CN110592946B - Flame-retardant finishing method for polyacrylonitrile carbon fibers - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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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
- 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
- D06M13/10—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 oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3564—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing phosphorus
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Abstract
The invention relates to a flame-retardant finishing method of polyacrylonitrile-based carbon fibers, which is characterized in that the polyacrylonitrile-based carbon fibers are firstly ungelled, the prepared flame-retardant sizing agent is used for sizing and finishing the carbon fibers, and then cationic poly (diallyl dimethyl ammonium chloride) and anionic flame retardant are respectively and alternately adsorbed by adopting a layer-by-layer self-assembly technology. The flame retardant experiment shows that: the initial limit oxygen index of the flame-retardant finished carbon fiber reaches over 29 percent; after 10 times of water washing, the limiting oxygen index is not obviously reduced and still reaches more than 28 percent. The carbon fiber prepared by the method has strong flame retardance, simple whole production process, low price and small environmental pollution in the production process.
Description
Technical Field
The invention belongs to the technical field of carbon fiber microspheres, and particularly relates to a flame-retardant finishing method of polyacrylonitrile-based carbon fibers.
Background
The carbon fiber is a novel fiber material with the carbon content of more than 92 percent or formed by taking carbon allotropes as structural units, has the characteristics of high strength, high modulus, light weight, stable chemical property and the like, and is widely applied in the fields of aerospace, military, automobiles, buildings and the like. At present, polyacrylonitrile is the main raw material of carbon fibers, the carbon fibers occupy more than 90% of the market, and the rest is derived from viscose, asphalt and the like.
With the rapid development of carbon fibers, the carbon fibers are widely applied in more and more fields, and many fields have higher requirements on the flame retardant property of the carbon fibers, so that the development of the carbon fibers with the flame retardant property becomes a problem to be solved urgently at present. At present, more scholars widely research the flame retardant property of carbon fibers, and Chinese patent application No. 201410157894.5 discloses a flame retardant carbon fiber impregnating material and a preparation method thereof, wherein the flame retardant carbon fiber impregnating material comprises a carbon fiber layer and flame retardant epoxy resin, and the preparation method is relatively complex in preparation process; chinese patent application No. 201510571583.8 discloses an environment-friendly flame-retardant carbon fiber reinforced polyamide composite material, and a preparation method and application thereof, wherein the composite material comprises polyamide, carbon fiber, polyvinylidene fluoride, a composite flame retardant, a dispersing agent and the like, and the composite flame retardant in the method can influence the performance of the composite material. In view of the defects of the prior art, a carbon fiber flame-retardant finishing method which is simple in application operation and wide in application range is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a flame-retardant finishing method of polyacrylonitrile-based carbon fibers. The preparation method comprises the steps of firstly ungelatinizing polyacrylonitrile-based carbon fibers, carrying out sizing finishing on the carbon fibers by using the prepared flame-retardant sizing agent, and then respectively and alternately adsorbing cationic poly (diallyldimethylammonium chloride) PDAC and an anionic flame retardant by adopting a layer-by-layer self-assembly technology.
The invention aims to provide a flame-retardant finishing method of polyacrylonitrile-based carbon fibers, which comprises the following steps:
the method comprises the following steps: degumming the carbon fibers: placing the carbon fibers in an acetone solvent, adjusting the temperature to be 50-55 ℃, degumming time to be 1-2 h, and bath ratio to be 1: 20-30;
step two: sizing and finishing of carbon fibers: the carbon fiber enters a sizing groove filled with a flame-retardant sizing agent through a guide roller, is soaked and then enters a drying furnace for drying through a glue squeezing roller, and the sizing amount is controlled to be 1.0-1.5%;
step three: immersing polyacrylonitrile-based carbon fibers into 1-5% of PDAC for 5-10 min, taking out, naturally drying, immersing the dried polyacrylonitrile-based carbon fibers into a flame retardant solution for 5-10 min, taking out, and naturally drying;
step four: and (4) performing immersion and air drying operation on the polyacrylonitrile-based carbon fiber treated in the third step by adopting the method in the third step, and repeating for 2 times to obtain the flame-retardant polyacrylonitrile-based carbon fiber.
