the further development of the field of fiber reinforced composite materials.
Disclosure of Invention
In view of the above problems, the present invention aims to provide an environment-friendly aging-resistant fiber-reinforced composite material with excellent aging resistance, mechanical properties, environmental protection, flame retardancy and heat resistance, good performance stability and long service life, and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: an environment-friendly anti-aging fiber reinforced composite material is prepared from the following raw materials in parts by weight: 70-80 parts of triazine-based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, 8-10 parts of thermoplastic polyester elastomer TPEE, 15-25 parts of glass fiber, 3-5 parts of nano boron fiber, 1-3 parts of coupling agent, 0.3-1 part of antioxidant, 0.5-1.5 parts of lubricant, 1-3 parts of anhydrous aluminum chloride, 5-8 parts of 4,4' -diacyl diphenyl ether and 90-120 parts of solvent; the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate is prepared by amidation condensation polymerization of 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid and bis (4-carboxyphenyl) phenylphosphine oxide.
Preferably, the solvent is chloroform.
Preferably, the lubricant is at least one of pentaerythritol stearate, N' -ethylene bis stearamide and silicone powder 6105.
Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 164.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the average diameter of the nano boron fiber is 300-500nm, and the length-diameter ratio is (20-30): 1.
Preferably, the glass fiber is alkali-free chopped glass fiber, the diameter of each monofilament is 7-11 micrometers, and the length of each monofilament is 3-4.5 millimeters.
Preferably, the thermoplastic polyester elastomer TPEE is selected from any one of the thermoplastic polyester elastomer TPEE with the trademark EM550 and the thermoplastic polyester elastomer TPEE with the trademark EM 630.
Preferably, the preparation method of the triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate comprises the following steps: adding 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent, uniformly mixing to obtain a solution, then placing the solution into a reaction kettle, replacing the air in the kettle with inert gas, reacting at 100-110 ℃ for 2-4 hours under normal pressure, then heating to 130-150 ℃ for 3-5 hours, then heating to 220-240 ℃, reacting for 6-8 hours, then vacuumizing to 500Pa, heating to 240-250 ℃, reacting for 7-12 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with methanol for 3-5 times, and then carrying out rotary evaporation to remove the desmethyl alcohol to obtain the triazinyl fluorine-containing phenylphosphine oxide based polyamide based polycondensate.
Preferably, the molar ratio of the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, the 2,3,5, 6-tetrafluoroterephthalic acid, the bis (4-carboxyphenyl) phenylphosphine oxide, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the 4-dimethylaminopyridine and the high-boiling solvent is 1.
Preferably, the high boiling point solvent is sulfolane; the inert gas is any one of nitrogen, helium, neon and argon.
Another objective of the present invention is to provide a method for preparing the environment-friendly aging-resistant fiber-reinforced composite material, comprising the following steps: uniformly mixing triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, thermoplastic polyester elastomer TPEE, glass fiber, nano boron fiber, coupling agent, antioxidant and lubricant in parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating, then performing injection molding through an injection molding machine, and demolding to obtain a crude composite material; and then uniformly mixing anhydrous aluminum chloride, 4' -diacyl chloride diphenyl ether and a solvent to obtain a dispersion system, finally soaking the crude product of the composite material in the dispersion system at the temperature of 40-55 ℃ for 8-10 hours, taking out the crude product, washing the crude product for 3-6 times by using chloroform, and then placing the crude product in a vacuum drying oven at the temperature of 85-95 ℃ for drying until the weight is constant, thereby obtaining the environment-friendly aging-resistant fiber reinforced composite material.
Preferably, the extrusion temperature of the double-screw extruder is 250-280 ℃, and the main machine rotating speed of the double-screw extruder is 210-450 rpm.
Preferably, the injection molding temperature is 250-280 ℃; the demolding temperature is 50-80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the environment-friendly anti-aging fiber reinforced composite material disclosed by the invention can be realized by adopting a conventional process method and equipment, does not need special equipment, has the advantages of low capital investment, low labor intensity, low energy consumption and high preparation efficiency and finished product qualification rate, and is suitable for continuous large-scale production.
