CN116731473B - Flame-retardant composite master batch based on fiber reinforcement and preparation method thereof - Google Patents

Flame-retardant composite master batch based on fiber reinforcement and preparation method thereof Download PDF

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CN116731473B
CN116731473B CN202310860352.3A CN202310860352A CN116731473B CN 116731473 B CN116731473 B CN 116731473B CN 202310860352 A CN202310860352 A CN 202310860352A CN 116731473 B CN116731473 B CN 116731473B
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reaction
fiber
flame
modified polyimide
master batch
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CN116731473A (en
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颜光宇
贺志军
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Guangzhou Yinsu Flame Retardant New Material Co ltd
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Guangzhou Yinsu Flame Retardant New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts
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    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Abstract

The invention discloses a fiber-reinforced-based flame-retardant composite master batch and a preparation method thereof, wherein the flame-retardant composite master batch is prepared from the following raw materials: the modified polyimide fiber, kaolin, montmorillonite, brominated epoxy resin, sodium antimonate, a coupling agent and an antioxidant are used as main materials, flexible ether bonds are introduced into a molecular main chain of the modified polyimide fiber, the processability of the polyimide fiber is improved, the branched chain contains phosphorus-containing groups and nitrogen-containing groups, the synergistic flame-retardant effect can be achieved, the Schiff base compound is introduced, the antibacterial effect is good, the imidazoline has a curing effect on the epoxy resin, the compatibility of the modified polyimide fiber and the epoxy resin can be improved, the master batch has the high adhesive property of the epoxy resin, and the thermal stability and self-extinguishing property of the modified polyimide fiber, and meanwhile, the components are not easy to migrate and exude, and the uniform dispersion is realized.

Description

Flame-retardant composite master batch based on fiber reinforcement and preparation method thereof
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a fiber-reinforced flame-retardant composite master batch and a preparation method thereof.
Background
Polyimide is used as a special engineering material, is widely applied to the fields of aviation, aerospace, microelectronics, nanometer, liquid crystal, separation membrane, laser and the like, is one of the most promising engineering plastics in the 21 st century in research, development and utilization of polyimide in the 20 th century, has huge application prospect in terms of performance and synthesis due to the outstanding characteristics of polyimide, not only as a structural material or a functional material, but also has poor adhesion, and the flame retardant technology becomes the key point of research along with the wide application of polyimide in the fields of construction, electric appliances, traffic, communication and the like, however, most of flame retardants can influence the mechanical properties of products when being applied to polyimide products, and meanwhile, have the problems of difficult dispersion, difficult processing, large dust amount and the like, and the defects are to be improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a fiber-reinforced-based flame-retardant composite master batch and a preparation method thereof.
The invention takes brominated epoxy resin and modified polyimide fiber as main materials, polyimide is used as a special engineering material, the prepared fiber has higher strength, flexible ether bond is introduced into the molecular main chain of the obtained modified polyimide fiber, the processability of the polyimide fiber is improved, the branched chain contains phosphorus-containing groups and nitrogen-containing groups, the synergistic flame retardant effect can be achieved, schiff base compound is introduced, the antibacterial and antifungal effects are good, the imidazoline has a curing effect on the epoxy resin, the compatibility of the modified polyimide fiber and the epoxy resin can be improved, the master batch has the high adhesive property of the epoxy resin, the thermal stability and self-extinguishing property of the modified polyimide fiber, and the components are not easy to migrate and exude, so that the uniform dispersion is realized.
The aim of the invention can be achieved by the following technical scheme:
a flame-retardant composite master batch based on fiber reinforcement is prepared from the following raw materials in parts by weight: 20-30 parts of modified polyimide fiber, 5-10 parts of kaolin, 3-5 parts of montmorillonite, 30-40 parts of brominated epoxy resin, 3-5 parts of sodium antimonate, 1-3 parts of coupling agent and 0.2-0.5 part of antioxidant.
Further, the coupling agent is one or more of KH560, KH580, KH791, KH901 and KH 902.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 300 and antioxidant 168.