In the flame-retardant finishing method of polyacrylonitrile-based carbon fibers, the preparation method of the flame-retardant sizing agent in the second step comprises the following steps:
weighing a proper amount of sodium dodecyl benzene sulfonate, an octyl phenol polyoxyethylene ether emulsifier, acrylic acid, vinyl phosphate and an ammonium persulfate initiator, dissolving all the sodium dodecyl benzene sulfonate, the octyl phenol polyoxyethylene ether emulsifier and the acrylic acid, the vinyl phosphate and the ammonium persulfate initiator accounting for 1/3 of the total amount in a proper amount of deionized water, controlling the temperature to be 75-85 ℃, and stirring for 1-2 hours; then dissolving the rest 2/3 of acrylic acid, vinyl phosphate and ammonium persulfate initiator in a small amount of deionized water, then dropwise adding into the mixed solution which is just stirred, controlling the dropwise adding time to be 2-3 h, after the dropwise adding is finished, preserving the heat for 2-3 h, and after the heat preservation is finished, neutralizing with NaOH solution until the pH value is 7-8 to obtain sizing agent emulsion; preferably, the mass ratio of the sodium dodecyl benzene sulfonate (g), the octyl phenol polyoxyethylene ether emulsifier (g), the acrylic acid (mol), the vinyl phosphate (mol) and the ammonium persulfate (g) is as follows: 0.5-1: 1-2: 0.1-0.2: 0.2-0.4: 0.5-1.
The flame retardant finishing method of polyacrylonitrile-based carbon fiber comprises the following steps:
simultaneously dissolving a certain mass of acrylic acid and vinyl phosphate into a proper amount of deionized water to prepare a monomer solution for later use, wherein preferably, the molar ratio of the acrylic acid to the vinyl phosphate is 1: 0.2-0.4; then under the condition of stirring, controlling the temperature to be 79-81 ℃, and respectively dropwise adding the prepared monomer and an ammonium persulfate initiator into a four-neck flask filled with a certain amount of deionized water, wherein preferably, the mass of the ammonium persulfate accounts for 0.1-0.4% of the total mass of the monomer; the dripping time is controlled to be 2-3 h, after the dripping is finished, the temperature is kept for 3-4 h, and finally the flame retardant solution is prepared after cooling; the weight average molecular weight of the flame retardant is 8000-15000 measured by a gel permeation chromatograph.
The invention has the following remarkable characteristics:
(1) the preparation method comprises the steps of firstly ungelatinizing polyacrylonitrile-based carbon fibers, carrying out sizing finishing on the carbon fibers by using the prepared flame-retardant sizing agent, and then respectively and alternately adsorbing cationic poly (diallyldimethylammonium chloride) (PDAC) and an anionic flame retardant by adopting a layer-by-layer self-assembly technology. The flame-retardant sizing agent and the anionic flame retardant are wrapped on the surface of the carbon fiber to play a flame-retardant role together.
(2) The vinyl phosphate is an excellent organic flame retardant, and is prepared into a sizing agent and an anionic flame retardant by adopting a polymerization method.
(3) The initial limit oxygen index of the carbon fiber prepared by the method reaches more than 29 percent; after 10 times of water washing, the limiting oxygen index is not obviously reduced and still reaches more than 28 percent; the flame retardant effect of the carbon fiber is not obviously weakened, which shows that the carbon fiber has stronger flame retardant effect. The carbon fiber prepared by the method has strong flame retardance, simple whole production process, low price and small environmental pollution in the production process.
Detailed Description
The examples described below illustrate the invention in detail.
Example 1
In this embodiment, a method for flame-retardant finishing of polyacrylonitrile-based carbon fibers includes the following steps:
the method comprises the following steps: degumming the carbon fibers: placing the carbon fiber in an acetone solvent, adjusting the temperature to 55 ℃, degumming time to 1.5h and bath ratio to 1: 25.
Step two: sizing and finishing of carbon fibers: the carbon fiber enters a sizing groove filled with a flame-retardant sizing agent through a guide roller, is soaked and then enters a drying furnace for drying through a glue squeezing roller, and the sizing amount is controlled to be 1.2%;
the preparation method of the flame-retardant sizing agent comprises the following steps:
weighing 0.8g of sodium dodecyl benzene sulfonate, 1.5g of octyl phenol polyoxyethylene ether emulsifier, 0.15mol of acrylic acid, 0.3mol of vinyl phosphate and 0.8g of ammonium persulfate initiator, dissolving all the sodium dodecyl benzene sulfonate, the octyl phenol polyoxyethylene ether emulsifier and the acrylic acid, the vinyl phosphate and the ammonium persulfate initiator accounting for 1/3 of the total amount in 200mL of deionized water, controlling the temperature to be 80-82 ℃, and stirring for 1.5 h; and then dissolving the rest 2/3 of acrylic acid, vinyl phosphate and ammonium persulfate initiator in 50mL of deionized water, then dropwise adding the solution into the mixed solution which is just stirred, controlling the dropwise adding time to be 2.5h, after the dropwise adding is finished, preserving the heat for 2.5h, and neutralizing the solution with NaOH until the pH value is 7-8 after the heat preservation is finished, thus obtaining the sizing agent emulsion.
