CN112853537A - Flame-retardant lignin grafted polyacrylonitrile composite fiber and preparation method thereof - Google Patents
Flame-retardant lignin grafted polyacrylonitrile composite fiber and preparation method thereof Download PDFInfo
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- CN112853537A CN112853537A CN202110024757.4A CN202110024757A CN112853537A CN 112853537 A CN112853537 A CN 112853537A CN 202110024757 A CN202110024757 A CN 202110024757A CN 112853537 A CN112853537 A CN 112853537A
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- 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
- D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
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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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Abstract
The invention relates to the technical field of polyacrylonitrile composite fibers, and discloses a flame-retardant lignin-grafted polyacrylonitrile composite fiber, wherein 2-bromoisobutylated lignin is used as an ATRP macromolecular initiator, pentamethyldiethylenetriamine is used as a ligand, cuprous bromide is used as a catalyst, initiating acrylonitrile monomer to polymerize in situ in the lignin matrix by ATRP atom transfer radical polymerization to obtain lignin grafted polyacrylonitrile, wherein phenolic hydroxyl in the lignin has the characteristic of capturing free radicals, the high-temperature flame retardant has the advantages that the high-temperature free radical degradation reaction of polyacrylonitrile can be inhibited, the thermal oxidation of the polyacrylonitrile can be promoted to generate the ionic cyclization reaction, the thermal stability and the heat resistance of the polyacrylonitrile can be improved, the phosphate group is used as an active flame retardant component, the ammonium cation is used as an expansion gas source, the lignin with high char yield is used as an expansion carbon source, an expansion flame retardant system is formed, and the excellent smoke suppression effect and the flame retardant property are achieved.
Description
Technical Field
The invention relates to the technical field of polyacrylonitrile composite fibers, in particular to a flame-retardant lignin grafted polyacrylonitrile composite fiber and a preparation method thereof.
Background
The polyacrylonitrile fiber is a fiber material obtained by polymerizing monomers such as acrylonitrile and the like through processes such as electrostatic spinning, wet spinning and the like, has the performance similar to wool, has good elasticity, high stretchability, excellent weather resistance and sun-proof performance, has the advantages of softness, bulkiness, bright color, light resistance and the like, can be woven into materials such as blankets, carpets, clothing materials, indoor articles and the like, is a natural high polymer with a three-dimensional network, has rich carbon content and high char yield, has wide prospect in carbon fiber materials, has the characteristics of certain bacteria resistance, oxidation resistance, ultraviolet resistance and the like, can be blended and spun with fibers such as polyacrylonitrile and the like to obtain a composite fiber material with excellent performance, but the traditional polyacrylonitrile fiber has poor flame resistance, solution combustion and can generate toxic gases such as hydrogen cyanide and the like, seriously pollutes the environment and harms the human health, so that the improvement of the thermal stability and the flame retardance of the polyacrylonitrile fiber becomes a research hotspot.
The flame retardant is a functional material for endowing a high polymer material with flame retardancy, the commonly used flame retardants mainly comprise nitrogen-phosphorus flame retardants, intumescent flame retardants, halogen flame retardants and the like, and can be divided into additive flame retardants and reactive flame retardants according to the addition mode, wherein the reactive flame retardants enable the flame retardant components to be organically combined with the high polymer material through copolymerization, chemical modification and other modes, so that the material is endowed with permanent high flame retardancy, and the reactive flame retardants have small influence on the service performance of the material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the flame-retardant lignin grafted polyacrylonitrile composite fiber and the preparation method thereof, and solves the problems of poor thermal stability and flame retardance of the polyacrylonitrile fiber.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the flame-retardant lignin grafted polyacrylonitrile composite fiber comprises the following steps:
(1) adding N, N-dimethylformamide solvent, lignin and catalyst 4-dimethylaminopyridine into a flask, adding 2-bromoisobutyryl bromide at the temperature of-5 to 5 ℃, controlling the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide to be 100:6-15:10-25, uniformly stirring, carrying out esterification reaction for 18 to 36 hours at the temperature of 20 to 35 ℃, adding distilled water to separate out a precipitate, filtering the solvent, and washing and purifying by using distilled water to obtain the 2-bromoisobutyrated lignin.
