CN113736252A - Composite material of phosphorus-containing polyamide modified montmorillonite modified nylon and preparation method thereof - Google Patents

Composite material of phosphorus-containing polyamide modified montmorillonite modified nylon and preparation method thereof Download PDF

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CN113736252A
CN113736252A CN202111105380.1A CN202111105380A CN113736252A CN 113736252 A CN113736252 A CN 113736252A CN 202111105380 A CN202111105380 A CN 202111105380A CN 113736252 A CN113736252 A CN 113736252A
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phosphorus
montmorillonite
nylon
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李红梅
王桂平
曾欢
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Shenzhen Jijia Paper Packaging Co ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/02—Flame or fire retardant/resistant

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Abstract

The invention relates to the technical field of nylon, and discloses a composite material of phosphorus-containing polyamide modified montmorillonite modified nylon, wherein montmorillonite is modified to obtain acyl chloride montmorillonite, the acyl chloride montmorillonite is reacted with phosphorus oxide of tri (4-aminophenoxy) to obtain phosphorus-containing montmorillonite, hyperbranched reaction is further carried out to obtain phosphorus-containing hyperbranched modified montmorillonite, the montmorillonite is uniformly dispersed to play a role in gluing and supplementing the nylon, and the hyperbranched polymer contains a large number of rigid benzene rings to improve the mechanical property of the nylon, when the composite material is heated, the phosphorus-containing polymer is decomposed to generate derivatives such as phosphoric acid and the like, so that on one hand, the free radical chain type decomposition speed is reduced, on the other hand, the dehydration and carbonization of the nylon are promoted to generate a layer of viscous layer to isolate combustible gases such as oxygen, and the montmorillonite and the nylon directly act to accelerate the formation of a compact carbon layer, insulate heat and isolate oxygen, the flame retardant property and char yield of the composite material are improved, and the phenomenon of dripping during combustion is inhibited.

Description

Composite material of phosphorus-containing polyamide modified montmorillonite modified nylon and preparation method thereof
Technical Field
The invention relates to the technical field of nylon, in particular to a composite material of phosphorus-containing polyamide modified montmorillonite modified nylon and a preparation method thereof.
Background
The ribbon is also called as a cable tie, a locking band and a cable tie, and can be divided into nylon ribbons, stainless steel ribbons and plastic-sprayed stainless steel ribbons according to the difference of materials, wherein the nylon ribbons are ribbons made of nylon as main materials, according to functions, the nylon ribbons can be divided into self-locking ribbons, slipknot ribbons, fixing head ribbons, label ribbons, packaging ribbons and the like, the nylon ribbons have the advantages of difficult aging, better acid resistance, excellent insulativity and the like, and the nylon ribbons are widely applied in places such as gifts, toys, general merchandise, fresh food and the like, but have poor mechanical property and poor flame retardant property, and the application range of the nylon ribbons is greatly limited, so that the nylon ribbons are required to be chemically modified, the comprehensive performance of the nylon ribbons is improved, and the application range of the nylon ribbons is widened.
Aiming at the flame retardant modification of polymers, a flame retardant is generally added for modification, the flame retardant can be divided into an inorganic flame retardant and an organic flame retardant, graphene, carbon nano tubes, lithium hydroxide, montmorillonite and the like in the inorganic flame retardant have better flame retardant performance, wherein the montmorillonite has the advantages of more excellent flame retardant performance, unique lamellar structure, better mechanical property and the like, and can be used as a modifier for modifying nylon so as to improve the comprehensive performance of the nylon, but the montmorillonite is an inorganic substance, has poor dispersibility in a nylon matrix and is easy to agglomerate, so that the modification effect can be greatly reduced, the organic flame retardant can be divided into a halogen-containing flame retardant, a phosphorus flame retardant, a nitrogen flame retardant and the like, wherein the phosphorus flame retardant has more excellent flame retardant performance compared with the phosphorus flame retardant, can be used as a modifier for modifying the nylon so as to further improve the comprehensive performance of the nylon, thereby widening the application range of the nylon.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a composite material of phosphorus-containing polyamide modified montmorillonite modified nylon and a preparation method thereof, and solves the problems of poor mechanical property and poor flame retardant property of a nylon cable tie.