(2) The invention discloses an environment-friendly anti-aging fiber reinforced composite material, which takes triazine-based fluorine-containing phenyl phosphine oxide based polyamide polycondensate as a composite material resin base material, wherein a molecular chain of the polycondensate simultaneously contains triazine, fluorine-containing phenyl, phenyl phosphine oxide and amide, and the groups have excellent anti-aging performance, mechanical and mechanical properties, environmental protection, flame retardance and heat resistance, good performance stability and long service life under the multiple actions of electronic effect, steric effect, conjugation effect and the like; the thermoplastic polyester elastomer TPEE is added to play a toughening role, and the molecular chains of the thermoplastic polyester elastomer TPEE have benzene ring structures, so that the compatibility is good, and the product performance stability is good.
(3) The environment-friendly anti-aging fiber reinforced composite material disclosed by the invention takes the glass fiber and the nano boron fiber as reinforcements, and the glass fiber and the nano boron fiber have good compatibility with a resin base material under the coupling action of a coupling agent; the components are mutually matched and act together, so that the cost can be controlled, and the mechanical property and the property stability of the composite material can be effectively improved.
(4) According to the environment-friendly anti-aging fiber reinforced composite material disclosed by the invention, in the forming process of the composite material, through soaking a dispersion system, acyl chloride groups on 4,4' -diacyl chloride diphenyl ether can perform Friedel-crafts acylation reaction with benzene rings on the surface of the composite material under the catalysis of anhydrous aluminum chloride to form an interpenetrating network structure, so that the physical property and the performance stability of the composite material are effectively improved, the anti-aging property, the mechanical property, the environment-friendly property, the flame retardance and the heat resistance of a final product are better, and the service life is longer.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following provides a detailed description of the product of the present invention with reference to the examples.
Example 1
An environment-friendly anti-aging fiber reinforced composite material is prepared from the following raw materials in parts by weight: 70 parts of triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, 8 parts of thermoplastic polyester elastomer TPEE, 15 parts of glass fiber, 3 parts of nano boron fiber, 1 part of coupling agent, 0.3 part of antioxidant, 0.5 part of lubricant, 1 part of anhydrous aluminum chloride, 5 parts of 4,4' -diacyl diphenyl ether and 90 parts of solvent; the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate is prepared by carrying out amidation condensation polymerization on 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid and bis (4-carboxyphenyl) phenylphosphine oxide.
The solvent is chloroform; the lubricant is pentaerythritol stearate; the antioxidant is 1010; the coupling agent is a silane coupling agent KH550; the average diameter of the nano boron fiber is 300nm, and the length-diameter ratio is 20; the glass fiber is alkali-free chopped glass fiber, the diameter of a monofilament is 7 micrometers, and the length of the monofilament is 3 millimeters; the thermoplastic polyester elastomer TPEE is selected from thermoplastic polyester elastomer TPEE with the trade name of EM 550.
The preparation method of the triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate comprises the following steps: adding 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent, uniformly mixing to obtain a solution, then placing the solution into a reaction kettle, replacing the air in the kettle with inert gas, reacting at 100 ℃ for 2 hours under normal pressure, heating to 130 ℃ for 3 hours, then heating to 220 ℃, reacting for 6 hours, then vacuumizing to 500Pa, heating to 240 ℃, reacting for 7 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with methanol for 3 times, and then carrying out rotary evaporation to remove the methanol to obtain a triazinyl fluorine-containing phenyl phosphine oxide based polyamide based polycondensate; the molar ratio of the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, high boiling solvent is 1; the high boiling point solvent is sulfolane; the inert gas is nitrogen. The M of the copolymer was determined by GPC measurement, U.S. Waters 515-2410 n ＝21200g/mol，M W /M n =1.25; it was confirmed by elemental analysis that the molar ratio of the structural unit 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide in the polycondensate was the same as the theoretical value.