Further, the modified polyimide fiber is prepared by the following steps:
s1, adding 3-hydroxy-2, 2-bis (hydroxymethyl) -propionaldehyde into a three-necked flask under the protection of nitrogen, adding DMF as a solvent, adding potassium carbonate, stirring for 10min, then adding p-chloronitrobenzene into a DMF solution dropping funnel, slowly dropping into the three-necked flask, controlling the heating temperature to be 100 ℃ after the dropping is completed, reacting for 6h, slowly adding the reaction solution into ice water after the reaction is completed, precipitating solids, carrying out suction filtration, drying, carrying out column chromatography separation by using ethyl acetate and petroleum ether, and collecting chromatographic liquid for reduced pressure rotary evaporation to obtain an intermediate 1; the dosage ratio of 3-hydroxy-2, 2-bis (hydroxymethyl) -propionaldehyde, potassium carbonate and p-chloronitrobenzene is 10g:10.3g:11.7g;
nucleophilic substitution reaction is carried out on-OH on 3-hydroxy-2, 2-bis (hydroxymethyl) -propionaldehyde molecules and-Cl on p-chloronitrobenzene molecules, and the molar ratio of the two is controlled to be close to 1:2, so as to obtain an intermediate 1, wherein the specific reaction process is as follows:
s2, placing the intermediate 1 and dimethyl phosphono chloride into a flask, adding acetonitrile as a solvent, absorbing tail gas by using 10% sodium hydroxide aqueous solution, controlling the heating temperature to be 85 ℃ under the protection of nitrogen, carrying out reflux reaction for 5 hours, carrying out freeze-drying treatment on the reaction solution after the reaction is finished, washing twice after freeze-drying, and then placing the solution into a vacuum drying oven at 80 ℃ for drying for 6 hours to obtain an intermediate 2; the dosage ratio of the intermediate 1, the dimethyl phosphonic acid chloride and the acetonitrile is 10g to 3g to 100mL;
nucleophilic substitution reaction is carried out on-OH on the intermediate 1 molecule and-Cl on the dimethyl phosphonic chloride molecule, and the following chemical reaction is carried out by controlling the molar ratio of the-OH to the-Cl to be close to 1:1, so as to obtain an intermediate 2:
s3, placing the intermediate 2 in a three-necked flask, adding absolute ethyl alcohol as a solvent, and stirring for 5min; dissolving 4-aminoimidazole in absolute ethyl alcohol, slowly dripping the solution into a flask, heating and refluxing for reaction for 4 hours after dripping, decompressing and steaming a product after the reaction is finished, and recrystallizing the product by using absolute ethyl alcohol to obtain an intermediate 3; the ratio of the dosage of the intermediate 2, 4-aminoimidazole is 10g to 1.8g;
the amino on the 4-amino imidazole molecule and the aldehyde group on the intermediate 2 molecule are subjected to condensation reaction to generate Schiff base, so as to obtain an intermediate 3; the specific reaction process is as follows:
s4, adding the intermediate 3 and Raney nickel into a reaction kettle, adding 1, 4-dioxane as a solvent, and sequentially introducing N 2 、H 2 Performing replacement, and introducing H 2 The pressure is 3.7MPa, the reaction is carried out for 7 hours at 80 ℃, after the reaction is finished, the catalyst is filtered out while the reaction is hot, the filtrate is added into cold water, solid is separated out and filtered out, and then the solid is placed into a vacuum drying oven at 80 ℃ for drying for 6 hours, thus obtaining an intermediate 4; the dosage ratio of the intermediate 3, the Raney nickel and the 1, 4-dioxane is 10g to 1g to 100mL;
the nitro group on the intermediate 3 molecule is hydrogenated into amino group through Raney nickel catalytic hydrogenation, thus obtaining an intermediate 4, and the specific reaction process is as follows:
s5, at N 2 Under the protection, adding the intermediate 4 and dimethylacetamide into a flask, stirring for 20min, adding pyromellitic dianhydride in batches, controlling the temperature to be 0 ℃ for reaction for 2h, then reacting for 8h at room temperature, decompressing and steaming after the reaction is finished,intermediate 5 is obtained; the dosage ratio of the intermediate 4 to the dimethylacetamide to the pyromellitic dianhydride is 10g to 100mL to 4.8g;
the intermediate 4 molecules and pyromellitic dianhydride molecules are condensed to obtain an intermediate 5, and the specific reaction process is as follows:
