CN118461219A - Lyocell fiber non-woven fabric and preparation method thereof - Google Patents
Lyocell fiber non-woven fabric and preparation method thereof Download PDFInfo
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- CN118461219A CN118461219A CN202410560134.2A CN202410560134A CN118461219A CN 118461219 A CN118461219 A CN 118461219A CN 202410560134 A CN202410560134 A CN 202410560134A CN 118461219 A CN118461219 A CN 118461219A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
- D04H1/4258—Regenerated cellulose series
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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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
- D06M11/68—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
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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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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Abstract
The invention relates to a lyocell fiber non-woven fabric and a preparation method thereof, wherein the non-woven fabric comprises, by weight, 20-30 parts of cellulose pulp, 4-6 parts of modified cellulose, 150-180 parts of N-methylmorpholine-N-oxide solution, 1-2 parts of antioxidant, 12-15 parts of cross-linking impregnating compound, 2-4 parts of sodium phosphate, 140-150 parts of ethanol and 30-40 parts of water, wherein the mass fraction of the N-methylmorpholine-N-oxide solution is 50%; modified cellulose is added in the preparation process of the lyocell fiber non-woven fabric, so that the crystallinity and orientation of the lyocell fiber non-woven fabric are changed, and the lyocell fiber non-woven fabric is subjected to aftertreatment by a soaking method, so that cellulose molecular chains are mutually crosslinked, and meanwhile, a nitrogen-phosphorus-sulfur flame-retardant system is introduced, so that the lyocell fiber non-woven fabric is prepared, and has good flame retardant property and antigen fibrillation capability.
Description
Technical Field
The invention relates to the technical field of fibers, in particular to a lyocell fiber non-woven fabric and a preparation method thereof.
Background
The lyocell fiber is novel and environment-friendly, and is prepared by dissolving natural cellulose serving as a raw material in an organic solvent N-methylmorpholine-N-oxide to prepare cellulose pulp, spinning by a dry-wet spinning method, solidifying and forming by a low-temperature water bath system, and performing a series of processes such as air-blowing cooling, oiling, stretching, winding and forming;
However, the lyocell fiber and its fabric are easy to burn, the limiting oxygen index value is low, and is a flammable fiber, this main disadvantage severely limits the applicability of the lyocell fiber in places with fire risk sensitivity, and at the same time, after the lyocell fiber and its fabric are subjected to the friction action of mechanical external force in wet state, fine fibrils split along the fiber axis can be separated on the surface of the fibrils, so that hairiness is easily generated on the surface of the fabric yarn, and this fibrillation phenomenon can bring adverse effects to the use of the lyocell fabric, for example, defects such as dead folds, scratches, frosting and the like are easily generated in the dyeing and finishing process, or fibrillation occurs in the home washing process, so that the appearance of the fabric is affected.
Disclosure of Invention
The invention aims to provide a lyocell fiber non-woven fabric and a preparation method thereof, which solve the problems of poor flame retardant property and easy fibrillation of the conventional lyocell fiber non-woven fabric.
The aim of the invention can be achieved by the following technical scheme:
the lyocell fiber non-woven fabric is prepared by the following steps: step S1: weighing the following raw materials in parts by weight: 20-30 parts of cellulose pulp, 4-6 parts of modified cellulose, 150-180 parts of N-methylmorpholine-N-oxide solution, 1-2 parts of antioxidant, 12-15 parts of cross-linking impregnating agent, 2-4 parts of sodium phosphate, 140-150 parts of ethanol and 30-40 parts of water, wherein the mass fraction of the N-methylmorpholine-N-oxide solution is 50%;
Step S2: mixing cellulose pulp, modified cellulose, an antioxidant and an N-methylmorpholine-N-oxide solution to prepare a spinning solution, adding the spinning solution into a spinning melt-blowing device, spinning, melt-blowing, forming a net, and leaching to prepare non-infiltrated non-woven fabrics;
Step S3: mixing the cross-linking impregnating compound, sodium phosphate, ethanol and water to prepare a cross-linking impregnating solution, soaking non-impregnated non-woven fabrics in the cross-linking impregnating solution at the temperature of 70 ℃ for 30-40min, performing double-soaking and double-bundling by using a padder, controlling the rolling surplus rate to be 80%, taking out, washing with water, pre-drying at 80 ℃, and baking at 140 ℃ to prepare the lyocell fiber non-woven fabrics.