A preparation method of the environment-friendly anti-aging fiber reinforced composite material comprises the following steps: uniformly mixing triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, thermoplastic polyester elastomer TPEE, glass fiber, nano boron fiber, coupling agent, antioxidant and lubricant in parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating, then performing injection molding through an injection molding machine, and demolding to obtain a crude composite material; then uniformly mixing anhydrous aluminum chloride, 4' -diacyl chloride diphenyl ether and a solvent to obtain a dispersion system, finally soaking the crude product of the composite material in the dispersion system at 40 ℃ for 8 hours, taking out the crude product, washing the crude product with chloroform for 3 times, and drying the crude product in a vacuum drying oven at 85 ℃ to constant weight to obtain the environment-friendly aging-resistant fiber reinforced composite material; the extrusion temperature of the double-screw extruder is 250-280 ℃, and the main machine rotating speed of the double-screw extruder is 210 revolutions per minute; the injection molding temperature is 250 ℃; the demolding temperature is 50 ℃.
Example 2
An environment-friendly anti-aging fiber reinforced composite material is prepared from the following raw materials in parts by weight: 72 parts of triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate, 8.5 parts of thermoplastic polyester elastomer TPEE, 17 parts of glass fiber, 3.5 parts of nano boron fiber, 1.5 parts of coupling agent, 0.5 part of antioxidant, 0.7 part of lubricant, 1.5 parts of anhydrous aluminum chloride, 6 parts of 4,4' -diacyl diphenyl ether and 100 parts of solvent; the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate is prepared by amidation condensation polymerization of 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid and bis (4-carboxyphenyl) phenylphosphine oxide.
The solvent is chloroform; the lubricant is N, N' -ethylene bis stearamide; the antioxidant is antioxidant 168; the coupling agent is a silane coupling agent KH560; the average diameter of the nano boron fiber is 350nm, and the length-diameter ratio is 23; the glass fiber is alkali-free chopped glass fiber, the diameter of a monofilament is 8 microns, and the length of the monofilament is 3.5 millimeters; the thermoplastic polyester elastomer TPEE is selected from thermoplastic polyester elastomer TPEE with the trade name of EM 630.
The preparation method of the triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate comprises the following steps: adding 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent, uniformly mixing to obtain a solution, then placing the solution into a reaction kettle, replacing the air in the kettle with inert gas, reacting at 103 ℃ under normal pressure for 2.5 hours, then heating to 135 ℃ for 3.5 hours, then heating to 225 ℃, reacting for 6.5 hours, then vacuumizing to 500Pa, heating to 243 ℃, reacting for 8 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with methanol for 4 times, and then evaporating to remove the methanol to obtain the triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate.
The molar ratio of the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, high boiling solvent is 1; the high boiling point solvent is sulfolane; the inert gas is helium.
The preparation method of the environment-friendly anti-aging fiber reinforced composite material comprises the following steps: uniformly mixing triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, thermoplastic polyester elastomer TPEE, glass fiber, nano boron fiber, coupling agent, antioxidant and lubricant in parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating, then performing injection molding through an injection molding machine, and demolding to obtain a crude composite material; then uniformly mixing anhydrous aluminum chloride, 4' -diacyl chloride diphenyl ether and a solvent to obtain a dispersion system, finally soaking the crude product of the composite material in the dispersion system at 45 ℃ for 8.5 hours, taking out the crude product, washing the crude product with chloroform for 4 times, and then placing the crude product in a vacuum drying oven at 87 ℃ for drying until the weight is constant to obtain the environment-friendly aging-resistant fiber reinforced composite material; the extrusion temperature of the double-screw extruder is 250-280 ℃, and the main machine rotating speed of the double-screw extruder is 300 revolutions per minute; the injection molding temperature is 260 ℃; the demolding temperature is 60 ℃.
Example 3
An environment-friendly anti-aging fiber reinforced composite material is prepared from the following raw materials in parts by weight: 75 parts of triazine-based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, 9 parts of thermoplastic polyester elastomer TPEE, 20 parts of glass fiber, 4 parts of nano boron fiber, 2 parts of coupling agent, 0.7 part of antioxidant, 1 part of lubricant, 2 parts of anhydrous aluminum chloride, 6.5 parts of 4,4' -diacyl diphenyl ether and 105 parts of solvent; the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate is prepared by amidation condensation polymerization of 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid and bis (4-carboxyphenyl) phenylphosphine oxide.