s6, placing the intermediate 5 into a three-neck flask, adding a 1-methyl-2-pyrrolidone and N, N-dimethylformamide 1:3 mixed solvent, stirring for 20min, performing reduced pressure bubble removal, filtering to obtain a spinning solution, performing wet spinning through a spinneret to obtain primary fibers, performing multiple water washing, placing into a tubular furnace, and performing thermal drafting and filament collection according to a programmed temperature (190 ℃/1h,230 ℃/1h,250 ℃/0.5h,300 ℃/1 h) to obtain modified polyimide fibers; the method comprises the steps of carrying out a first treatment on the surface of the
The intermediate 5 molecules are subjected to thermal imidization at high temperature to obtain the modified polyimide fiber, and the specific reaction process is as follows:
the main chain of the obtained modified polyimide fiber is introduced with flexible ether bond, so that the processability of the polyimide fiber is improved, the branched chain contains phosphorus-containing groups and nitrogen-containing groups, the polyphosphoric acid film which can be generated when the phosphorus element burns wraps the substrate, and the nitrogen element can generate NO and NO when the nitrogen element burns 2 、N 2 、NH 3 The flame retardant polyurethane foam is characterized in that the flame retardant polyurethane foam is made of a non-combustible gas, heat insulation and oxygen absorption, and has a synergistic flame retardant effect, schiff base compounds are introduced, the Schiff base has good antibacterial and antifungal effects, and N, NH groups on the connected imidazoline heterocycle can form chemical bonds with bases on DNA of protein in bacteria, so that the structure of the DNA in cells is destroyed, the replication capacity of the DNA in cells is lost, the cell death is caused, the DNA of bacterial cells is in a naked state, and the DNA of human cells is in a coated state, so that the flame retardant polyurethane foam is safer in the processing and use processes, and is the same asThe imidazoline can catalyze the ring-opening polymerization of epoxy groups, so that linear molecules can generate netlike macromolecules, the epoxy resin is cured, the compatibility of the modified polyimide fibers and the epoxy resin can be improved, the epoxy resin can be interpenetrating reacted with the modified polyimide fibers to form a double continuous phase structure when being cured, the dispersion stress and the original performance are facilitated, the master batch has the high bonding performance of the epoxy resin, the thermal stability and the self-extinguishing performance of the modified polyimide fibers, and meanwhile, the components are not easy to migrate and exude, and the uniform dispersion is realized.
The invention also aims to provide a preparation method of the fiber-reinforced-based flame-retardant composite master batch, which comprises the following steps of;
firstly, placing brominated epoxy resin and a coupling agent into a kneader for uniform mixing, then adding kaolin and montmorillonite, stirring for 30min, and continuously adding modified polyimide fibers, sodium antimonate and an antioxidant, and stirring for 10min at a high speed to obtain a mixture;
and secondly, putting the mixture into a double-cone feeding single-screw machine for plasticizing and granulating, and cooling to obtain the fiber-reinforced-based flame-retardant composite master batch.
The invention has the beneficial effects that:
the invention takes brominated epoxy resin and modified polyimide fiber as main materials, polyimide is used as a special engineering material, the prepared fiber has higher strength, flexible ether bond is introduced into the molecular main chain of the obtained modified polyimide fiber, the processability of the polyimide fiber is improved, the branched chain contains phosphorus-containing groups and nitrogen-containing groups, the synergistic flame retardant effect can be achieved, schiff base compound is introduced, the antibacterial and antifungal effects are good, the imidazoline has a curing effect on the epoxy resin, the compatibility of the modified polyimide fiber and the epoxy resin can be improved, the master batch has the high adhesive property of the epoxy resin, the thermal stability and self-extinguishing property of the modified polyimide fiber, and the components are not easy to migrate and exude, so that the uniform dispersion is realized.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