The modified cellulose is prepared by the following steps:
Step A1: mixing cellulose with deionized water, performing ultrasonic dispersion, adding sodium periodate at 50-60 ℃ in the dark, standing for 3-4h, cooling to room temperature, adding ethylene glycol, and continuing to react for 1-2h to obtain cellulose aldehyde;
The molar concentration of the sodium periodate is 1.5mol/L, and the dosage ratio of the cellulose, the sodium periodate and the glycol is 6-8g:50-60mL:6mL;
In the reaction process of the step A1, cellulose and deionized water are mixed and ultrasonically dispersed, the mixture is reacted with sodium periodate, secondary hydroxyl at the C 2-C3 ortho position in a glucose unit in the cellulose is selectively oxidized into aldehyde group due to the strong oxidizing property of the sodium periodate, and then ethylene glycol is added to react with the sodium periodate to terminate the reaction, so that the cellulose aldehyde is prepared;
Step A2: mixing 2-acrylamide and deionized water, stirring and adding mercaptoethylamine and ammonium persulfate under the protection of nitrogen at the stirring speed of 120-150rpm and the temperature of 60 ℃, reacting for 8-10 hours to obtain amino-terminated polyacrylamide, mixing graphene oxide, isophorone diisocyanate and N, N-dimethylformamide, performing ultrasonic dispersion, reacting for 24 hours under the protection of nitrogen at the stirring speed of 240-300rpm and the temperature of 80 ℃, adding amino-terminated polyacrylamide, and continuously reacting for 24 hours to obtain grafted graphene oxide;
The dosage ratio of the 2-acrylamide, the mercaptoethylamine and the ammonium persulfate is 0.1 to 0.15mol:0.01-0.015mol:0.005mol; the dosage ratio of the graphene oxide, isophorone diisocyanate and amino-terminated polyacrylamide is 2g:0.02-0.03mol:8-10g;
In the reaction process of the step A2, 2-acrylamide is polymerized under the action of an initiator ammonium persulfate and is blocked by the reaction of sulfhydryl groups and double bonds to prepare amino-terminated polyacrylamide, in N, N-dimethylformamide, hydroxyl groups in graphene oxide react with isophorone diisocyanate isocyanate groups to form aminomethylate groups, so that the surface of the graphene oxide contains isocyanate groups, the isocyanate groups react with amino-terminated groups in the amino-terminated polyacrylamide to form ureido groups, and the acrylamide is grafted on the graphene oxide to prepare grafted graphene oxide;
step A3: mixing trifluoroacetic acid, triethylsilane, grafted graphene oxide and acetonitrile, stirring and adding cellulose hydroformylation at a stirring speed of 120-150rpm and a temperature of 110 ℃, reacting for 18 hours, adding acetic anhydride, cooling to 35 ℃, and continuously reacting for 0.5-1 hour to obtain modified cellulose;
Trifluoroacetic acid, triethylsilane, grafted graphene oxide, acetonitrile, hydroformylation cellulose and acetic anhydride in an amount ratio of 60-70mL:50mL:2g:300mL:6-8g:30-40mL;
in the reaction process of the step A3, in acetonitrile, aldehyde groups in cellulose aldehyde and amide in grafted graphene oxide are subjected to N-reduction alkylation reaction under the action of trifluoroacetic acid and triethylsilane, wherein the aldehyde groups are firstly subjected to dehydration condensation with the amide to form aminal, then reduced hydrogenation is carried out to become amino groups, a cellulose graphene oxide system is prepared, acetic anhydride is added, and hydroxyl groups in cellulose aldehyde are subjected to acetylation reaction with acetic anhydride under the catalysis of trifluoroacetic acid to prepare modified cellulose;
the cross-linking impregnating compound is prepared by the following steps:
Step B1: mixing 2-chloro-4.6-diamino-1.3.5-sym-triazine, sodium bis (trimethylsilyl) amide and tetrahydrofuran, stirring and adding di-tert-butyl dicarbonate under the conditions of nitrogen protection and stirring speed of 90-120rpm and room temperature, reacting for 16-18h to obtain an intermediate 1, mixing the intermediate 1, sodium hydrosulfide and absolute ethyl alcohol, reacting for 8h under the conditions of stirring speed of 90-120rpm and temperature of 85 ℃ to obtain an intermediate 2, mixing the intermediate 2 and tetrahydrofuran, adding hydrogen peroxide under the conditions of stirring speed of 90-120rpm and room temperature, and reacting for 0.5-1h to obtain an intermediate 3;