The solvent is chloroform; the lubricant is silicone powder 6105; the antioxidant is an antioxidant 1076; the coupling agent is a silane coupling agent KH570; the average diameter of the nano boron fiber is 400nm, and the length-diameter ratio is 25; the glass fiber is alkali-free chopped glass fiber, the diameter of a single filament is 9 micrometers, and the length of the single filament is 3.9 millimeters; the thermoplastic polyester elastomer TPEE is selected from thermoplastic polyester elastomer TPEE with the trade name of EM 550.
The preparation method of the triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate comprises the following steps: adding 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent, uniformly mixing to obtain a solution, then placing the solution into a reaction kettle, replacing the air in the kettle with inert gas, reacting at 105 ℃ for 3 hours under normal pressure, heating to 140 ℃ for 4 hours, then heating to 230 ℃, reacting for 7 hours, then vacuumizing to 500Pa, heating to 245 ℃, reacting for 9 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with methanol for 4 times, and then carrying out rotary evaporation to remove the methanol to obtain the triazinyl fluorine-containing phenyl phosphine oxide based polyamide based polycondensate.
The molar ratio of the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, high boiling solvent is 1; the high boiling point solvent is sulfolane; the inert gas is neon.
A preparation method of the environment-friendly anti-aging fiber reinforced composite material comprises the following steps: uniformly mixing triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, thermoplastic polyester elastomer TPEE, glass fiber, nano boron fiber, coupling agent, antioxidant and lubricant in parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating, then performing injection molding through an injection molding machine, and demolding to obtain a crude composite material; then uniformly mixing anhydrous aluminum chloride, 4' -diacyl chloride diphenyl ether and a solvent to obtain a dispersion system, finally soaking the crude product of the composite material in the dispersion system at 49 ℃ for 9 hours, taking out the crude product, washing the crude product with chloroform for 5 times, and drying the crude product in a vacuum drying oven at 90 ℃ to constant weight to obtain the environment-friendly aging-resistant fiber reinforced composite material; the extrusion temperature of the double-screw extruder is 250-280 ℃, and the main machine rotating speed of the double-screw extruder is 350 revolutions per minute; the injection molding temperature is 265 ℃; the demolding temperature was 65 ℃.
Example 4
An environment-friendly anti-aging fiber reinforced composite material is prepared from the following raw materials in parts by weight: 78 parts of triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate, 9.5 parts of thermoplastic polyester elastomer TPEE, 23 parts of glass fiber, 4.5 parts of nano boron fiber, 2.5 parts of coupling agent, 0.9 part of antioxidant, 1.3 parts of lubricant, 2.5 parts of anhydrous aluminum chloride, 7.5 parts of 4,4' -diacyl diphenyl ether and 110 parts of solvent; the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate is prepared by carrying out amidation condensation polymerization on 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid and bis (4-carboxyphenyl) phenylphosphine oxide.
The solvent is chloroform; the lubricant is a mixture formed by mixing pentaerythritol stearate, N' -ethylene bis stearamide and silicone powder 6105 according to the mass ratio of 1; the antioxidant is a mixture formed by mixing an antioxidant 1010, an antioxidant 168, an antioxidant 1076 and an antioxidant 164 according to a mass ratio of 1; the coupling agent is a mixture formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 3.
The average diameter of the nano boron fiber is 480nm, and the length-diameter ratio is 28; the glass fiber is alkali-free chopped glass fiber, the diameter of a monofilament is 10 micrometers, and the length of the monofilament is 4.2 millimeters; the thermoplastic polyester elastomer TPEE is a mixture formed by mixing a thermoplastic polyester elastomer TPEE with the trademark EM550 and a thermoplastic polyester elastomer TPEE with the trademark EM630 according to the mass ratio of 3.
The preparation method of the triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate comprises the following steps: adding 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent, uniformly mixing to obtain a solution, then placing the solution into a reaction kettle, replacing the air in the kettle with inert gas, reacting at 108 ℃ under normal pressure for 3.5 hours, then heating to 145 ℃ for 4.5 hours, then heating to 235 ℃, reacting for 7.5 hours, then vacuumizing to 500Pa, heating to 248 ℃, reacting for 11 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with methanol for 5 times, and then removing methanol by rotary evaporation to obtain the triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate.