Example 1
Preparing modified polyimide fibers:
s1, under the protection of nitrogen, adding 10g of 3-hydroxy-2, 2-bis (hydroxymethyl) -propionaldehyde into a three-necked flask, adding DMF as a solvent, adding 10.3g of potassium carbonate, stirring for 10min, then dissolving 11.7g of p-chloronitrobenzene in DMF, adding into a dropping funnel, slowly dropping into the three-necked flask, controlling the heating temperature to be 100 ℃ after the dropping is completed, reacting for 6h, slowly adding the reaction solution into ice water after the reaction is completed, precipitating solids for suction filtration, separating by column chromatography with ethyl acetate and petroleum ether after drying, and collecting the chromatographic liquid for reduced pressure rotary evaporation to obtain an intermediate 1;
s2, putting 10g of intermediate 1 and 3g of dimethylphosphonyl chloride into a flask, adding 100mL of acetonitrile as a solvent, absorbing tail gas by using 10% sodium hydroxide aqueous solution, controlling the heating temperature to be 85 ℃ under the protection of nitrogen, carrying out reflux reaction for 5 hours, carrying out freeze-drying treatment on the reaction liquid after the reaction is finished, washing twice after freeze-drying, and then drying in a vacuum drying oven at 80 ℃ for 6 hours to obtain intermediate 2;
s3, placing 10g of the intermediate 2 into a three-necked flask, adding absolute ethyl alcohol as a solvent, and stirring for 5min; dissolving 1.8g of 4-aminoimidazole in absolute ethyl alcohol, slowly dripping the solution into a flask, heating and refluxing for reaction for 4 hours after dripping, decompressing and steaming a product after the reaction is finished, and recrystallizing the product by using absolute ethyl alcohol to obtain an intermediate 3;
s4, adding 10g of intermediate 3 and 1g of Raney nickel into a reaction kettle, adding 100mL of 1, 4-dioxane as a solvent, and sequentially introducing N 2 、H 2 Performing replacement, and introducing H 2 The pressure is 3.7MPa, the reaction is carried out for 7 hours at 80 ℃, after the reaction is finished, the catalyst is filtered out while the reaction is hot, the filtrate is added into cold water, the solid is separated out and filtered, and then the mixture is placed into a vacuum drying oven at 80 ℃ for dryingDrying for 6h to obtain an intermediate 4;
s5, at N 2 Under the protection, adding 10g of intermediate 4 and 100mL of dimethylacetamide into a flask, stirring for 20min, adding 4.8g of pyromellitic dianhydride in batches, controlling the temperature to be 0 ℃ for reaction for 2h, then reacting for 8h at room temperature, and performing reduced pressure rotary evaporation after the reaction is completed to obtain an intermediate 5;
s6, placing 10g of intermediate 5 into a three-necked flask, adding 100mL of a mixed solvent of 1-methyl-2-pyrrolidone and N, N-dimethylformamide 1:3, stirring for 20min, decompressing and removing bubbles, filtering to obtain a spinning solution, performing wet spinning through a spinneret to obtain nascent fibers, washing with water for multiple times, placing into a tube furnace, heating according to a program (190 ℃/1h,230 ℃/1h,250 ℃/0.5h,300 ℃/1 h), and performing hot drawing and filament collection to obtain the modified polyimide fibers.
Example 2
Preparing modified polyimide fibers:
s1, under the protection of nitrogen, adding 20g of 3-hydroxy-2, 2-bis (hydroxymethyl) -propionaldehyde into a three-necked flask, adding DMF as a solvent, adding 20.6g of potassium carbonate, stirring for 10min, then dissolving 23.4g of p-chloronitrobenzene in DMF, adding into a dropping funnel, slowly dropping into the three-necked flask, controlling the heating temperature to be 100 ℃ after the dropping is completed, reacting for 6h, slowly adding the reaction solution into ice water after the reaction is completed, precipitating solids for suction filtration, separating by column chromatography with ethyl acetate and petroleum ether after drying, and collecting the chromatographic liquid for reduced pressure rotary evaporation to obtain an intermediate 1;
