CN114990877B - Novel flame-retardant composite material for protective clothing and preparation method and application thereof - Google Patents

Novel flame-retardant composite material for protective clothing and preparation method and application thereof Download PDF

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CN114990877B
CN114990877B CN202210697282.XA CN202210697282A CN114990877B CN 114990877 B CN114990877 B CN 114990877B CN 202210697282 A CN202210697282 A CN 202210697282A CN 114990877 B CN114990877 B CN 114990877B
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porous graphene
phosphorus
ionic liquid
containing ionic
product
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CN114990877A (en
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王增喜
潘海平
游嫔芳
张劲林
汪兴怡
冯劲松
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Shenzhen X&y International Industrial Co ltd
Guangdong Vocational and Technical College
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Shenzhen X&y International Industrial Co ltd
Guangdong Vocational and Technical College
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
    • D06M13/447—Phosphonates or phosphinates containing nitrogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to a novel flame-retardant composite material for protective clothing, and a preparation method and application thereof, and the novel flame-retardant composite material comprises the following steps of S10: preparing porous graphene; s20: preparing a phosphorus-containing ionic liquid; s30: mixing the phosphorus-containing ionic liquid with porous graphene to obtain a phosphorus-containing ionic liquid/porous graphene composite material; converting graphene oxide into porous graphene with a graphitized structure through calcination and activation, and compositing the porous graphene with a phosphorus-containing ionic liquid under the action of ultrasound, wherein the phosphorus-containing ionic liquid is not only on the surface of the porous graphene, but also enters the porous structure of the porous graphene with high specific surface area, pi-pi stacking interaction exists between the porous graphene and the porous graphene, so that agglomeration among porous graphene particles is remarkably reduced, agglomeration among the porous graphene particles is remarkably reduced, and the specific surface area of the porous graphene is increased; the composite material prepared by the method has higher comprehensive performance, good flame retardance of the phosphorus-containing ionic liquid, excellent chemical stability and physical and mechanical properties of the porous graphene, and the like.

Description

Novel flame-retardant composite material for protective clothing and preparation method and application thereof
Technical Field
The invention relates to the technical field of new materials, in particular to a novel flame-retardant composite material for protective clothing, and a preparation method and application thereof.
Background
Flame-retardant protective clothing has become one of the most used varieties in individual protective articles, and the protective principle is mainly to protect people from being damaged by open flame or heat sources through the effects of heat insulation, reflection, absorption, carbonization isolation and the like. Human skin is very sensitive to heat and may be exposed to high temperatures, burns of degree I, II or III, even if completely burnt (Zhao Yang, teng Jinshan. Flame retardant protective clothing [ J ]. Labor protection, 2006, (8): 95-97.). Therefore, flame retardant protective clothing is widely used in industries such as industrial furnaces, chemical industry, petroleum, machinery, construction, coal, fire protection and the like. When in direct contact with a flame or hot object, it can prevent itself from being ignited, flaming and smoldering for a certain period of time, thereby protecting the safety and health of workers. The flame-retardant protective clothing has one special side, belongs to labor protection articles, has the function of protecting workers, and therefore, special fabrics are generally selected, flame-retardant fibers in the fabrics greatly slow the burning speed, have the characteristic of self-extinguishing when leaving fire, enable burning parts to be quickly carbonized without melting, dropping or perforating, and the like, reduce or avoid burn and scald, and further achieve the aim of protection;
the combination of properties of the flame retardants commonly used today is critical for improving the properties of the product. However, most flame retardants have poor overall properties, and their strength to fabric is limited, sometimes even reducing certain properties (such as mechanical properties) of the fabric, so much intensive research is still needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel flame-retardant composite material for protective clothing, and a preparation method and application thereof.