(2) Adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran with the volume ratio of 6-10:1 into a three-necked bottle, adding 2-bromo-isobutyl lignin, stirring to dissolve, adding acrylonitrile and ligand pentamethyldiethylenetriamine, freezing, vacuumizing, filling nitrogen, adding a catalyst cuprous bromide, controlling the mass ratio of the 2-bromo-isobutyl lignin, the acrylonitrile, the pentamethyldiethylenetriamine and the cuprous bromide to be 4-15:100:1.5-4:1.2-3, carrying out ATRP atom transfer radical polymerization reaction for 6-12h at 70-90 ℃ in a nitrogen atmosphere, placing the mixture in an ice water bath for cooling, adding methanol for precipitation, filtering the solvent, washing with methanol and distilled water, and purifying to obtain the lignin grafted polyacrylonitrile.
(3) Adding distilled water solvent, phosphoric acid with the mass ratio of 30-80:4-10:100, urea and lignin grafted polyacrylonitrile into a reaction bottle, carrying out phosphoric acid amination modification reaction for 1-3h at the temperature of 60-90 ℃, filtering the solvent, washing and purifying by distilled water, and obtaining ammonium phosphate modified lignin grafted polyacrylonitrile.
(4) Adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 12-24h to form electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:50-60 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
in the flame-retardant lignin-grafted polyacrylonitrile composite fiber, an esterification reaction is carried out on acyl bromide groups of 2-bromoisobutyryl bromide and partial hydroxyl groups of lignin to obtain 2-bromoisobutyrated lignin, the 2-bromoisobutyrated lignin is used as an ATRP macromolecular initiator, pentamethyldiethylenetriamine is used as a ligand, cuprous bromide is used as a catalyst, and an acrylonitrile monomer is initiated to polymerize in situ in a lignin matrix through efficient and controllable ATRP atom transfer radical polymerization to obtain lignin-grafted polyacrylonitrile, the bonding degree and the interface affinity of the lignin and the polyacrylonitrile are enhanced through a chemical covalent bond grafting method, because the polyacrylonitrile and the lignin both contain strong polar groups and strong intermolecular forces, if the polyacrylonitrile and the lignin are simply and physically mixed, the polyacrylonitrile and the lignin are easy to separate, so that the internal pore defect is formed, and the comprehensive performances of the material, such as thermal stability, flame retardance and the like, are influenced, chemical covalent bond grafting solves these problems very well.
The flame-retardant lignin-grafted polyacrylonitrile composite fiber has the characteristic of capturing free radicals, can inhibit the free radical degradation reaction of polyacrylonitrile at high temperature and promote the thermal oxidation of the polyacrylonitrile to generate the ionic cyclization reaction, thereby improving the thermal stability and the heat resistance of the polyacrylonitrile, the hydroxyl in the lignin-grafted polyacrylonitrile reacts with phosphoric acid and urea to obtain ammonium phosphate modified lignin-grafted polyacrylonitrile, and then the flame-retardant lignin-grafted polyacrylonitrile composite fiber is obtained by a wet spinning method, wherein the ammonium phosphate modified lignin component is used as a reactive flame retardant, the phosphoric acid group is used as an active flame retardant component, the ammonium cation is used as an expansion gas source, and the lignin with high char yield is used as an expansion carbon source to form an expansion flame retardant system, so that the flame-retardant lignin-grafted polyacrylonitrile composite fiber generates a compact and continuous carbon layer under the high-temperature combustion, inhibits the permeation of oxygen and heat into the material, hinders the combustion process, and plays a role in excellent smoke suppression effect and flame retardant property under the synergistic effect.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of the flame-retardant lignin grafted polyacrylonitrile composite fiber is as follows:
(1) adding N, N-dimethylformamide solvent, lignin and catalyst 4-dimethylaminopyridine into a flask, adding 2-bromoisobutyryl bromide at the temperature of-5 to 5 ℃, controlling the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide to be 100:6-15:10-25, uniformly stirring, carrying out esterification reaction for 18 to 36 hours at the temperature of 20 to 35 ℃, adding distilled water to separate out a precipitate, filtering the solvent, and washing and purifying by using distilled water to obtain the 2-bromoisobutyrated lignin.