The molar ratio of the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, high boiling solvent is 1.0.8; the high boiling point solvent is sulfolane; the inert gas is argon.
A preparation method of the environment-friendly anti-aging fiber reinforced composite material comprises the following steps: uniformly mixing triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, thermoplastic polyester elastomer TPEE, glass fiber, nano boron fiber, coupling agent, antioxidant and lubricant in parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating, then performing injection molding through an injection molding machine, and demolding to obtain a crude composite material; then uniformly mixing anhydrous aluminum chloride, 4' -diacyl chloride diphenyl ether and a solvent to obtain a dispersion system, finally soaking the crude product of the composite material in the dispersion system at 53 ℃ for 9.5 hours, taking out the crude product, washing the crude product with chloroform for 6 times, and drying the crude product in a vacuum drying oven at 93 ℃ to constant weight to obtain the environment-friendly aging-resistant fiber reinforced composite material; the extrusion temperature of the double-screw extruder is 250-280 ℃, and the main machine rotating speed of the double-screw extruder is 420 r/min; the injection molding temperature is 275 ℃; the demolding temperature is 75 ℃.
Example 5
An environment-friendly anti-aging fiber reinforced composite material is prepared from the following raw materials in parts by weight: 80 parts of triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate, 10 parts of thermoplastic polyester elastomer TPEE, 25 parts of glass fiber, 5 parts of nano boron fiber, 3 parts of coupling agent, 1 part of antioxidant, 1.5 parts of lubricant, 3 parts of anhydrous aluminum chloride, 8 parts of 4,4' -diacyl diphenyl ether and 120 parts of solvent; the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate is prepared by carrying out amidation condensation polymerization on 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid and bis (4-carboxyphenyl) phenylphosphine oxide.
The solvent is chloroform; the lubricant is pentaerythritol stearate; the antioxidant is antioxidant 164; the coupling agent is a silane coupling agent KH550; the average diameter of the nano boron fiber is 500nm, and the length-diameter ratio is 30; the glass fiber is alkali-free chopped glass fiber, the diameter of a single filament is 11 micrometers, and the length of the single filament is 4.5 millimeters; the thermoplastic polyester elastomer TPEE is selected from thermoplastic polyester elastomer TPEE with the trade name of EM 550.
The preparation method of the triazinyl fluorine-containing phenyl phosphine oxide based polyamide polycondensate comprises the following steps: adding 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent, uniformly mixing to obtain a solution, then placing the solution into a reaction kettle, replacing the air in the kettle with inert gas, reacting at the normal pressure of 110 ℃ for 4 hours, heating to 150 ℃ for 5 hours, then heating to 240 ℃, reacting for 8 hours, then vacuumizing to 500Pa, heating to 250 ℃, reacting for 12 hours, then cooling to room temperature, adjusting to the normal pressure, precipitating in water, washing the precipitated polymer with methanol for 5 times, and then removing the methanol by rotary evaporation to obtain the triazinyl fluorine-containing phenyl phosphine oxide based polyamide based polycondensate.
The molar ratio of the 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, high boiling solvent is 1.0.8; the high boiling point solvent is sulfolane; the inert gas is nitrogen.
A preparation method of the environment-friendly anti-aging fiber reinforced composite material comprises the following steps: uniformly mixing triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, thermoplastic polyester elastomer TPEE, glass fiber, nano boron fiber, coupling agent, antioxidant and lubricant in parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating, then performing injection molding through an injection molding machine, and demolding to obtain a crude composite material; then uniformly mixing anhydrous aluminum chloride, 4' -diacyl chloride diphenyl ether and a solvent to obtain a dispersion system, finally soaking the crude product of the composite material in the dispersion system at the temperature of 55 ℃ for 10 hours, taking out the crude product, washing the crude product with chloroform for 6 times, and then placing the crude product in a vacuum drying oven to dry the crude product at the temperature of 95 ℃ to constant weight to obtain the environment-friendly aging-resistant fiber reinforced composite material; the extrusion temperature of the double-screw extruder is 250-280 ℃, and the main machine rotating speed of the double-screw extruder is 450 revolutions per minute; the injection molding temperature is 280 ℃; the demolding temperature is 80 ℃.