The technical scheme for solving the technical problems is as follows: a method for preparing a novel flame retardant composite material for protective clothing, comprising the steps of:
s10: preparing porous graphene: weighing the following components in percentage by mass: 3-5 of graphene oxide and alkali are mixed, and react for 2-3 hours at a high temperature of 800-950 ℃ under the protection of nitrogen, so that a product A is obtained after calcination and activation reaction, and porous graphene is obtained after washing and freeze drying treatment of the product A;
s20: preparing a phosphorus-containing ionic liquid: adding 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide containing phosphoric acid, triethylamine and methylene dichloride into a flask, uniformly mixing, adding ethylsulfonyl chloride into the flask, reacting for 4-6 hours to obtain a product B, washing, drying to obtain a product C, stirring the product C and 1-methylimidazole, cleaning, and precipitating to obtain a phosphorus-containing ionic liquid;
s30: the mass ratio is 13-18: 100, mixing the phosphorus-containing ionic liquid and the porous graphene at a high temperature of 80-90 ℃ for 45-60 min, and performing ultrasonic treatment to obtain a phosphorus-containing ionic liquid/porous graphene composite material;
the preparation method of the invention, wherein the specific surface area of the porous graphene is 550-750 m 2 G, the weight loss at 1000 ℃ is 3-5 wt%;
the preparation method of the invention comprises the steps that the alkali is one of potassium hydroxide, sodium hydroxide, barium hydroxide and calcium hydroxide;
the preparation method of the invention comprises the steps of washing the product A with deionized water for 3-5 times;
the preparation method of the invention comprises the following steps of: 1 to 1.5;
the preparation method of the invention, wherein the dosage of the methylene dichloride is 250-450 mL; the dosage of the ethyl sulfonyl chloride is 1 to 1.5mol; the dosage of the 1-methylimidazole is 120-180 mL;
the preparation method of the invention, wherein, the product B is washed 2-3 times by hot ethanol;
the preparation method of the invention comprises the steps of stirring the product C and the 1-methylimidazole at 75-85 ℃ for 48-72 h, and then sequentially cleaning with acetonitrile and diethyl ether for 2-3 times;
the invention also discloses a novel flame-retardant composite material for protective clothing, wherein the preparation method of the novel flame-retardant composite material is applied;
the invention also discloses an application of the preparation method of the novel flame-retardant composite material for the protective clothing, wherein the novel flame-retardant composite material is applied to the polypropylene fabric for the flame-retardant protective clothing.
The beneficial effects of the invention are as follows: (1) The porous graphene with high specific surface area is used as a carrier, so that the phosphorus-containing ionic liquid can be better loaded and uniformly dispersed, the active area of the phosphorus-containing ionic liquid is increased, and the flame retardant property of the phosphorus-containing ionic liquid is obviously enhanced;
(2) The porous graphene has the characteristic of excellent chemical stability, and can improve the stability of the phosphorus-containing ionic liquid, so that the durability of the material is enhanced;
(3) The phosphorus-containing ionic liquid not only covers the surface of the porous graphene, but also can enter the porous structure of the porous graphene with high specific surface area, pi-pi stacking interaction exists between the porous graphene and the phosphorus-containing ionic liquid, so that agglomeration among particles of the porous graphene is obviously reduced, and the specific surface area of the porous graphene is increased;
(4) The prepared phosphorus-containing ionic liquid and the porous graphene are mixed, so that the phosphorus-containing ionic liquid has the advantages of good flame retardance, chemical stability, physical and mechanical properties and the like, and the comprehensive performance of the flame-retardant protective clothing matrix can be enhanced;
(5) The composite material obtained by the invention has higher comprehensive performance, good flame retardance of phosphorus-containing ionic liquid, excellent chemical stability, physical and mechanical properties and the like, and when the composite material is applied to flame-retardant protective clothing polypropylene fabrics, the obtained fabrics have the characteristics of excellent flame retardance, mechanical properties and the like, and the composite material has the advantages of simple preparation process, low price, safe use and wide prospect in practical flame-retardant protective application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the present invention will be further described with reference to the accompanying drawings and embodiments, in which the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained by those skilled in the art without inventive effort:
FIG. 1 is a flow chart of a method of preparing a novel flame retardant composite for protective apparel in accordance with a preferred embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in detail with reference to the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without any inventive effort, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
The terms "first," "second," "third," and "fourth" and the like in the description and in the claims and drawings are used for distinguishing between different objects and not necessarily for describing a particular sequential or chronological order. Furthermore, the terms "comprise" and "have," as well as any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed steps or elements but may include other steps or elements not listed or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the invention. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
"plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in detail with reference to the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without any inventive effort, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
The invention discloses a novel flame-retardant composite material for protective clothing, a preparation method and application thereof, and a specific flow chart of the preparation method is shown in figure 1.