(2) Adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran with the volume ratio of 6-10:1 into a three-necked bottle, adding 2-bromo-isobutyl lignin, stirring to dissolve, adding acrylonitrile and ligand pentamethyldiethylenetriamine, freezing, vacuumizing, filling nitrogen, adding a catalyst cuprous bromide, controlling the mass ratio of the 2-bromo-isobutyl lignin, the acrylonitrile, the pentamethyldiethylenetriamine and the cuprous bromide to be 4-15:100:1.5-4:1.2-3, carrying out ATRP atom transfer radical polymerization reaction for 6-12h at 70-90 ℃ in a nitrogen atmosphere, placing the mixture in an ice water bath for cooling, adding methanol for precipitation, filtering the solvent, washing with methanol and distilled water, and purifying to obtain the lignin grafted polyacrylonitrile.
(3) Adding distilled water solvent, phosphoric acid with the mass ratio of 30-80:4-10:100, urea and lignin grafted polyacrylonitrile into a reaction bottle, carrying out phosphoric acid amination modification reaction for 1-3h at the temperature of 60-90 ℃, filtering the solvent, washing and purifying by distilled water, and obtaining ammonium phosphate modified lignin grafted polyacrylonitrile.
(4) Adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 12-24h to form electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:50-60 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
Example 1
(1) Adding N, N-dimethylformamide solvent, lignin and catalyst 4-dimethylaminopyridine into a flask, adding 2-bromoisobutyryl bromide at-5 ℃, controlling the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide to be 100:6:10, uniformly stirring, carrying out esterification reaction for 18h at 20 ℃, adding distilled water to precipitate, filtering the solvent, washing and purifying by using distilled water, and thus obtaining the 2-bromoisobutyrated lignin.
(2) Adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran in a volume ratio of 6:1 into a three-necked bottle, adding 2-bromo-isobutyl-esterified lignin, stirring to dissolve, adding acrylonitrile and ligand pentamethyl diethylenetriamine, freezing, vacuumizing, filling nitrogen, adding a catalyst cuprous bromide, controlling the mass ratio of the 2-bromo-isobutyl-esterified lignin, the acrylonitrile, the pentamethyl diethylenetriamine and the cuprous bromide to be 4:100:1.5:1.2, carrying out ATRP atom transfer radical polymerization reaction for 6 hours at 70 ℃ in a nitrogen atmosphere, placing the mixture in an ice water bath to cool, adding methanol to precipitate, filtering the solvent, washing with methanol and distilled water, and purifying to obtain the lignin-grafted polyacrylonitrile.
(3) Adding a distilled water solvent, phosphoric acid, urea and lignin grafted polyacrylonitrile with the mass ratio of 30:4:100 into a reaction bottle, carrying out phosphoric acid amination modification reaction for 1h at 60 ℃, filtering the solvent, washing with distilled water and purifying to obtain ammonium phosphate modified lignin grafted polyacrylonitrile.
(4) Adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 12 hours to form an electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:50 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
Example 2
(1) Adding N, N-dimethylformamide solvent, lignin and catalyst 4-dimethylaminopyridine into a flask, adding 2-bromoisobutyryl bromide at the temperature of 5 ℃, controlling the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide to be 100:8:15, uniformly stirring, carrying out esterification reaction for 18h at the temperature of 35 ℃, adding distilled water to precipitate out precipitate, filtering the solvent, washing and purifying by using distilled water, and thus obtaining the 2-bromoisobutyrylated lignin.
(2) Adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran in a volume ratio of 7:1 into a three-necked bottle, adding 2-bromo-isobutyl-esterified lignin, stirring to dissolve, adding acrylonitrile and ligand pentamethyldiethylenetriamine, freezing, vacuumizing, filling nitrogen, adding a catalyst cuprous bromide, controlling the mass ratio of the 2-bromo-isobutyl-esterified lignin, the acrylonitrile, the pentamethyldiethylenetriamine and the cuprous bromide to be 8:100:2.2:1.8, carrying out ATRP atom transfer radical polymerization reaction for 12 hours at 90 ℃ in a nitrogen atmosphere, placing the mixture in an ice water bath to cool, adding methanol to precipitate, filtering the solvent, washing with methanol and distilled water, and purifying to obtain the lignin-grafted polyacrylonitrile.