Step three: immersing the polyacrylonitrile-based carbon fiber into 3% PDAC for 8min, taking out, naturally drying, immersing the dried polyacrylonitrile-based carbon fiber into a flame retardant solution for 8min, taking out, and naturally drying;
the preparation method of the flame retardant solution comprises the following steps:
dissolving 0.1mol of acrylic acid and 0.03mol of vinyl phosphate into 50mL of deionized water simultaneously to prepare a monomer solution; then, under the stirring condition, controlling the temperature to be 79-81 ℃, and respectively dropwise adding the prepared monomer and an ammonium persulfate initiator into a four-neck flask filled with 50mL of deionized water, wherein preferably, the mass of the ammonium persulfate accounts for 0.2% of the total mass of the monomer; the dripping time is controlled to be 2.5h, after the dripping is finished, the heat is preserved for 3.5h, and finally, the flame retardant solution is prepared after cooling; the weight average molecular weight of the flame retardant was 9500 as determined by gel permeation chromatography.
Step four: and (4) performing immersion and air drying operation on the polyacrylonitrile-based carbon fiber treated in the third step by adopting the method in the third step, and repeating for 2 times to obtain the flame-retardant polyacrylonitrile-based carbon fiber a.
Example 2
In this embodiment, a method for flame-retardant finishing of polyacrylonitrile-based carbon fibers includes the following steps:
the method comprises the following steps: degumming the carbon fibers: placing the carbon fiber in an acetone solvent, adjusting the temperature to 50 ℃, degumming time to 1.5h and bath ratio to 1: 20.
Step two: sizing and finishing of carbon fibers: the carbon fiber enters a sizing groove filled with a flame-retardant sizing agent through a guide roller, is soaked and then enters a drying furnace for drying through a glue squeezing roller, and the sizing amount is controlled to be 1.0%;
the preparation method of the flame-retardant sizing agent comprises the following steps:
weighing 0.5g of sodium dodecyl benzene sulfonate, 1g of octyl phenol polyoxyethylene ether emulsifier, 0.1mol of acrylic acid, 0.2mol of vinyl phosphate and 0.5g of ammonium persulfate initiator, dissolving all the sodium dodecyl benzene sulfonate, the octyl phenol polyoxyethylene ether emulsifier and the acrylic acid, the vinyl phosphate and the ammonium persulfate initiator accounting for 1/3 of the total amount in 200mL of deionized water, controlling the temperature to be 75-78 ℃, and stirring for 1.5 h; and then dissolving the rest 2/3 of acrylic acid, vinyl phosphate and ammonium persulfate initiator in 50mL of deionized water, then dropwise adding into the stirred mixed solution, controlling the dropwise adding time to be 2h, after the dropwise adding is finished, preserving the heat for 3h, and after the heat preservation is finished, neutralizing with NaOH solution until the pH value is 7-8 to obtain the sizing agent emulsion.
Step three: immersing the polyacrylonitrile-based carbon fiber into 1% PDAC for 5min, taking out, naturally drying, immersing the dried polyacrylonitrile-based carbon fiber into a flame retardant solution for 5min, taking out, and naturally drying;
the preparation method of the flame retardant solution comprises the following steps:
dissolving 0.1mol of acrylic acid and 0.02mol of vinyl phosphate into 50mL of deionized water to prepare a monomer solution for later use; then under the condition of stirring, controlling the temperature to be 79-81 ℃, and respectively dropwise adding the prepared monomer and an ammonium persulfate initiator into a four-neck flask filled with 100mL of deionized water, wherein preferably, the mass of the ammonium persulfate accounts for 0.1% of the total mass of the monomer; the dripping time is controlled to be 2 hours, after the dripping is finished, the temperature is kept for 3 hours, and finally, the flame retardant solution is prepared after cooling; the weight average molecular weight of the flame retardant was measured by gel permeation chromatography to be 12600.
Step four: and (4) performing immersion and air drying operation on the polyacrylonitrile-based carbon fiber treated in the third step by adopting the method in the third step, and repeating for 2 times to obtain the flame-retardant polyacrylonitrile-based carbon fiber b.