Example 1:
(1) Preparing graphene oxide: graphene oxide was prepared according to the modified Hummer method (Kovtyukhova NI, ollivier P J, martin B R, mallouk T E, chizhik S A, buzaniva E V, gorchinskiy A D.layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polymers.chemistry of Materials,1999,11 (3): 771-778.).
(2) Preparing porous graphene: weighing 1g of graphene oxide prepared by an improved Hummer method, adding 3g of potassium hydroxide, calcining and activating at a high temperature of 800 ℃ for 2 hours under the protection of nitrogen to obtain a product A1, taking out after the reaction is finished, washing the product A1 with deionized water for 3 times, and freeze-drying for later use to obtain porous graphene;
wherein the specific surface area of the porous graphene is 550m 2 G, weight loss at 1000℃of 3% by weight; the phosphorus-containing ionic liquid can be loaded and uniformly dispersed, so that the active area of the phosphorus-containing ionic liquid is increased, and the flame retardant property of the phosphorus-containing ionic liquid is obviously enhanced;
(3) Preparing a phosphorus-containing ionic liquid: adding 1mol of 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide containing phosphoric acid, 1mol of triethylamine and 250mL of dichloromethane into a three-necked flask, uniformly mixing, adding 1mol of ethyl sulfonyl chloride into the flask, reacting at room temperature for 4 hours under a reflux state to obtain a product B1, washing the product B1 with hot ethanol for 2 times, vacuum drying at a high temperature of 75 ℃ for 7 hours to obtain a product C1, stirring the product C1 and 120mL of 1-methylimidazole at a high temperature of 75 ℃ for 48 hours, sequentially washing with acetonitrile and diethyl ether for 2 times, and precipitating to obtain the phosphorus-containing ionic liquid.
(4) Mixing 100g of the porous graphene in the step (1) and 13g of the phosphorus-containing ionic liquid in the step (2) at a high temperature of 80 ℃ for 45min, and performing ultrasonic treatment at room temperature for 45min to obtain the phosphorus-containing ionic liquid/porous graphene composite material.
Example 2:
(1) Preparing graphene oxide: graphene oxide was prepared according to the modified Hummer method (Kovtyukhova NI, ollivier P J, martin B R, mallouk T E, chizhik S A, buzaniva E V, gorchinskiy A D.layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polymers.chemistry of Materials,1999,11 (3): 771-778.).
(2) Preparing porous graphene: weighing 1g of graphene oxide prepared by an improved Hummer method, adding 3.5g of sodium hydroxide, calcining at a high temperature of 800 ℃ under the protection of nitrogen for 3 hours to obtain a product A2, taking out after the reaction is finished, washing the product A2 with deionized water for 3 times, and freeze-drying for later use to obtain porous graphene;
wherein, the specific surface area of the porous graphene is 590m 2 G, weight loss at 1000℃of 3% by weight; the phosphorus-containing ionic liquid can be loaded and uniformly dispersed, so that the active area of the phosphorus-containing ionic liquid is increased, and the flame retardant property of the phosphorus-containing ionic liquid is obviously enhanced;
(3) Preparing a phosphorus-containing ionic liquid: adding 1mol of 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide containing phosphoric acid, 1mol of triethylamine and 200mL of dichloromethane into a three-necked flask, uniformly mixing, adding 1mol of ethyl sulfonyl chloride into the flask, reacting for 4.5 hours at room temperature under a reflux state to obtain a product B2, washing the product B2 with hot ethanol for 2 times, vacuum drying at a high temperature of 75 ℃ for 9 hours to obtain a product C2, stirring the product C2 and 120mL of 1-methylimidazole at a high temperature of 75 ℃ for 60 hours, sequentially washing with acetonitrile and diethyl ether for 2 times, and precipitating to obtain the phosphorus-containing ionic liquid.