(3) Adding a distilled water solvent, phosphoric acid, urea and lignin grafted polyacrylonitrile with a mass ratio of 45:6:100 into a reaction bottle, carrying out phosphoric acid amination modification reaction for 2 hours at 70 ℃, filtering the solvent, washing with distilled water, and purifying to obtain ammonium phosphate modified lignin grafted polyacrylonitrile.
(4) Adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 12 hours to form an electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:54 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
Example 3
(1) Adding N, N-dimethylformamide solvent, lignin and catalyst 4-dimethylaminopyridine into a flask, adding 2-bromoisobutyryl bromide at 0 ℃, controlling the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide to be 100:12:20, uniformly stirring, carrying out esterification reaction for 24 hours at 25 ℃, adding distilled water to precipitate, filtering the solvent, washing and purifying by using distilled water, and thus obtaining the 2-bromoisobutyrated lignin.
(2) Adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran in a volume ratio of 8:1 into a three-necked bottle, adding 2-bromo-isobutyl lignin, stirring to dissolve, adding acrylonitrile and ligand pentamethyldiethylenetriamine, freezing, vacuumizing, filling nitrogen, adding a catalyst cuprous bromide, controlling the mass ratio of the 2-bromo-isobutyl lignin, the acrylonitrile, the pentamethyldiethylenetriamine and the cuprous bromide to be 12:100:3:2.4, carrying out ATRP atom transfer radical polymerization reaction for 10 hours at 80 ℃ in a nitrogen atmosphere, placing the mixture in an ice water bath to cool, adding methanol to precipitate, filtering the solvent, washing with methanol and distilled water, and purifying to obtain the lignin grafted polyacrylonitrile.
(3) Adding a distilled water solvent, phosphoric acid, urea and lignin grafted polyacrylonitrile with the mass ratio of 60:8:100 into a reaction bottle, carrying out phosphoric acid amination modification reaction for 2 hours at 80 ℃, filtering the solvent, washing with distilled water and purifying to obtain ammonium phosphate modified lignin grafted polyacrylonitrile.
(4) Adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 18h to form an electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:57 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
Example 4
(1) Adding N, N-dimethylformamide solvent, lignin and catalyst 4-dimethylaminopyridine into a flask, adding 2-bromoisobutyryl bromide at the temperature of 5 ℃, controlling the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide to be 100:15:25, uniformly stirring, carrying out esterification reaction for 36 hours at the temperature of 35 ℃, adding distilled water to precipitate, filtering the solvent, washing and purifying by using distilled water, and thus obtaining the 2-bromoisobutyrated lignin.
(2) Adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran in a volume ratio of 10:1 into a three-necked bottle, adding 2-bromo-isobutyl-esterified lignin, stirring to dissolve, adding acrylonitrile and ligand pentamethyldiethylenetriamine, freezing, vacuumizing, filling nitrogen, adding a catalyst cuprous bromide, controlling the mass ratio of the 2-bromo-isobutyl-esterified lignin, the acrylonitrile, the pentamethyldiethylenetriamine and the cuprous bromide to be 15:100:4:3, carrying out ATRP atom transfer radical polymerization reaction for 12 hours at 90 ℃ in a nitrogen atmosphere, placing the mixture in an ice water bath to cool, adding methanol to precipitate, filtering the solvent, washing the methanol and distilled water, and purifying to obtain the lignin-grafted polyacrylonitrile.
(3) Adding a distilled water solvent, phosphoric acid, urea and lignin grafted polyacrylonitrile with a mass ratio of 80:10:100 into a reaction bottle, carrying out phosphoric acid amination modification reaction for 3 hours at 90 ℃, filtering the solvent, washing with distilled water and purifying to obtain ammonium phosphate modified lignin grafted polyacrylonitrile.
(4) Adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 24 hours to form an electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:60 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
Comparative example 1
(1) Adding N, N-dimethylformamide solvent, lignin and catalyst 4-dimethylaminopyridine into a flask, adding 2-bromoisobutyryl bromide at 0 ℃, controlling the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide to be 100:2:25, uniformly stirring, carrying out esterification reaction for 36 hours at 25 ℃, adding distilled water to precipitate, filtering the solvent, washing and purifying by using distilled water, and thus obtaining the 2-bromoisobutyrated lignin.