(II) technical scheme
(1) Carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) p-nitrophenol and phosphorus oxychloride are subjected to chemical reaction to obtain the phosphorus oxide tris (4-nitrophenoxy) with the molecular formula of C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding an N, N-dimethylacetamide solvent, tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into a reaction bottle, ultrasonically dispersing uniformly, carrying out amidation reaction, cooling to room temperature, carrying out centrifugal separation, washing with deionized water, and drying to obtain phosphorus-containing montmorillonite;
(4) adding N, N-dimethylacetamide solvent, 4-biphenylacetyl chloride and phosphorus-containing montmorillonite into a reaction bottle, uniformly dispersing by ultrasonic, adding tris (4-aminophenoxy) phosphorus oxide, uniformly dispersing by ultrasonic, performing hyperbranched reaction, cooling to room temperature, performing centrifugal separation, washing with acetone and deionized water, and drying to obtain phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a toughening agent polyamide elastomer, a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into a reaction bottle, uniformly mixing, placing the mixture in a double-screw extruder for extrusion and drying, and placing the mixture in an injection molding machine for injection molding to obtain the composite material of phosphorus-containing polyamide modified montmorillonite modified nylon.
Preferably, the mass ratio of the tris (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite in the step (3) is 40-72: 10.
Preferably, the amidation reaction in the step (3) is carried out at 60-80 ℃ for 1-3 h.
Preferably, the mass ratio of the 4, 4-biphenylyl acetyl chloride, the phosphorus-containing montmorillonite and the tris (4-aminophenoxy) phosphorus oxide in the step (4) is 50-90:10: 30-62.
Preferably, the hyperbranched reaction in the step (4) is carried out at 80-100 ℃ for 8-12 h.
Preferably, the mass ratio of the polyamide elastomer, dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 in the step (5) is 5-17:8-20:4-8: 100.
Preferably, the extrusion temperature of the twin-screw extruder in the step (5) is 240-280 ℃, and the temperature of the injection molding machine is 220-260 ℃.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the composite material of phosphorus-containing polyamide modified montmorillonite modified nylon, adipic acid and montmorillonite are subjected to esterification reaction to obtain carboxylated montmorillonite, a carboxyl group is introduced, thionyl chloride is further used for treatment to obtain acyl chloride montmorillonite, an acyl chloride group is introduced, p-nitrophenol and phosphorus oxychloride are used as raw materials, nucleophilic substitution and hydrogenation reduction are carried out to obtain tris (4-aminophenoxy) phosphorus oxide, amidation reaction is further carried out with acyl chloride montmorillonite to obtain phosphorus-containing montmorillonite, an amino group on the phosphorus-containing montmorillonite is used as a reaction active site, and hyperbranched reaction is carried out with tris (4-aminophenoxy) phosphorus oxide and 4, 4-biphenyl acetyl chloride to obtain hyperbranched modified montmorillonite which is used as a filler to further obtain the composite material of phosphorus-containing polyamide modified montmorillonite modified nylon.
The hyperbranched polymer is large in molecular volume and indefinite in chain segment length, and is added into a nylon matrix as a filler, so that 'hydrogen bond' dislocation in a molecular chain can be caused, and 'gaps' can be generated between molecular chains, and the montmorillonite is covalently grafted with the montmorillonite, so that montmorillonite particles are filled in the 'gaps' between the molecular chains, the dispersity of the montmorillonite in the nylon matrix is improved, the agglomeration phenomenon of the montmorillonite is reduced, the effects of 'gluing' and 'supplementing' are achieved, the mechanical property of the nylon is improved, meanwhile, the hyperbranched polymer contains a large number of rigid benzene rings, and the mechanical property of the nylon is further improved.
According to the composite material of phosphorus-containing polyamide modified montmorillonite modified nylon, montmorillonite is uniformly dispersed in 'gaps' of hyperbranched polymer, so that the surface effect of montmorillonite and polymer molecular chains form strong interaction, when the composite material is heated, the phosphorus-containing hyperbranched polymer is decomposed to generate derivatives such as phosphoric acid and the like, phosphorus-containing free radicals are further generated, and H in an active system is captured-Reactive free radicals or OH-The active free radicals reduce the concentration of free radicals in the system, so that the chain decomposition speed of the free radicals is reduced, meanwhile, the generated derivatives such as phosphoric acid can promote the dehydration and carbonization of nylon to generate a layer of fused viscous layer to isolate combustible gas such as oxygen, meanwhile, montmorillonite and the molecular chain of the nylon directly interact to accelerate the formation of a layer of compact glass-shaped carbon layer, so that a heat-insulating and oxygen-isolating carbonized protective layer is formed, the flame retardant property and the carbonization rate of the composite material are improved, and the dripping phenomenon in the combustion process is inhibited.