(4) Mixing 100g of the porous graphene in the step (1) and 14g of the phosphorus-containing ionic liquid in the step (2) at a high temperature of 80 ℃ for 60min, and performing ultrasonic treatment at room temperature for 45min to obtain the phosphorus-containing ionic liquid/porous graphene composite material.
Example 3:
(1) Preparing graphene oxide: graphene oxide was prepared according to the modified Hummer method (Kovtyukhova NI, ollivier P J, martin B R, mallouk T E, chizhik S A, buzaniva E V, gorchinskiy A D.layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polymers.chemistry of Materials,1999,11 (3): 771-778.).
(2) Preparing porous graphene: weighing 1g of graphene oxide prepared by an improved Hummer method, adding 4.5g of sodium hydroxide, calcining at a high temperature of 850 ℃ under the protection of nitrogen for 3 hours to obtain a product A3, taking out after the reaction is finished, washing the product A3 with deionized water for 4 times, and freeze-drying for later use to obtain porous graphene;
wherein, the specific surface area of the porous graphene is 630m 2 G, weight loss at 1000℃of 4 wt.%; the phosphorus-containing ionic liquid can be loaded and uniformly dispersed, so that the active area of the phosphorus-containing ionic liquid is increased, and the flame retardant property of the phosphorus-containing ionic liquid is obviously enhanced;
(3) Preparing a phosphorus-containing ionic liquid: adding 1mol of 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide containing phosphoric acid, 1.1mol of triethylamine and 300mL of dichloromethane into a three-necked flask, uniformly mixing, adding 1.1mol of ethyl sulfonyl chloride into the flask, reacting for 4.5 hours at room temperature under a reflux state to obtain a product B3, washing the product B3 with hot ethanol for 3 times, vacuum drying at a high temperature of 80 ℃ for 9 hours to obtain a product C3, stirring the product C3 and 140mL of 1-methylimidazole at a high temperature of 80 ℃ for 60 hours, sequentially washing with acetonitrile and diethyl ether for 2 times, and precipitating to obtain the phosphorus-containing ionic liquid.
(4) Mixing 100g of the porous graphene in the step (1) and 15g of the phosphorus-containing ionic liquid in the step (2) at a high temperature of 85 ℃ for 45min, and performing ultrasonic treatment at room temperature for 60min to obtain the phosphorus-containing ionic liquid/porous graphene composite material.
Example 4:
(1) Preparing graphene oxide: graphene oxide was prepared according to the modified Hummer method (Kovtyukhova NI, ollivier P J, martin B R, mallouk T E, chizhik S A, buzaniva E V, gorchinskiy A D.layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polymers.chemistry of Materials,1999,11 (3): 771-778.).