(2) Adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran in a volume ratio of 8:1 into a three-necked bottle, adding 2-bromo-isobutyl-esterified lignin, stirring to dissolve, adding acrylonitrile and ligand pentamethyldiethylenetriamine, freezing, vacuumizing, filling nitrogen, adding a catalyst cuprous bromide, controlling the mass ratio of the 2-bromo-isobutyl-esterified lignin, the acrylonitrile, the pentamethyldiethylenetriamine and the cuprous bromide to be 1.5:100:0.8:0.6, carrying out ATRP atom transfer radical polymerization reaction for 12 hours at 80 ℃ in a nitrogen atmosphere, placing the mixture in a water bath for ice cooling, adding methanol for precipitation, filtering the solvent, washing and purifying by using the methanol and distilled water, and obtaining the lignin-grafted polyacrylonitrile.
(3) Adding a distilled water solvent, phosphoric acid, urea and lignin grafted polyacrylonitrile with the mass ratio of 15:2:100 into a reaction bottle, carrying out phosphoric acid amination modification reaction for 2 hours at 80 ℃, filtering the solvent, washing with distilled water and purifying to obtain ammonium phosphate modified lignin grafted polyacrylonitrile.
(4) Adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 24 hours to form an electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:46 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
Comparative example 2
(1) Adding N, N-dimethylformamide solvent, lignin and catalyst 4-dimethylaminopyridine into a flask, adding 2-bromoisobutyryl bromide at-5 ℃, controlling the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide to be 100:3:5, uniformly stirring, carrying out esterification reaction for 24 hours at 35 ℃, adding distilled water to precipitate, filtering the solvent, washing and purifying by using distilled water, and thus obtaining the 2-bromoisobutyrated lignin.
(2) Adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran in a volume ratio of 10:1 into a three-necked bottle, adding 2-bromo-isobutyl-esterified lignin, stirring to dissolve, adding acrylonitrile and ligand pentamethyl diethylenetriamine, freezing, vacuumizing, filling nitrogen, adding a catalyst cuprous bromide, controlling the mass ratio of the 2-bromo-isobutyl-esterified lignin, the acrylonitrile, the pentamethyl diethylenetriamine and the cuprous bromide to be 18:100:5:3.8, carrying out ATRP atom transfer radical polymerization reaction for 12 hours at 80 ℃ in a nitrogen atmosphere, placing the mixture in an ice water bath to cool, adding methanol to precipitate, filtering the solvent, washing with methanol and distilled water, and purifying to obtain the lignin-grafted polyacrylonitrile.
(3) Adding a distilled water solvent, phosphoric acid, urea and lignin grafted polyacrylonitrile with the mass ratio of 100:12:100 into a reaction bottle, carrying out phosphoric acid amination modification reaction for 2 hours at 70 ℃, filtering the solvent, washing with distilled water and purifying to obtain ammonium phosphate modified lignin grafted polyacrylonitrile.
(4) Adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 18h to form an electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:64 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
And (3) testing the initial decomposition temperature and the complete decomposition temperature of the flame-retardant lignin grafted polyacrylonitrile composite fiber by using a TGA-1000 thermogravimetric analyzer, wherein the national standard is GB/T37631-2019.
The limiting oxygen index of the composite fiber is tested by using an F101D limiting oxygen index meter, and the national standard is GB/T5454-1997.
Claims (7)
1. A fire-retardant lignin graft polyacrylonitrile composite fiber is characterized in that: the preparation method of the flame-retardant lignin grafted polyacrylonitrile composite fiber comprises the following steps:
(1) adding an N, N-dimethylformamide solvent, lignin and a catalyst into a flask, adding 2-bromoisobutyryl bromide at the temperature of between 5 ℃ below zero and 5 ℃, uniformly stirring, and carrying out an esterification reaction to obtain 2-bromoisobutyrated lignin;
(2) adding a mixed solvent of N, N-dimethylformamide solvent and tetrahydrofuran with the volume ratio of 6-10:1 into a three-necked bottle, adding 2-bromo-isobutyl lignin, stirring for dissolving, adding acrylonitrile and a ligand, freezing, vacuumizing, filling nitrogen, adding a catalyst, and performing ATRP (atom transfer radical polymerization) in a nitrogen atmosphere to obtain lignin grafted polyacrylonitrile;
(3) adding distilled water solvent, phosphoric acid and urea into a reaction bottle, uniformly stirring, adding lignin grafted polyacrylonitrile, and carrying out phosphoric acid amination modification to obtain ammonium phosphate modified lignin grafted polyacrylonitrile;
(4) adding a dimethyl sulfoxide solvent and ammonium phosphate modified lignin grafted polyacrylonitrile into a reaction bottle, stirring for 12-24h to form electrostatic spinning solution, performing a wet spinning method, taking a mixed solvent of dimethyl sulfoxide and distilled water with a volume ratio of 100:50-60 as a coagulating bath phase, and performing washing drafting treatment, high-temperature densification treatment and high-power drafting treatment to obtain the flame-retardant lignin grafted polyacrylonitrile composite fiber.