The dosage ratio of 2-chloro-4.6-diamino-1.3.5-s-triazine, sodium bis (trimethylsilyl) amide and di-tert-butyl dicarbonate is 0.02mol:0.04-0.05mol:0.04-0.05mol; the ratio of the amount of intermediate 1 to the amount of sodium hydrosulfide is 0.02mol:1.2-1.4g; the mass concentration of the hydrogen peroxide is 30%, and the dosage ratio of the intermediate 2 to the hydrogen peroxide is 0.02mol:1.5-1.6g;
In the reaction process of the step B1, in tetrahydrofuran, 2-chloro-4.6-diamino-1.3.5-s-triazine amino reacts with di-tert-butyl dicarbonate under the action of sodium bis (trimethylsilyl) amide to form an intermediate 1 of double Boc protected amino, chlorine in the intermediate 1 reacts with sodium hydrosulfide in absolute ethyl alcohol to generate sulfhydryl, so as to obtain an intermediate 2, and in tetrahydrofuran, the sulfhydryl in the intermediate 2 is condensed under the action of hydrogen peroxide to form disulfide bonds, so as to obtain an intermediate 3;
Step B2: mixing the intermediate 3, tertiary butyl disilyl trifluoro methane sulfonate and methylene dichloride, reacting for 6 hours at room temperature under the condition of stirring speed of 120-150rpm to obtain an intermediate 4, mixing the intermediate 4, parahydroxyben-zaldehyde and tetrahydrofuran, reacting for 4-6 hours under the condition of nitrogen protection and stirring speed of 120-150rpm and temperature of 50 ℃, adding DOPO, heating to 60 ℃, and reacting for 12 hours to obtain an intermediate 5;
Intermediate 3, t-butyldisilyl triflate and dichloromethane in a ratio of 0.01mol:0.01mol:120mL; the dosage ratio of the intermediate 4, the parahydroxyben-zaldehyde and DOPO is 0.01mol:0.04-0.05mol:0.04-0.05mol;
In the reaction process of the step B2, firstly, performing Boc deprotection on the intermediate 3 by using a tertiary butyl disilyl triflate and methylene dichloride system to form primary amine, then reacting with aldehyde groups in parahydroxybenzaldehyde to form imine bonds, then adding DOPO, and reacting P-H bonds in the DOPO with the imine bonds to enable the DOPO to be grafted in the intermediate 4 to prepare an intermediate 5;
step B3: mixing the intermediate 5, triethylamine and tetrahydrofuran, stirring at a stirring speed of 80-120rpm and at room temperature, adding acryloyl chloride, and reacting for 12 hours to obtain a crosslinking sizing agent;
The dosage ratio of the intermediate 5, triethylamine and acryloyl chloride is 0.01mol:5g:0.08-0.1mol;
in the reaction process of the step B3, in tetrahydrofuran, hydroxyl in the intermediate 5 reacts with acyl chloride in acrylic chloride to form ester groups, so as to prepare a crosslinking impregnating compound;
The invention has the beneficial effects that: the invention discloses a lyocell fiber non-woven fabric and a preparation method thereof, wherein modified cellulose is added in the preparation process of the lyocell fiber non-woven fabric, and the modified cellulose is subjected to aftertreatment by an infiltration method to prepare the lyocell fiber non-woven fabric, so that the lyocell fiber non-woven fabric has better flame retardant property and antigen fibrillation capability; the modified cellulose is prepared by mixing polyacrylamide grafted graphene oxide and cellulose aldehyde and connecting the graphene oxide and cellulose aldehyde through chemical bonds, hydroxyl groups in cellulose are acetylated, after the base material in the modified cellulose is blended, the modified cellulose is unfavorable for orientation and crystallization of cellulose molecules due to the steric hindrance effect of acetyl groups, meanwhile, aggregation among macromolecular celluloses is reduced due to reduction of hydroxyl groups, crystallinity of cellulose molecules in the spinning solidification forming process is reduced, molecular structure of an amorphous region of the cellulose molecules is improved, orientation of lyocell fibers is reduced, fibrillation capability of the lyocell fiber nonwoven fabric is weakened, meanwhile, the modified cellulose is also connected with polyacrylamide grafted graphene oxide through chemical bonds, dispersion of the graphene oxide in the base