(2) Preparing porous graphene: weighing 1g of graphene oxide prepared by an improved Hummer method, adding 4g of barium hydroxide, calcining and activating at a high temperature of 900 ℃ for 2 hours under the protection of nitrogen to obtain a product A4, taking out after the reaction is finished, washing the product A4 with deionized water for 4 times, and freeze-drying for later use to obtain porous graphene;
wherein the specific surface area of the porous graphene is 660m 2 G, weight loss at 1000℃of 4 wt.%; the phosphorus-containing ionic liquid can be loaded and uniformly dispersed, so that the active area of the phosphorus-containing ionic liquid is increased, and the flame retardant property of the phosphorus-containing ionic liquid is obviously enhanced;
(3) Preparing a phosphorus-containing ionic liquid: adding 1mol of 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide containing phosphoric acid, 1.2mol of triethylamine and 350mL of dichloromethane into a three-neck flask, uniformly mixing, adding 1.2mol of ethyl sulfonyl chloride into the flask, reacting at room temperature under a reflux state for 5 hours to obtain a product B4, washing the product B4 with hot ethanol for 2 times, vacuum drying at 80 ℃ for 10 hours to obtain a product C4, stirring the product C4 and 150mL of 1-methylimidazole at 80 ℃ for 72 hours, sequentially washing with acetonitrile and diethyl ether for 2 times, and precipitating to obtain the phosphorus-containing ionic liquid.
(4) Mixing 100g of the porous graphene in the step (1) and 16g of the phosphorus-containing ionic liquid in the step (2) at a high temperature of 85 ℃ for 60min, and performing ultrasonic treatment at room temperature for 60min to obtain the phosphorus-containing ionic liquid/porous graphene composite material.
Example 5:
(1) Preparing graphene oxide: graphene oxide was prepared according to the modified Hummer method (Kovtyukhova NI, ollivier P J, martin B R, mallouk T E, chizhik S A, buzaniva E V, gorchinskiy A D.layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polymers.chemistry of Materials,1999,11 (3): 771-778.).
(2) Preparing porous graphene: weighing 1g of graphene oxide prepared by an improved Hummer method, adding 5g of barium hydroxide, calcining and activating at a high temperature of 900 ℃ for 3 hours under the protection of nitrogen to obtain a product A5, taking out after the reaction is finished, washing the product A5 with deionized water for 5 times, and freeze-drying for later use to obtain porous graphene;
wherein, the specific surface area of the porous graphene is 710m 2 G, weight loss at 1000℃of 5% by weight; the phosphorus-containing ionic liquid can be loaded and uniformly dispersed, so that the active area of the phosphorus-containing ionic liquid is increased, and the flame retardant property of the phosphorus-containing ionic liquid is obviously enhanced;
(3) Preparing a phosphorus-containing ionic liquid: adding 1mol of 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide containing phosphoric acid, 1.4mol of triethylamine and 400mL of dichloromethane into a three-neck flask, uniformly mixing, adding 1.4mol of ethyl sulfonyl chloride into the flask, reacting for 5.5 hours at room temperature under a reflux state to obtain a product B5, washing the product B5 with hot ethanol for 3 times, vacuum drying at a high temperature of 85 ℃ for 8 hours to obtain a product C5, stirring the product C5 and 170mL of 1-methylimidazole at a high temperature of 85 ℃ for 60 hours, sequentially washing with acetonitrile and diethyl ether for 3 times, and precipitating to obtain the phosphorus-containing ionic liquid.
(4) Mixing 100g of the porous graphene in the step (1) and 17g of the phosphorus-containing ionic liquid in the step (2) at a high temperature of 90 ℃ for 45min, and performing ultrasonic treatment at room temperature for 60min to obtain the phosphorus-containing ionic liquid/porous graphene composite material.
Example 6:
(1) Preparing graphene oxide: graphene oxide was prepared according to the modified Hummer method (Kovtyukhova NI, ollivier P J, martin B R, mallouk T E, chizhik S A, buzaniva E V, gorchinskiy A D.layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polymers.chemistry of Materials,1999,11 (3): 771-778.).