2. The flame retardant lignin grafted polyacrylonitrile composite fiber according to claim 1, wherein: the catalyst in the step (1) is 4-dimethylaminopyridine, and the mass ratio of the lignin, the 4-dimethylaminopyridine and the 2-bromoisobutyryl bromide is 100:6-15: 10-25.
3. The flame retardant lignin grafted polyacrylonitrile composite fiber according to claim 1, wherein: the temperature of the esterification reaction in the step (1) is 20-35 ℃, and the reaction lasts for 18-36 h.
4. The flame retardant lignin grafted polyacrylonitrile composite fiber according to claim 1, wherein: the ligand in the step (2) is pentamethyldiethylenetriamine, the catalyst is cuprous bromide, and the mass ratio of the 2-bromoisobutylated lignin, the acrylonitrile, the pentamethyldiethylenetriamine and the cuprous bromide is 4-15:100:1.5-4: 1.2-3.
5. The flame retardant lignin grafted polyacrylonitrile composite fiber according to claim 1, wherein: the reaction temperature of the ATRP atom transfer radical polymerization in the step (2) is 70-90 ℃, and the reaction lasts for 6-12 h.
6. The flame retardant lignin grafted polyacrylonitrile composite fiber according to claim 1, wherein: the mass ratio of the phosphoric acid, the urea and the lignin grafted polyacrylonitrile in the step (3) is 30-80:4-10: 100.
7. The flame retardant lignin grafted polyacrylonitrile composite fiber according to claim 1, wherein: and (3) carrying out amination modification on the phosphoric acid in the step (3) at the temperature of 60-90 ℃ for 1-3 h.
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| US20130292615A1 (en) * | 2012-05-03 | 2013-11-07 | Empire Technology Development Llc | Phosphonate-substituted lignin as a flame retardant |
| CN103484966A (en) * | 2013-08-15 | 2014-01-01 | 苏州龙杰特种纤维股份有限公司 | Polyacrylonitrile fiber with flame resistance and preparation method thereof |
| CN104356318A (en) * | 2014-11-10 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Lignin-based starlike thermoplastic elastomer and preparation method thereof |
| CN109627453A (en) * | 2018-12-12 | 2019-04-16 | 怀化学院 | For the fire retardant of polylactic acid, flame-retardant polylactic acid material and preparation method thereof |
| CN109943920A (en) * | 2019-03-08 | 2019-06-28 | 华南理工大学 | A kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130292615A1 (en) * | 2012-05-03 | 2013-11-07 | Empire Technology Development Llc | Phosphonate-substituted lignin as a flame retardant |
| CN103484966A (en) * | 2013-08-15 | 2014-01-01 | 苏州龙杰特种纤维股份有限公司 | Polyacrylonitrile fiber with flame resistance and preparation method thereof |
| CN104356318A (en) * | 2014-11-10 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Lignin-based starlike thermoplastic elastomer and preparation method thereof |
| CN109627453A (en) * | 2018-12-12 | 2019-04-16 | 怀化学院 | For the fire retardant of polylactic acid, flame-retardant polylactic acid material and preparation method thereof |
| CN109943920A (en) * | 2019-03-08 | 2019-06-28 | 华南理工大学 | A kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115043631A (en) * | 2022-07-12 | 2022-09-13 | 张飞 | Ecological pervious concrete and preparation method thereof |
| CN115043631B (en) * | 2022-07-12 | 2023-08-25 | 安新县宏胜商品混凝土有限公司 | Ecological permeable concrete and preparation method thereof |
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