s2, putting 20g of intermediate 1 and 6g of dimethylphosphonyl chloride into a flask, adding 200mL of acetonitrile as a solvent, absorbing tail gas by using 10% sodium hydroxide aqueous solution, controlling the heating temperature to be 85 ℃ under the protection of nitrogen, carrying out reflux reaction for 5 hours, carrying out freeze-drying treatment on the reaction liquid after the reaction is finished, washing twice after freeze-drying, and then drying in a vacuum drying oven at 80 ℃ for 6 hours to obtain intermediate 2;
s3, placing 20g of the intermediate 2 into a three-necked flask, adding absolute ethyl alcohol as a solvent, and stirring for 5min; dissolving 3.6g of 4-aminoimidazole in absolute ethyl alcohol, slowly dripping the solution into a flask, heating and refluxing for reaction for 4 hours after dripping, decompressing and steaming a product after the reaction is finished, and recrystallizing the product by using absolute ethyl alcohol to obtain an intermediate 3;
s4, adding 20g of intermediate 3 and 2g of Raney nickel into a reaction kettle, adding 200mL of 1, 4-dioxane as a solvent, and sequentially introducing N 2 、H 2 Performing replacement, and introducing H 2 The pressure is 3.7MPa, the reaction is carried out for 7 hours at 80 ℃, after the reaction is finished, the catalyst is filtered out while the reaction is hot, the filtrate is added into cold water, solid is separated out and filtered out, and then the solid is placed into a vacuum drying oven at 80 ℃ for drying for 6 hours, thus obtaining an intermediate 4;
s5, at N 2 Under the protection, adding 20g of intermediate 4 and 200mL of dimethylacetamide into a flask, stirring for 20min, adding 9.6g of pyromellitic dianhydride in batches, controlling the temperature to be 0 ℃ for reaction for 2h, then reacting for 8h at room temperature, and performing reduced pressure rotary evaporation after the reaction is completed to obtain an intermediate 5;
s6, placing 10g of intermediate 5 into a three-necked flask, adding 100mL of a mixed solvent of 1-methyl-2-pyrrolidone and N, N-dimethylformamide 1:3, stirring for 20min, decompressing and removing bubbles, filtering to obtain a spinning solution, performing wet spinning through a spinneret to obtain nascent fibers, washing with water for multiple times, placing into a tube furnace, heating according to a program (190 ℃/1h,230 ℃/1h,250 ℃/0.5h,300 ℃/1 h), and performing hot drawing and filament collection to obtain the modified polyimide fibers.
Example 3
Firstly, putting 30g of brominated epoxy resin and 1g of KH560 coupling agent into a kneader for uniform mixing, then adding 5g of kaolin and 3g of montmorillonite, stirring for 30min, and continuously adding 20g of modified polyimide fiber prepared in example 1, 3g of sodium antimonate and 0.2g of antioxidant 1010, and stirring at a high speed for 10min to obtain a mixture;
and secondly, putting the mixture into a double-cone feeding single-screw machine for plasticizing and granulating, and cooling to obtain the fiber-reinforced-based flame-retardant composite master batch.
Example 4
Firstly, placing 35g of brominated epoxy resin and 2g of KH580 coupling agent into a kneader for uniform mixing, then adding 7.5g of kaolin and 4g of montmorillonite, stirring for 30min, and continuously adding 25g of modified polyimide fiber prepared in example 2, 4g of sodium antimonate and 0.35g of antioxidant 300, and stirring at a high speed for 10min to obtain a mixture;
and secondly, putting the mixture into a double-cone feeding single-screw machine for plasticizing and granulating, and cooling to obtain the fiber-reinforced-based flame-retardant composite master batch.
Example 5
Firstly, placing 40g of brominated epoxy resin and 3g of KH791 coupling agent into a kneader for uniform mixing, then adding 10g of kaolin and 5g of montmorillonite, stirring for 30min, and continuously adding 30g of modified polyimide fiber prepared in example 1, 5g of sodium antimonate and 0.5g of antioxidant 168, and stirring at a high speed for 10min to obtain a mixture;
and secondly, putting the mixture into a double-cone feeding single-screw machine for plasticizing and granulating, and cooling to obtain the fiber-reinforced-based flame-retardant composite master batch.
Comparative example 1
Compared with example 3, polyimide fibers are used for replacing modified polyimide fibers in the preparation process, and the rest raw materials and the preparation process are kept unchanged, so that the obtained protective layer granules are obtained.