(2) Preparing porous graphene: weighing 1g of graphene oxide prepared by an improved Hummer method, adding 5g of calcium hydroxide, calcining and activating at a high temperature of 950 ℃ for 3 hours under the protection of nitrogen to obtain a product A6, taking out after the reaction is finished, washing the product A6 with deionized water for 5 times, and freeze-drying for later use to obtain porous graphene;
wherein, the specific surface area of the porous graphene is 750m 2 G, weight loss at 1000℃of 5% by weight; the ionic liquid containing phosphorus can be loaded,the active area of the phosphorus-containing ionic liquid is increased, and the flame retardant property of the phosphorus-containing ionic liquid is obviously enhanced;
(3) Preparing a phosphorus-containing ionic liquid: adding 1mol of 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide containing phosphoric acid, 1.5mol of triethylamine and 450mL of dichloromethane into a three-neck flask, uniformly mixing, adding 1.5mol of ethyl sulfonyl chloride into the flask, reacting at room temperature under a reflux state for 6 hours to obtain a product B6, washing the product B6 with hot ethanol for 3 times, vacuum drying at a high temperature of 85 ℃ for 10 hours to obtain a product C6, stirring the product C6 and 180mL of 1-methylimidazole at a high temperature of 85 ℃ for 72 hours, sequentially washing with acetonitrile and diethyl ether for 3 times, and precipitating to obtain the phosphorus-containing ionic liquid.
(4) Mixing 100g of the porous graphene in the step (1) and 18g of the phosphorus-containing ionic liquid in the step (2) at a high temperature of 90 ℃ for 60min, and performing ultrasonic treatment at room temperature for 60min to obtain the phosphorus-containing ionic liquid/porous graphene composite material.
Example 7:
the composite material of the phosphorus-containing ionic liquid/porous graphene prepared in the examples 1-6 has higher comprehensive performance, good flame retardance of the phosphorus-containing ionic liquid, excellent chemical stability, physical and mechanical properties and the like, and when the composite material is applied to a polypropylene fabric for flame-retardant protection clothing, the obtained fabric has the characteristics of excellent flame retardance, mechanical properties and the like, and is applied to the polypropylene fabric for flame-retardant protection clothing, and relevant tests are carried out. The specific process and steps are as follows:
the phosphorus-containing ionic liquid/porous graphene composite materials prepared in examples 1-6 are ultrasonically dispersed in water to form an aqueous solution with the concentration of 2g/L, and the bath ratio is 1:30, adding polypropylene fabric, stirring and soaking for 120min at 300rpm, pulping, vacuum baking at 80 ℃ for 15min, treating in 10g/L adhesive solution for 10min, soaking, and vacuum drying at 80 ℃ for 10min to obtain the composite flame-retardant fabric.
The prepared composite flame-retardant fabric has the characteristics of excellent flame-retardant property, mechanical property and the like, is simple in process, low in price and safe to use, and has wide prospects in actual flame-retardant protection application.
And (3) converting graphene oxide into porous graphene with a graphitized structure through calcination and activation, and compositing the porous graphene with the phosphorus-containing ionic liquid under the action of ultrasound. The phosphorus-containing ionic liquid is not only on the surface of the porous graphene, but also enters the porous structure of the porous graphene with high specific surface area, and pi-pi stacking interaction exists between the porous graphene and the phosphorus-containing ionic liquid, so that agglomeration among porous graphene particles is remarkably reduced. Thereby, the effective contact area between the components is increased, and a synergistic effect is generated, so that the properties of the components are improved more remarkably. The obtained composite material combines the advantages of the phosphorus-containing ionic liquid, and has good flame retardance of the phosphorus-containing ionic liquid, excellent chemical stability, physical and mechanical properties and the like of the porous graphene.
Based on the synergistic effect, the composite material has superior comprehensive performance compared with single components. When the composite material is used for the polypropylene fabric for flame-retardant protective clothing, the obtained fabric has the characteristics of excellent flame-retardant property, mechanical property and the like.
The mechanical property and the flame retardant property of the novel flame retardant fabric which can be used for protective clothing are inspected, and the specific testing process and steps are as follows:
a: mechanical properties
The breaking strength and breaking elongation of the test samples were measured by an electronic fabric strength tester according to GB/T3923.1-1997. The experiment was repeated 5 times, and the results were averaged as shown in table 1.