material is ensured, binding force of a fiber amorphous region can be increased due to existence of polyacrylamide chain segments, formation of hydrogen bonds among celluloses is reduced, regular arrangement of cellulose crystallization units is destroyed, antigen fibrillation capability of fibers is enhanced, and the self-property of the graphene oxide can improve the lyocell performance to a certain extent; the intermediate 3 containing disulfide bonds is prepared by thiolating and self-condensing 2-chloro-4, 6-diamino-1, 3, 5-sym-triazine, the intermediate 3 reacts with p-hydroxybenzaldehyde after being subjected to Boc protection, DOPO is introduced to prepare intermediate 5, the intermediate 5 reacts with acrylic chloride to prepare a cross-linking impregnating compound which takes triazine compounds as a matrix and contains disulfide bonds, DOPO flame retardant groups and multiple double bonds, non-woven fabrics are soaked in the cross-linking impregnating compound, under the action of sodium phosphate as a catalyst, the double bonds in the cross-linking impregnating compound react with cellulose hydroxyl groups to form ether bonds through cross linking, so that the interaction between cellulose macromolecular chains is enhanced, the effect of increasing the transverse combination force of fibers is achieved, inhibiting the occurrence of fibrillation, so that the lyocell fiber nonwoven fabric has good anti-fibrillation capability, and because the cross-linking impregnating compound takes triazine compounds as a matrix and contains disulfide bonds and DOPO groups, the cross-linking impregnating compound can form a nitrogen-phosphorus-sulfur flame-retardant system, and when combustion occurs, the cross-linking impregnating compound is heated to decompose and release sulfur free radicals, thereby effectively capturing the free radicals at the initial stage of combustion, delaying the progress of chain reaction, promoting the rapid carbon formation of fibers, forming a stable and compact carbon layer under the action of phosphorus elements, and simultaneously, sulfur-containing and nitrogen-containing nonflammable gas generated by the combustion of sulfur elements and nitrogen elements can also play a role of diluting combustible gas to block the combustion, so that the lyocell fiber nonwoven fabric has good flame retardant property;
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The modified cellulose is prepared by the following steps:
Step A1: mixing 30 mu m cellulose sold in the market with deionized water, performing ultrasonic dispersion, adding sodium periodate at 50 ℃ in the dark, standing for 4 hours, cooling to room temperature, adding ethylene glycol, and continuing to react for 1 hour to obtain cellulose aldehyde;
The molar concentration of the sodium periodate is 1.5mol/L, and the dosage ratio of the cellulose, the sodium periodate and the glycol is 6g:50mL:6mL;
Step A2: mixing 2-acrylamide and deionized water, stirring and adding mercaptoethylamine and ammonium persulfate under the protection of nitrogen at the stirring speed of 120rpm and the temperature of 60 ℃, reacting for 10 hours to obtain amino-terminated polyacrylamide, mixing and ultrasonically dispersing commercially available graphene oxide with the size of 10 mu m, isophorone diisocyanate and N, N-dimethylformamide, reacting for 24 hours under the protection of nitrogen at the stirring speed of 240rpm and the temperature of 80 ℃, adding amino-terminated polyacrylamide, and continuously reacting for 24 hours to obtain grafted graphene oxide;
The dosage ratio of the 2-acrylamide, the mercaptoethylamine and the ammonium persulfate is 0.1mol:0.01mol:0.005mol; the dosage ratio of the graphene oxide, isophorone diisocyanate and amino-terminated polyacrylamide is 2g:0.02mol:8g;
Step A3: mixing trifluoroacetic acid, triethylsilane, grafted graphene oxide and acetonitrile, stirring and adding cellulose hydroformylation at a stirring speed of 120rpm and a temperature of 110 ℃, reacting for 18 hours, adding acetic anhydride, cooling to 35 ℃, and continuing to react for 0.5 hour to obtain modified cellulose;
Trifluoroacetic acid, triethylsilane, grafted graphene oxide, acetonitrile, hydroformylation cellulose and acetic anhydride in an amount ratio of 60mL:50mL:2g:300mL:6g:30mL.