Comparative example 1
An environmentally friendly, aging resistant fiber reinforced composite material substantially the same as in example 1, except that bis (4-carboxyphenyl) phenylphosphine oxide was replaced with 2,3,5, 6-tetrafluoroterephthalic acid, and 4,4' -diacyloxydiphenyl ether was not added.
Comparative example 2
An environmentally friendly, aging resistant fiber reinforced composite material was substantially the same as in example 1, except that the boron nanofiber was replaced with a glass fiber and no 4,4' -diacyl chloride diphenyl ether was added.
In order to further illustrate the unexpected positive technical effects of the products of the embodiments of the present invention, the environmental-friendly aging-resistant fiber reinforced composite material prepared by the embodiments of the present invention is subjected to a related performance test, the test results are shown in table 1, and the test methods are as follows:
(1) Tensile strength: the test was performed with reference to GB/T1447-2005.
(2) Aging resistance: the products of each example are placed in a heat aging box for artificial accelerated hot air aging under the condition of 80 ℃ aging for 80 hours, the aging resistance is measured by the retention rate of the tensile strength after aging, and the larger the retention rate value is, the better the aging resistance is.
(3) Limiting oxygen index: the test was performed with reference to GB/T2406-1993.
TABLE 1
| Test item | Tensile strength | Aging resistance | Limiting oxygen index |
| Unit | MPa | ％ | ％ |
| Example 1 | 175 | 98.69 | 39 |
| Example 2 | 179 | 98.85 | 40 |
| Example 3 | 187 | 99.05 | 42 |
| Example 4 | 192 | 99.38 | 43 |
| Example 5 | 198 | 99.70 | 45 |
| Comparative example 1 | 140 | 95.42 | 34 |
| Comparative example 2 | 129 | 96.01 | 37 |
As can be seen from table 1, the environment-friendly aging-resistant fiber reinforced composite material disclosed in the embodiment of the present invention has more excellent mechanical properties, aging resistance and flame retardancy compared with the comparative example product.
The foregoing is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the invention in any way; one of ordinary skill in the art can readily practice the present invention as described above; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The environment-friendly anti-aging fiber reinforced composite material is characterized by being prepared from the following raw materials in parts by weight: 70-80 parts of triazine-based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, 8-10 parts of thermoplastic polyester elastomer TPEE, 15-25 parts of glass fiber, 3-5 parts of nano boron fiber, 1-3 parts of coupling agent, 0.3-1 part of antioxidant, 0.5-1.5 parts of lubricant, 1-3 parts of anhydrous aluminum chloride, 5-8 parts of 4,4' -diacyl diphenyl ether and 90-120 parts of solvent; the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate is prepared by amidation condensation polymerization of 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid and bis (4-carboxyphenyl) phenylphosphine oxide.
2. The environment-friendly aging-resistant fiber-reinforced composite material of claim 1, wherein the solvent is chloroform; the lubricant is at least one of pentaerythritol stearate, N' -ethylene bis stearamide and silicone powder 6105.
3. The environment-friendly aging-resistant fiber reinforced composite material of claim 1, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant 164; the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
4. The environment-friendly aging-resistant fiber reinforced composite material of claim 1, wherein the nano boron fibers have an average diameter of 300-500nm, an aspect ratio (20-30): 1; the glass fiber is alkali-free chopped glass fiber, the diameter of each monofilament is 7-11 micrometers, and the length of each monofilament is 3-4.5 millimeters.
5. The environmentally friendly aging resistant fiber reinforced composite of claim 1, wherein the thermoplastic polyester elastomer TPEE is selected from any one of the thermoplastic polyester elastomer TPEE designated as EM550 and the thermoplastic polyester elastomer TPEE designated as EM 630.