Drawings
FIG. 1 is a schematic diagram of the reaction of phosphorus-containing montmorillonite;
FIG. 2 is a reaction schematic diagram of phosphorus-containing hyperbranched modified montmorillonite.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a composite material of phosphorus-containing polyamide modified montmorillonite modified nylon is prepared by the following steps:
(1) carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) p-nitrophenol and phosphorus oxychloride are subjected to chemical reaction to obtain the phosphorus oxide tris (4-nitrophenoxy) with the molecular formula of C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding N, N-dimethylacetamide solvent, tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into a reaction bottle, wherein the mass ratio of the N, N-dimethylacetamide solvent to the tris (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite is 40-72:10, performing ultrasonic dispersion uniformly, performing amidation reaction for 1-3h at 60-80 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain phosphorus-containing montmorillonite;
(4) adding N, N-dimethylacetamide solvent, 4-biphenylacetyl chloride and phosphorus-containing montmorillonite into a reaction bottle, ultrasonically dispersing uniformly, adding tris (4-aminophenoxy) phosphorus oxide, wherein the mass ratio of the 4, 4-biphenylacetyl chloride to the phosphorus-containing montmorillonite to the tris (4-aminophenoxy) phosphorus oxide is 50-90:10:30-62, ultrasonically dispersing uniformly, carrying out hyperbranched reaction at 80-100 ℃ for 8-12h, cooling to room temperature, carrying out centrifugal separation, washing with acetone and deionized water, and drying to obtain the phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a toughening agent polyamide elastomer, a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into a reaction bottle, wherein the mass ratio of the toughening agent polyamide elastomer to the cold-resistant plasticizer dioctyl adipate to the phosphorus-containing hyperbranched modified montmorillonite to the nylon 66 is 5-17:8-20:4-8:100, uniformly mixing, extruding and drying in a double-screw extruder, wherein the extrusion temperature of the double-screw extruder is 240-280 ℃, and placing in an injection molding machine for injection molding, wherein the temperature of the injection molding machine is 220-260 ℃, so as to obtain the composite material of the phosphorus-containing polyamide modified montmorillonite modified nylon.
Example 1
(1) Carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) the p-nitrophenol and the phosphorus oxychloride are subjected to chemical reaction to obtain the tri (4-nitrobenzeneOxy) phosphorus oxide of the formula C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding N, N-dimethylacetamide solvent, tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into a reaction bottle, wherein the mass ratio of the N, N-dimethylacetamide solvent to the tris (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite is 40:10, performing ultrasonic dispersion uniformly, performing amidation reaction for 1h at 60 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain phosphorus-containing montmorillonite;
(4) adding N, N-dimethylacetamide solvent, 4-biphenylacetyl chloride and phosphorus-containing montmorillonite into a reaction bottle, ultrasonically dispersing uniformly, adding tris (4-aminophenoxy) phosphorus oxide, wherein the mass ratio of the 4, 4-biphenylacetyl chloride to the phosphorus-containing montmorillonite to the tris (4-aminophenoxy) phosphorus oxide is 50:10:30, ultrasonically dispersing uniformly, carrying out hyperbranched reaction for 8 hours at 80 ℃, cooling to room temperature, carrying out centrifugal separation, washing with acetone and deionized water, and drying to obtain the phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a toughening agent polyamide elastomer, a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into a reaction bottle, wherein the mass ratio of the toughening agent polyamide elastomer to the cold-resistant plasticizer dioctyl adipate to the phosphorus-containing hyperbranched modified montmorillonite to the nylon 66 is 5:8:4:100, uniformly mixing, placing the mixture into a double-screw extruder for extrusion and drying, wherein the extrusion temperature of the double-screw extruder is 240 ℃, placing the mixture into an injection molding machine for injection molding, and the temperature of the injection molding machine is 220 ℃, so as to obtain the phosphorus-containing polyamide modified montmorillonite modified nylon composite material.