Example 3
In this embodiment, a method for flame-retardant finishing of polyacrylonitrile-based carbon fibers includes the following steps:
the method comprises the following steps: degumming the carbon fibers: placing the carbon fiber in an acetone solvent, adjusting the temperature to 53 ℃, degumming time to 2h and bath ratio to 1: 30.
Step two: sizing and finishing of carbon fibers: the carbon fiber enters a sizing groove filled with a flame-retardant sizing agent through a guide roller, is soaked and then enters a drying furnace for drying through a glue squeezing roller, and the sizing amount is controlled to be 1.5%;
the preparation method of the flame-retardant sizing agent comprises the following steps:
weighing 1g of sodium dodecyl benzene sulfonate, 2g of an octyl phenol polyoxyethylene ether emulsifier, 0.2mol of acrylic acid, 0.4mol of vinyl phosphate and 1g of an ammonium persulfate initiator, dissolving all of the sodium dodecyl benzene sulfonate, the octyl phenol polyoxyethylene ether emulsifier and 1/3 parts of acrylic acid, vinyl phosphate and the ammonium persulfate initiator in 200mL of deionized water, controlling the temperature to be 80-85 ℃, and stirring for 2 hours; and then dissolving the rest 2/3 of acrylic acid, vinyl phosphate and ammonium persulfate initiator in 50mL of deionized water, then dropwise adding the deionized water into the mixed solution which is just stirred, controlling the dropwise adding time to be 3h, after the dropwise adding is finished, preserving the heat for 3h, and neutralizing the mixed solution with NaOH solution until the pH value is 7-8 after the heat preservation is finished, thus obtaining the sizing agent emulsion.
Step three: immersing the polyacrylonitrile-based carbon fiber into 5% PDAC for 10min, taking out, naturally drying, immersing the dried polyacrylonitrile-based carbon fiber into a flame retardant solution for 10min, taking out, and naturally drying;
the preparation method of the flame retardant solution comprises the following steps:
dissolving 0.1mol of acrylic acid and 0.04mol of vinyl phosphate into 50mL of deionized water to prepare a monomer solution for later use; then under the condition of stirring, controlling the temperature to be 79-81 ℃, and respectively dropwise adding the prepared monomer and an ammonium persulfate initiator into a four-neck flask filled with 100mL of deionized water, wherein preferably, the mass of the ammonium persulfate accounts for 0.4% of the total mass of the monomer; the dripping time is controlled to be 3 hours, after the dripping is finished, the temperature is kept for 4 hours, and finally, the flame retardant solution is prepared after cooling; the weight average molecular weight of the flame retardant was 14400 as measured by gel permeation chromatography.
Step four: and (4) performing immersion and air drying operation on the polyacrylonitrile-based carbon fiber treated in the third step by adopting the method in the third step, and repeating for 2 times to obtain the flame-retardant polyacrylonitrile-based carbon fiber c.
In order to better detect the flame retardance of the carbon fibers prepared in the invention, the flame retardance of the carbon fibers a, b and c prepared in the above specific embodiments 1-3 and purchased carbon fibers are tested, the test method adopts an oxygen index test method, namely, the carbon fibers are subjected to standard washing 10 times according to GB/T5454-1997 textile combustion performance test oxygen index method, and GB/T20944.1-2007 washing fastness tester washing method, and the test results are shown in Table 1.
TABLE 1 flame retardancy test results of carbon fibers a, b, c and purchased carbon fibers at different washing times
The limit oxygen index LOI is one of important indexes of flame-retardant materials, the oxygen index of common viscose fibers is less than 20 percent, the common viscose fibers are very easy to burn, and materials with the limit oxygen index of more than 28 percent generally belong to flame-retardant materials. As can be seen from Table 1, the initial limiting oxygen index of the carbon fiber prepared by the invention reaches more than 29 percent, and belongs to the range of flame-retardant materials; after 10 times of water washing, the limiting oxygen index is not obviously reduced and still reaches more than 28 percent; the limit oxygen index of the purchased carbon fiber is lower and is only 13.4 percent. The flame retardant property test shows that: the carbon fiber prepared by the invention has good flame retardant effect and is a qualified flame retardant fiber.