6. The environment-friendly aging-resistant fiber reinforced composite material as claimed in claim 1, wherein the preparation method of the triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate comprises the following steps: adding 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a high boiling point solvent, uniformly mixing to obtain a solution, then placing the solution into a reaction kettle, replacing the air in the kettle with inert gas, reacting at 100-110 ℃ for 2-4 hours under normal pressure, then heating to 130-150 ℃ for 3-5 hours, then heating to 220-240 ℃, reacting for 6-8 hours, then vacuumizing to 500Pa, heating to 240-250 ℃, reacting for 7-12 hours, then cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with methanol for 3-5 times, and then carrying out rotary evaporation to remove the desmethyl alcohol to obtain the triazinyl fluorine-containing phenylphosphine oxide based polyamide based polycondensate.
7. The environmentally friendly, aging resistant fiber reinforced composite of claim 6, wherein the molar ratio of 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2,3,5, 6-tetrafluoroterephthalic acid, bis (4-carboxyphenyl) phenylphosphine oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, high boiling point solvent is 1.
8. The environmentally friendly, aging resistant fiber-reinforced composite of claim 6, wherein the high boiling point solvent is sulfolane; the inert gas is any one of nitrogen, helium, neon and argon.
9. A method for preparing an environmentally friendly, aging resistant fiber reinforced composite as claimed in any of claims 1 to 8, comprising the steps of: uniformly mixing triazine based fluorine-containing phenyl phosphine oxide based polyamide polycondensate, thermoplastic polyester elastomer TPEE, glass fiber, nano boron fiber, coupling agent, antioxidant and lubricant in parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating, then performing injection molding through an injection molding machine, and demolding to obtain a crude composite material; and then uniformly mixing anhydrous aluminum chloride, 4' -diacyl chloride diphenyl ether and a solvent to obtain a dispersion system, finally soaking the crude product of the composite material in the dispersion system at the temperature of 40-55 ℃ for 8-10 hours, taking out the crude product, washing the crude product for 3-6 times by using chloroform, and then placing the crude product in a vacuum drying oven at the temperature of 85-95 ℃ for drying until the weight is constant, thereby obtaining the environment-friendly aging-resistant fiber reinforced composite material.
10. The method for preparing the environment-friendly aging-resistant fiber reinforced composite material as claimed in claim 9, wherein the extrusion temperature of the twin-screw extruder is 250-280 ℃, and the main machine rotation speed of the twin-screw extruder is 210-450 rpm; the injection molding temperature is 250-280 ℃; the demolding temperature is 50-80 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246646A (en) * | 2006-03-15 | 2007-09-27 | Asahi Kasei Chemicals Corp | Polyamide resin composition and method for producing the same |
| CN111875959A (en) * | 2020-08-12 | 2020-11-03 | 康亚男 | Building template material and preparation method thereof |
| CN112457667A (en) * | 2020-11-27 | 2021-03-09 | 纪传生 | Environment-friendly polymer composite material and preparation method thereof |
| CN114350146A (en) * | 2022-01-06 | 2022-04-15 | 宁波群力紧固件制造有限公司 | High-strength bolt material and preparation method thereof |
| CN114907689A (en) * | 2022-05-07 | 2022-08-16 | 宁波金鼎紧固件有限公司 | High-toughness wear-resistant composite material for rail transit fastener |
-
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- 2022-09-02 CN CN202211074768.4A patent/CN115304914B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246646A (en) * | 2006-03-15 | 2007-09-27 | Asahi Kasei Chemicals Corp | Polyamide resin composition and method for producing the same |
| CN111875959A (en) * | 2020-08-12 | 2020-11-03 | 康亚男 | Building template material and preparation method thereof |
| CN112457667A (en) * | 2020-11-27 | 2021-03-09 | 纪传生 | Environment-friendly polymer composite material and preparation method thereof |
| CN114350146A (en) * | 2022-01-06 | 2022-04-15 | 宁波群力紧固件制造有限公司 | High-strength bolt material and preparation method thereof |
| CN114907689A (en) * | 2022-05-07 | 2022-08-16 | 宁波金鼎紧固件有限公司 | High-toughness wear-resistant composite material for rail transit fastener |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116397349A (en) * | 2023-03-24 | 2023-07-07 | 扬州乐康纺织科技有限公司 | Antistatic functional fiber material and preparation method and application thereof |
| CN116397349B (en) * | 2023-03-24 | 2023-11-28 | 扬州乐康纺织科技有限公司 | Antistatic functional fiber material and preparation method and application thereof |
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