Example 2
(1) Carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) p-nitrophenol and phosphorus oxychloride are subjected to chemical reaction to obtain the phosphorus oxide tris (4-nitrophenoxy) with the molecular formula of C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding N, N-dimethylacetamide solvent, tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into a reaction bottle, wherein the mass ratio of the N, N-dimethylacetamide solvent to the tris (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite is 48:10, performing ultrasonic dispersion uniformly, performing amidation reaction for 1.5h at 65 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain phosphorus-containing montmorillonite;
(4) adding N, N-dimethylacetamide solvent, 4-biphenylacetyl chloride and phosphorus-containing montmorillonite into a reaction bottle, ultrasonically dispersing uniformly, adding tris (4-aminophenoxy) phosphorus oxide, wherein the mass ratio of the 4, 4-biphenylacetyl chloride to the phosphorus-containing montmorillonite to the tris (4-aminophenoxy) phosphorus oxide is 60:10:38, ultrasonically dispersing uniformly, carrying out hyperbranched reaction at 85 ℃ for 9 hours, cooling to room temperature, carrying out centrifugal separation, washing with acetone and deionized water, and drying to obtain the phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a toughening agent polyamide elastomer, a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into a reaction bottle, wherein the mass ratio of the toughening agent polyamide elastomer to the cold-resistant plasticizer dioctyl adipate to the phosphorus-containing hyperbranched modified montmorillonite to the nylon 66 is 8:11:5:100, uniformly mixing, placing the mixture into a double-screw extruder for extrusion and drying, wherein the extrusion temperature of the double-screw extruder is 250 ℃, placing the mixture into an injection molding machine for injection molding, and the temperature of the injection molding machine is 230 ℃, so as to obtain the phosphorus-containing polyamide modified montmorillonite modified nylon composite material.
Example 3
(1) Carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) p-nitrophenol and phosphorus oxychloride are subjected to chemical reaction to obtain the phosphorus oxide tris (4-nitrophenoxy) with the molecular formula of C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding an N, N-dimethylacetamide solvent, tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into a reaction bottle, wherein the mass ratio of the N, N-dimethylacetamide solvent to the tris (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite is 56:10, performing ultrasonic dispersion uniformly, performing amidation reaction for 2 hours at 70 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain phosphorus-containing montmorillonite;
(4) adding N, N-dimethylacetamide solvent, 4-biphenylacetyl chloride and phosphorus-containing montmorillonite into a reaction bottle, ultrasonically dispersing uniformly, adding tris (4-aminophenoxy) phosphorus oxide, wherein the mass ratio of the 4, 4-biphenylacetyl chloride to the phosphorus-containing montmorillonite to the tris (4-aminophenoxy) phosphorus oxide is 70:10:46, ultrasonically dispersing uniformly, carrying out hyperbranched reaction for 10 hours at 90 ℃, cooling to room temperature, carrying out centrifugal separation, washing with acetone and deionized water, and drying to obtain the phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a toughening agent polyamide elastomer, a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into a reaction bottle in a mass ratio of 11:14:6:100, uniformly mixing, placing the mixture into a double-screw extruder for extrusion and drying, wherein the extrusion temperature of the double-screw extruder is 260 ℃, placing the mixture into an injection molding machine for injection molding, and the temperature of the injection molding machine is 240 ℃ to obtain the phosphorus-containing polyamide modified montmorillonite modified nylon composite material.
Example 4
(1) Carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) p-nitrophenol and phosphorus oxychloride are subjected to chemical reaction to obtain the phosphorus oxide tris (4-nitrophenoxy) with the molecular formula of C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding an N, N-dimethylacetamide solvent, tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into a reaction bottle, wherein the mass ratio of the N, N-dimethylacetamide solvent to the tris (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite is 64:10, performing ultrasonic dispersion uniformly, performing amidation reaction at 75 ℃ for 2.5 hours, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain phosphorus-containing montmorillonite;
(4) adding N, N-dimethylacetamide solvent, 4-biphenylacetyl chloride and phosphorus-containing montmorillonite into a reaction bottle, ultrasonically dispersing uniformly, adding tris (4-aminophenoxy) phosphorus oxide, wherein the mass ratio of the 4, 4-biphenylacetyl chloride to the phosphorus-containing montmorillonite to the tris (4-aminophenoxy) phosphorus oxide is 80:10:54, ultrasonically dispersing uniformly, carrying out hyperbranched reaction at 95 ℃ for 11 hours, cooling to room temperature, carrying out centrifugal separation, washing with acetone and deionized water, and drying to obtain the phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a toughening agent polyamide elastomer, a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into a reaction bottle, wherein the mass ratio of the toughening agent polyamide elastomer to the cold-resistant plasticizer dioctyl adipate to the phosphorus-containing hyperbranched modified montmorillonite to the nylon 66 is 14:17:7:100, uniformly mixing, placing the mixture into a double-screw extruder for extrusion and drying, wherein the extrusion temperature of the double-screw extruder is 270 ℃, placing the mixture into an injection molding machine for injection molding, and the temperature of the injection molding machine is 250 ℃, so as to obtain the phosphorus-containing polyamide modified montmorillonite modified nylon composite material.