Claims (1)
1. A flame-retardant finishing method of polyacrylonitrile-based carbon fibers is characterized by comprising the following steps:
the method comprises the following steps: degumming the carbon fibers: placing the carbon fibers in an acetone solvent, adjusting the temperature to be 50-55 ℃, degumming time to be 1-2 h, and bath ratio to be 1: 20-30;
step two: sizing and finishing of carbon fibers: the carbon fiber enters a sizing groove filled with the flame-retardant sizing agent emulsion through a guide roller, and is soaked and then enters a drying furnace for drying through a glue squeezing roller;
the preparation method of the flame-retardant sizing agent emulsion in the step two comprises the following steps: weighing sodium dodecyl benzene sulfonate, an octyl phenol polyoxyethylene ether emulsifier, acrylic acid, vinyl phosphate and an ammonium persulfate initiator, dissolving all the sodium dodecyl benzene sulfonate, the octyl phenol polyoxyethylene ether emulsifier and the acrylic acid, the vinyl phosphate and the ammonium persulfate initiator accounting for 1/3 in total amount in a proper amount of deionized water, controlling the temperature to be 75-85 ℃, and stirring for 1-2 hours; then dissolving the rest 2/3 of acrylic acid, vinyl phosphate and ammonium persulfate initiator in a small amount of deionized water, then dropwise adding into the mixed solution which is just stirred, controlling the dropwise adding time to be 2-3 h, after the dropwise adding is finished, preserving the heat for 2-3 h, and after the heat preservation is finished, neutralizing with NaOH solution until the pH value is 7-8 to obtain sizing agent emulsion; the ratio of the sodium dodecyl benzene sulfonate, the octyl phenol polyoxyethylene ether emulsifier, the acrylic acid, the vinyl phosphate and the ammonium persulfate is as follows: (0.5-1) g, (1-2) g, (0.1-0.2) mol, (0.2-0.4) mol and (0.5-1) g;
step three: immersing polyacrylonitrile-based carbon fibers into poly (diallyldimethylammonium chloride) with the mass fraction of 1-5%, immersing for 5-10 min, taking out, naturally drying, immersing the dried polyacrylonitrile-based carbon fibers into a flame retardant solution, immersing for 5-10 min, taking out, and naturally drying;
the preparation method of the flame retardant solution in the third step comprises the following steps: simultaneously dissolving acrylic acid and vinyl phosphate into deionized water to prepare a monomer solution for later use, wherein the molar ratio of the acrylic acid to the vinyl phosphate is 1: 0.2-0.4; then under the condition of stirring, controlling the temperature to be 79-81 ℃, and respectively dropwise adding the prepared monomer solution and an ammonium persulfate initiator into a four-neck flask filled with deionized water, wherein the mass of the ammonium persulfate accounts for 0.1-0.4% of the total mass of the monomers; the dripping time is controlled to be 2-3 h, after the dripping is finished, the temperature is kept for 3-4 h, and finally the flame retardant solution is prepared after cooling; measuring the weight average molecular weight of the flame retardant by using a gel permeation chromatograph to be 8000-15000;
step four: immersing and airing the polyacrylonitrile-based carbon fiber treated in the third step by adopting the method in the third step, and repeating for 2 times to obtain the flame-retardant polyacrylonitrile-based carbon fiber; and the sizing amount in the step two is controlled to be 1.0-1.5%.
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| US4067927A (en) * | 1971-06-14 | 1978-01-10 | Stauffer Chemical Company | Copolycondensed vinylphosphonates and their use as flame retardants |
| KR101863990B1 (en) * | 2011-12-27 | 2018-07-04 | 도레이 카부시키가이샤 | Carbon fiber coated with sizing agent, process for producing carbon fiber coated with sizing agent, prepreg, and carbon fiber reinforced composite material |
| MX2017006962A (en) * | 2015-03-06 | 2017-08-10 | Toray Industries | Sizing-agent-coated carbon fibers, process for producing sizing-agent-coated carbon fibers, carbon-fiber-reinforced composite material, and process for producing carbon-fiber-reinforced composite material. |
| CN107501466B (en) * | 2017-08-29 | 2020-05-08 | 广东工业大学 | Emulsion type carbon fiber sizing agent and preparation method thereof |
| CN108411629A (en) * | 2018-02-08 | 2018-08-17 | 四川大学 | A kind of surface has the carbon fiber of flame retardant coating, preparation method and applications |
| CN109610191B (en) * | 2018-11-20 | 2019-11-22 | 武汉纺织大学 | A kind of preparation method of organic/inorganic composite flame-proof cotton fabric coating |
| CN109897132A (en) * | 2018-12-25 | 2019-06-18 | 昆明理工大学 | A kind of acrylic acid ester emulsion and preparation method thereof with flame retarding function |
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