As can be seen from the data in the table, the comparative example 1, in which the polyimide fiber is not modified, has lower oxygen index and is easier to burn, and the smoke density generated during burning is higher, and the antibacterial property is poorer, so that the masterbatch obtained by modifying the polyimide fiber has good flame retardant and antibacterial properties.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims (4)

1. The flame-retardant composite master batch based on fiber reinforcement is characterized by being prepared from the following raw materials in parts by weight: 20-30 parts of modified polyimide fiber, 5-10 parts of kaolin, 3-5 parts of montmorillonite, 30-40 parts of brominated epoxy resin, 3-5 parts of sodium antimonate, 1-3 parts of coupling agent and 0.2-0.5 part of antioxidant;
wherein the modified polyimide fiber is prepared by the following steps:
s1, adding 3-hydroxy-2, 2-bis (hydroxymethyl) -propionaldehyde into a three-necked flask under the protection of nitrogen, adding DMF as a solvent, adding potassium carbonate, stirring for 10min, then adding p-chloronitrobenzene into a DMF solution dropping funnel, slowly dropping into the three-necked flask, controlling the heating temperature to be 100 ℃ after the dropping is completed, reacting for 6h, slowly adding the reaction solution into ice water after the reaction is completed, precipitating solids, carrying out suction filtration, drying, carrying out column chromatography separation by using ethyl acetate and petroleum ether, and collecting chromatographic liquid for reduced pressure rotary evaporation to obtain an intermediate 1;
s2, placing the intermediate 1 and dimethyl phosphono chloride into a flask, adding acetonitrile as a solvent, absorbing tail gas by using 10% sodium hydroxide aqueous solution, controlling the heating temperature to be 85 ℃ under the protection of nitrogen, carrying out reflux reaction for 5 hours, carrying out freeze-drying treatment on the reaction solution after the reaction is finished, washing twice after freeze-drying, and then placing the solution into a vacuum drying oven at 80 ℃ for drying for 6 hours to obtain an intermediate 2;
s3, placing the intermediate 2 in a three-necked flask, adding absolute ethyl alcohol as a solvent, and stirring for 5min; dissolving 4-aminoimidazole in absolute ethyl alcohol, slowly dripping the solution into a flask, heating and refluxing for reaction for 4 hours after dripping, decompressing and steaming a product after the reaction is finished, and recrystallizing the product by using absolute ethyl alcohol to obtain an intermediate 3;
s4, adding the intermediate 3 and Raney nickel into a reaction kettle, adding 1, 4-dioxane as a solvent, sequentially introducing N2 and H2 for replacement, introducing H2 to 3.7MPa, reacting at 80 ℃ for 7 hours, filtering out a catalyst when the reaction is finished, adding the filtrate into cold water, precipitating solid, carrying out suction filtration, and then placing the mixture in a vacuum drying oven at 80 ℃ for 6 hours to obtain the intermediate 4;
s5, at N 2 Under the protection, adding the intermediate 4 and dimethylacetamide into a flask, stirring for 20min, adding pyromellitic dianhydride in batches, controlling the temperature to be 0 ℃ for reaction for 2h, then reacting at room temperature for 8h, and performing reduced pressure rotary evaporation after the reaction is finished to obtain an intermediate 5;
s6, placing the intermediate 5 into a three-necked flask, adding a 1-methyl-2-pyrrolidone and N, N-dimethylformamide 1:3 mixed solvent, stirring for 20min, performing reduced pressure bubble removal, filtering to obtain a spinning solution, performing wet spinning through a spinneret to obtain primary fibers, performing multiple water washing, placing into a tubular furnace, heating 190 ℃/1h,230 ℃/1h,250 ℃/0.5h,300 ℃/1h according to a program, and performing hot drawing and filament collection to obtain modified polyimide fibers;
in the step S1, the dosage ratio of 3-hydroxy-2, 2-bis (hydroxymethyl) -propionaldehyde, potassium carbonate and p-chloronitrobenzene is 10g:10.3g:11.7g;
in the step S2, the dosage ratio of the intermediate 1 to the dimethyl phosphonic acid chloride to the acetonitrile is 10g to 3g to 100mL;
the ratio of the dosage of the intermediate 2, 4-aminoimidazole in the step S3 is 10g to 1.8g;
in the step S4, the dosage ratio of the intermediate 3, the Raney nickel and the 1, 4-dioxane is 10g to 1g to 100mL;
in step S5, the dosage ratio of the intermediate 4 to the dimethylacetamide to the pyromellitic dianhydride was 10 g/100 mL/4.8 g.
2. The fiber-reinforced flame-retardant composite masterbatch according to claim 1, characterized in that the coupling agent is one or more of KH560, KH580, KH791, KH901, KH 902.
3. The fiber reinforced flame retardant composite masterbatch of claim 1 wherein the antioxidant is one or more of antioxidant 1010, antioxidant 300, and antioxidant 168.
4. The method for preparing the fiber-reinforced flame-retardant composite master batch according to claim 1, which is characterized by comprising the following steps:
firstly, placing brominated epoxy resin and a coupling agent into a kneader for uniform mixing, then adding kaolin and montmorillonite, stirring for 30min, and continuously adding modified polyimide fibers, sodium antimonate and an antioxidant, and stirring for 10min at a high speed to obtain a mixture;
and secondly, putting the mixture into a double-cone feeding single-screw machine for plasticizing and granulating, and cooling to obtain the fiber-reinforced-based flame-retardant composite master batch.
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