Table 1 mechanical properties test results of the composite flame retardant fabrics obtained in examples
As can be seen from table 1, for the composite flame retardant fabric, the polypropylene fabric obtained the modification enhancement effect of the phosphorus-containing ionic liquid/porous graphene composite material, and the composite flame retardant fabric has excellent mechanical properties based on the synergistic enhancement effect, and shows higher breaking strength and lower breaking elongation.
b: flame retardant Properties
A vertical combustion tester is adopted to test the vertical combustion performance of the sample according to the UL94 standard, whether the sample is self-extinguished after leaving fire is observed, and the damage length is recorded after 12s in flame; the limiting oxygen index of the sample is tested by adopting a limiting oxygen index tester according to ASTMD 2863-08. The experiment was repeated 5 times, and the results were averaged as shown in table 2.
Table 2 results of flame retardant property test of the composite flame retardant fabrics obtained in examples
As can be seen from table 2, for the composite flame retardant fabric, the polypropylene fabric obtained a modification enhancement of the phosphorus-containing ionic liquid/porous graphene composite material. Based on the synergistic effect, the composite flame-retardant fabric has excellent flame retardance, shows a self-extinguishing phenomenon after leaving fire, has a shorter burning damage length and has a higher limiting oxygen index.
It should be understood that the foregoing examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the foregoing examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made as equivalent substitutions, and are included in the scope of the present invention.

Claims (9)

1. A method for preparing a novel flame retardant composite material for protective clothing, comprising the steps of:
s10: preparing porous graphene: weighing the following components in percentage by mass: 3-5 of graphene oxide and alkali are mixed, and are reacted for 2-3 hours at a high temperature of 800-950 ℃ under the protection of nitrogen, so that a product A is obtained after calcination and activation reaction, and the porous graphene is obtained after washing and freeze drying treatment of the product A;
s20: preparing a phosphorus-containing ionic liquid: adding 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine and methylene dichloride into a flask, uniformly mixing, adding ethylsulfonyl chloride into the flask, reacting for 4-6 hours to obtain a product B, washing, drying to obtain a product C, stirring the product C and 1-methylimidazole, cleaning, and precipitating to obtain a phosphorus-containing ionic liquid;
s30: the mass ratio is 13-18: 100 and mixing the phosphorus-containing ionic liquid and the porous graphene at a high temperature of 80-90 ℃ for 45-60 min, and performing ultrasonic treatment on the mixture to obtain the phosphorus-containing ionic liquid/porous graphene composite material.
2. The preparation method of claim 1, wherein the porous graphene has a specific surface area of 550-750 m 2 And/g, wherein the weight loss at 1000 ℃ is 3-5 wt%.
3. The method according to claim 2, wherein the base is one of potassium hydroxide, sodium hydroxide, barium hydroxide, and calcium hydroxide.
4. The method according to claim 3, wherein the product a is washed 3 to 5 times with deionized water.
5. The preparation method according to claim 1, wherein the mass ratio of the 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide to the triethylamine is 1:1 to 1.5.
6. The preparation method of claim 5, wherein the dosage of dichloromethane is 250-450 mL; the dosage of the ethyl sulfonyl chloride is 1-1.5 mol; the dosage of the 1-methylimidazole is 120-180 mL.
7. The method according to claim 6, wherein the product B is washed 2 to 3 times with hot ethanol.
8. The preparation method according to claim 7, wherein the product C and the 1-methylimidazole are stirred at a temperature of 75-85 ℃ for 48-72 hours, and then washed with acetonitrile and diethyl ether for 2-3 times.
9. A novel flame retardant composite for protective apparel, characterized in that it is prepared by the method of preparing a novel flame retardant composite according to any one of claims 1-8.
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