Example 5
(1) Carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) p-nitrophenol and phosphorus oxychloride are subjected to chemical reaction to obtain the phosphorus oxide tris (4-nitrophenoxy) with the molecular formula of C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding an N, N-dimethylacetamide solvent, tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into a reaction bottle, wherein the mass ratio of the N, N-dimethylacetamide solvent to the tris (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite is 72:10, performing ultrasonic dispersion uniformly, performing amidation reaction for 3 hours at 80 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain phosphorus-containing montmorillonite;
(4) adding N, N-dimethylacetamide solvent, 4-biphenylacetyl chloride and phosphorus-containing montmorillonite into a reaction bottle, ultrasonically dispersing uniformly, adding tris (4-aminophenoxy) phosphorus oxide, wherein the mass ratio of the 4, 4-biphenylacetyl chloride to the phosphorus-containing montmorillonite to the tris (4-aminophenoxy) phosphorus oxide is 90:10:62, ultrasonically dispersing uniformly, carrying out hyperbranched reaction at 100 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation, washing with acetone and deionized water, and drying to obtain the phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a toughening agent polyamide elastomer, a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into a reaction bottle, wherein the mass ratio of the toughening agent polyamide elastomer to the cold-resistant plasticizer dioctyl adipate to the phosphorus-containing hyperbranched modified montmorillonite to the nylon 66 is 17:20:8:100, uniformly mixing, placing the mixture in a double-screw extruder for extrusion and drying, wherein the extrusion temperature of the double-screw extruder is 280 ℃, placing the mixture in an injection molding machine for injection molding, and the temperature of the injection molding machine is 260 ℃, so as to obtain the phosphorus-containing polyamide modified montmorillonite modified nylon composite material.
Comparative example 1
(1) Carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) p-nitrophenol and phosphorus oxychloride are subjected to chemical reaction to obtain the phosphorus oxide tris (4-nitrophenoxy) with the molecular formula of C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding N, N-dimethylacetamide solvent, tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into a reaction bottle, wherein the mass ratio of the N, N-dimethylacetamide solvent to the tris (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite is 32:10, performing ultrasonic dispersion uniformly, performing amidation reaction for 2 hours at 70 ℃, cooling to room temperature, performing centrifugal separation, washing with deionized water, and drying to obtain phosphorus-containing montmorillonite;
(4) adding N, N-dimethylacetamide solvent, 4-biphenylacetyl chloride and phosphorus-containing montmorillonite into a reaction bottle, ultrasonically dispersing uniformly, adding tris (4-aminophenoxy) phosphorus oxide, wherein the mass ratio of the 4, 4-biphenylacetyl chloride to the phosphorus-containing montmorillonite to the tris (4-aminophenoxy) phosphorus oxide is 40:10:24, ultrasonically dispersing uniformly, carrying out hyperbranched reaction for 10 hours at 90 ℃, cooling to room temperature, carrying out centrifugal separation, washing with acetone and deionized water, and drying to obtain the phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a toughening agent polyamide elastomer, a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into a reaction bottle, uniformly mixing, placing the mixture into a double-screw extruder to extrude and dry, wherein the mass ratio of the toughening agent polyamide elastomer to the cold-resistant plasticizer dioctyl adipate to the phosphorus-containing hyperbranched modified montmorillonite to the nylon 66 is 4:6.4:3.2:100, the extrusion temperature of the double-screw extruder is 260 ℃, placing the double-screw extruder into an injection molding machine to perform injection molding, and the temperature of the injection molding machine is 240 ℃ to obtain the phosphorus-containing polyamide modified montmorillonite modified nylon composite material.
The composite materials of phosphorus-containing polyamide modified montmorillonite modified nylon obtained in the examples and comparative examples were tested for tensile strength and tensile elastic modulus using a PS-9305S type universal tester.