Example 2
The modified cellulose is prepared by the following steps:
Step A1: mixing 30 mu m cellulose sold in the market with deionized water, performing ultrasonic dispersion, adding sodium periodate at 60 ℃ in the dark, standing for 3 hours, cooling to room temperature, adding ethylene glycol, and continuing to react for 2 hours to obtain cellulose aldehyde;
The molar concentration of the sodium periodate is 1.5mol/L, and the dosage ratio of the cellulose, the sodium periodate and the glycol is 8g:50mL:6mL;
Step A2: mixing 2-acrylamide and deionized water, stirring and adding mercaptoethylamine and ammonium persulfate under the protection of nitrogen at the stirring speed of 150rpm and the temperature of 60 ℃, reacting for 8 hours to obtain amino-terminated polyacrylamide, mixing and ultrasonically dispersing commercially available graphene oxide with the size of 10 mu m, isophorone diisocyanate and N, N-dimethylformamide, reacting for 24 hours under the protection of nitrogen at the stirring speed of 300rpm and the temperature of 80 ℃, adding amino-terminated polyacrylamide, and continuously reacting for 24 hours to obtain grafted graphene oxide;
the dosage ratio of 2-acrylamide, mercaptoethylamine and ammonium persulfate is 0.15mol:0.01mol:0.005mol; the dosage ratio of the graphene oxide, isophorone diisocyanate and amino-terminated polyacrylamide is 2g:0.03mol:8g;
Step A3: mixing trifluoroacetic acid, triethylsilane, grafted graphene oxide and acetonitrile, stirring and adding cellulose hydroformylation at a stirring speed of 150rpm and a temperature of 110 ℃, reacting for 18 hours, adding acetic anhydride, cooling to 35 ℃, and continuing to react for 1 hour to obtain modified cellulose;
Trifluoroacetic acid, triethylsilane, grafted graphene oxide, acetonitrile, hydroformylation cellulose and acetic anhydride in an amount ratio of 60mL:50mL:2g:300mL:8g:30mL.
Example 3
The modified cellulose is prepared by the following steps:
step A1: mixing 30 mu m cellulose sold in the market with deionized water, performing ultrasonic dispersion, adding sodium periodate at 60 ℃ in the dark, standing for 4 hours, cooling to room temperature, adding ethylene glycol, and continuing to react for 2 hours to obtain cellulose aldehyde;
The molar concentration of the sodium periodate is 1.5mol/L, and the dosage ratio of the cellulose, the sodium periodate and the glycol is 8g:60mL:6mL;
Step A2: mixing 2-acrylamide and deionized water, stirring and adding mercaptoethylamine and ammonium persulfate under the protection of nitrogen at the stirring speed of 150rpm and the temperature of 60 ℃, reacting for 10 hours to obtain amino-terminated polyacrylamide, mixing and ultrasonically dispersing commercially available graphene oxide with the size of 10 mu m, isophorone diisocyanate and N, N-dimethylformamide, reacting for 24 hours under the protection of nitrogen at the stirring speed of 300rpm and the temperature of 80 ℃, adding amino-terminated polyacrylamide, and continuously reacting for 24 hours to obtain grafted graphene oxide;
The dosage ratio of 2-acrylamide, mercaptoethylamine and ammonium persulfate is 0.15mol:0.015mol:0.005mol; the dosage ratio of the graphene oxide, isophorone diisocyanate and amino-terminated polyacrylamide is 2g:0.03mol:10g;
Step A3: mixing trifluoroacetic acid, triethylsilane, grafted graphene oxide and acetonitrile, stirring and adding cellulose hydroformylation at a stirring speed of 150rpm and a temperature of 110 ℃, reacting for 18 hours, adding acetic anhydride, cooling to 35 ℃, and continuing to react for 1 hour to obtain modified cellulose;
trifluoroacetic acid, triethylsilane, grafted graphene oxide, acetonitrile, hydroformylation cellulose and acetic anhydride in a dosage ratio of 70mL:50mL:2g:300mL:8g:40mL.