Figure BDA0003272058000000101
The limit oxygen index of the composite materials of the phosphorus-containing polyamide modified montmorillonite modified nylon obtained in the examples and the comparative examples was measured by using an HC-2 type oxygen index tester.
Figure BDA0003272058000000102

Claims (7)

1. The composite material of phosphorus-containing polyamide modified montmorillonite modified nylon is characterized in that: the preparation method of the composite material of phosphorus-containing polyamide modified montmorillonite modified nylon comprises the following steps:
(1) carrying out carboxylation modification on montmorillonite by using adipic acid to obtain carboxylated montmorillonite, and further treating by using thionyl chloride to obtain acyl chloride montmorillonite;
(2) p-nitrophenol and phosphorus oxychloride are subjected to chemical reaction to obtain the phosphorus oxide tris (4-nitrophenoxy) with the molecular formula of C18H12N3O10P, further carrying out hydrogenation reduction treatment to obtain tri (4-aminophenoxy) phosphorus oxide with the molecular formula of C18H18N3O4P；
(3) Adding tris (4-aminophenoxy) phosphorus oxide and carboxylated montmorillonite into an N, N-dimethylacetamide solvent, carrying out ultrasonic dispersion uniformly, carrying out amidation reaction, cooling, carrying out centrifugal separation, washing and drying to obtain phosphorus-containing montmorillonite;
(4) adding 4, 4-biphenylyl acetyl chloride and phosphorus-containing montmorillonite into an N, N-dimethylacetamide solvent, ultrasonically dispersing uniformly, adding tris (4-aminophenoxy) phosphorus oxide, ultrasonically dispersing uniformly, performing hyperbranched reaction, cooling, centrifugally separating, washing and drying to obtain phosphorus-containing hyperbranched modified montmorillonite;
(5) adding a cold-resistant plasticizer dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 into the toughening agent polyamide elastomer, uniformly mixing, placing in a double-screw extruder for extrusion and drying, and placing in an injection molding machine for injection molding to obtain the composite material of phosphorus-containing polyamide modified montmorillonite modified nylon.
2. The composite material of phosphorus-containing polyamide modified montmorillonite modified nylon of claim 1, wherein: the mass ratio of the tri (4-aminophenoxy) phosphorus oxide to the carboxylated montmorillonite in the step (3) is 40-72: 10.
3. The composite material of phosphorus-containing polyamide modified montmorillonite modified nylon of claim 1, wherein: the amidation reaction in the step (3) is carried out for 1-3h at the temperature of 60-80 ℃.
4. The composite material of phosphorus-containing polyamide modified montmorillonite modified nylon of claim 1, wherein: in the step (4), the mass ratio of the 4, 4-biphenylyl acetyl chloride to the phosphorus-containing montmorillonite to the tris (4-aminophenoxy) phosphorus oxide is 50-90:10: 30-62.
5. The composite material of phosphorus-containing polyamide modified montmorillonite modified nylon of claim 1, wherein: the hyperbranched reaction condition in the step (4) is that the reaction is carried out for 8 to 12 hours at a temperature of between 80 and 100 ℃.
6. The composite material of phosphorus-containing polyamide modified montmorillonite modified nylon of claim 1, wherein: in the step (5), the mass ratio of the polyamide elastomer, dioctyl adipate, phosphorus-containing hyperbranched modified montmorillonite and nylon 66 is 5-17:8-20:4-8: 100.
7. The composite material of phosphorus-containing polyamide modified montmorillonite modified nylon of claim 1, wherein: the extrusion temperature of the twin-screw extruder in the step (5) is 240-280 ℃, and the temperature of the injection molding machine is 220-260 ℃.
CN202111105380.1A 2021-09-22 2021-09-22 Composite material of phosphorus-containing polyamide modified montmorillonite modified nylon and preparation method thereof Withdrawn CN113736252A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116278282A (en) * 2023-04-06 2023-06-23 临沂千源包装印刷有限公司 Preparation method of heat-resistant polyethylene-nylon composite film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116278282A (en) * 2023-04-06 2023-06-23 临沂千源包装印刷有限公司 Preparation method of heat-resistant polyethylene-nylon composite film
CN116278282B (en) * 2023-04-06 2023-08-08 临沂千源包装印刷有限公司 Preparation method of heat-resistant polyethylene-nylon composite film

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