Example 4
The cross-linking impregnating compound is prepared by the following steps:
Step B1: mixing 2-chloro-4.6-diamino-1.3.5-sym-triazine, sodium bis (trimethylsilyl) amide and tetrahydrofuran, stirring and adding di-tert-butyl dicarbonate under the conditions of nitrogen protection and stirring speed of 90rpm and room temperature, reacting for 18 hours to obtain an intermediate 1, mixing the intermediate 1, sodium hydrosulfide and absolute ethyl alcohol, reacting for 8 hours under the conditions of stirring speed of 90rpm and temperature of 85 ℃ to obtain an intermediate 2, mixing the intermediate 2 and tetrahydrofuran, adding hydrogen peroxide under the conditions of stirring speed of 90rpm and room temperature, and reacting for 1 hour to obtain an intermediate 3;
The dosage ratio of 2-chloro-4.6-diamino-1.3.5-s-triazine, sodium bis (trimethylsilyl) amide and di-tert-butyl dicarbonate is 0.02mol:0.04mol:0.04mol; the ratio of the amount of intermediate 1 to the amount of sodium hydrosulfide is 0.02mol:1.2g; the mass concentration of the hydrogen peroxide is 30%, and the dosage ratio of the intermediate 2 to the hydrogen peroxide is 0.02mol:1.5g;
step B2: mixing the intermediate 3, tertiary butyl disilyl trifluoro methane sulfonate and methylene dichloride, reacting for 6 hours at room temperature under the condition of stirring speed of 120rpm to obtain an intermediate 4, mixing the intermediate 4, parahydroxybenzaldehyde and tetrahydrofuran, reacting for 6 hours under the condition of stirring speed of 120rpm and temperature of 50 ℃ under the protection of nitrogen, adding DOPO, heating to 60 ℃, and reacting for 12 hours to obtain an intermediate 5;
Intermediate 3, t-butyldisilyl triflate and dichloromethane in a ratio of 0.01mol:0.01mol:120mL; the dosage ratio of the intermediate 4, the parahydroxyben-zaldehyde and DOPO is 0.01mol:0.04mol:0.04mol;
step B3: mixing the intermediate 5, triethylamine and tetrahydrofuran, stirring at a stirring speed of 80rpm at room temperature, adding acryloyl chloride, and reacting for 12 hours to obtain a crosslinking sizing agent;
The dosage ratio of the intermediate 5, triethylamine and acryloyl chloride is 0.01mol:5g:0.08mol.
Example 5
The cross-linking impregnating compound is prepared by the following steps:
Step B1: mixing 2-chloro-4.6-diamino-1.3.5-sym-triazine, sodium bis (trimethylsilyl) amide and tetrahydrofuran, stirring and adding di-tert-butyl dicarbonate under the conditions of nitrogen protection and stirring speed of 120rpm and room temperature, reacting for 16 hours to obtain an intermediate 1, mixing the intermediate 1, sodium hydrosulfide and absolute ethyl alcohol, reacting for 8 hours under the conditions of stirring speed of 120rpm and temperature of 85 ℃, obtaining an intermediate 2, mixing the intermediate 2 and tetrahydrofuran, adding hydrogen peroxide under the conditions of stirring speed of 120rpm and room temperature, and reacting for 0.5 hour to obtain an intermediate 3;
The dosage ratio of 2-chloro-4.6-diamino-1.3.5-s-triazine, sodium bis (trimethylsilyl) amide and di-tert-butyl dicarbonate is 0.02mol:0.05mol:0.04mol; the ratio of the amount of intermediate 1 to the amount of sodium hydrosulfide is 0.02mol:1.3g; the mass concentration of the hydrogen peroxide is 30%, and the dosage ratio of the intermediate 2 to the hydrogen peroxide is 0.02mol:1.5g;
Step B2: mixing the intermediate 3, tertiary butyl disilyl trifluoro methane sulfonate and methylene dichloride, reacting for 6 hours at room temperature with the stirring speed of 150rpm to obtain an intermediate 4, mixing the intermediate 4, parahydroxybenzaldehyde and tetrahydrofuran, reacting for 4 hours with the stirring speed of 150rpm and the temperature of 50 ℃ under the protection of nitrogen, adding DOPO, heating to 60 ℃, and reacting for 12 hours to obtain an intermediate 5;
intermediate 3, t-butyldisilyl triflate and dichloromethane in a ratio of 0.01mol:0.01mol:120mL; the dosage ratio of the intermediate 4, the parahydroxyben-zaldehyde and DOPO is 0.01mol:0.04mol:0.05mol;
step B3: mixing the intermediate 5, triethylamine and tetrahydrofuran, stirring at a stirring speed of 80-120rpm and at room temperature, adding acryloyl chloride, and reacting for 12 hours to obtain a crosslinking sizing agent;
The dosage ratio of the intermediate 5, triethylamine and acryloyl chloride is 0.01mol:5g:0.09mol.
Example 6
The cross-linking impregnating compound is prepared by the following steps:
Step B1: mixing 2-chloro-4.6-diamino-1.3.5-sym-triazine, sodium bis (trimethylsilyl) amide and tetrahydrofuran, stirring and adding di-tert-butyl dicarbonate under the conditions of nitrogen protection and stirring speed of 120rpm and room temperature, reacting for 18 hours to obtain an intermediate 1, mixing the intermediate 1, sodium hydrosulfide and absolute ethyl alcohol, reacting for 8 hours under the conditions of stirring speed of 120rpm and temperature of 85 ℃ to obtain an intermediate 2, mixing the intermediate 2 and tetrahydrofuran, adding hydrogen peroxide under the conditions of stirring speed of 120rpm and room temperature, and reacting for 1 hour to obtain an intermediate 3;
The dosage ratio of 2-chloro-4.6-diamino-1.3.5-s-triazine, sodium bis (trimethylsilyl) amide and di-tert-butyl dicarbonate is 0.02mol:0.05mol:0.05mol; the ratio of the amount of intermediate 1 to the amount of sodium hydrosulfide is 0.02mol:1.4g; the mass concentration of the hydrogen peroxide is 30%, and the dosage ratio of the intermediate 2 to the hydrogen peroxide is 0.02mol:1.6g;
Step B2: mixing the intermediate 3, tertiary butyl disilyl trifluoro methane sulfonate and methylene dichloride, reacting for 6 hours at room temperature with the stirring speed of 150rpm to obtain an intermediate 4, mixing the intermediate 4, parahydroxybenzaldehyde and tetrahydrofuran, reacting for 6 hours with the stirring speed of 150rpm and the temperature of 50 ℃ under the protection of nitrogen, adding DOPO, heating to 60 ℃, and reacting for 12 hours to obtain an intermediate 5;
intermediate 3, t-butyldisilyl triflate and dichloromethane in a ratio of 0.01mol:0.01mol:120mL; the dosage ratio of the intermediate 4, the parahydroxyben-zaldehyde and DOPO is 0.01mol:0.05mol:0.05mol;
Step B3: mixing the intermediate 5, triethylamine and tetrahydrofuran, stirring at a stirring speed of 120rpm at room temperature, adding acryloyl chloride, and reacting for 12 hours to obtain a crosslinking sizing agent;
the dosage ratio of the intermediate 5, triethylamine and acryloyl chloride is 0.01mol:5g:0.1mol.
Example 7
The lyocell fiber non-woven fabric is prepared by the following steps: step S1: weighing the following raw materials in parts by weight: 20 parts of commercially available Sidian 500 cellulose pulp, 4 parts of modified cellulose of example 1, 150 parts of N-methylmorpholine-N-oxide solution, 1 part of 1010 antioxidant, 12 parts of cross-linking impregnating compound of example 4, 2 parts of sodium phosphate, 140 parts of ethanol and 30 parts of water, wherein the mass fraction of the N-methylmorpholine-N-oxide solution is 50%;
Step S2: mixing cellulose pulp, modified cellulose, an antioxidant and an N-methylmorpholine-N-oxide solution to prepare a spinning solution, adding the spinning solution into a spinning melt-blowing device, spinning, melt-blowing, forming a net, and leaching to prepare non-infiltrated non-woven fabrics;
Step S3: mixing a cross-linking impregnating compound, sodium phosphate, ethanol and water to prepare a cross-linking impregnating solution, soaking non-impregnated non-woven fabrics in the cross-linking impregnating solution at the temperature of 70 ℃ for 40min, performing two-soaking and two-bundling by using a padder, controlling the rolling surplus rate to be 80%, taking out, washing with water, pre-drying at 80 ℃, and baking at 140 ℃ to prepare the lyocell fiber non-woven fabrics.
Example 8
The lyocell fiber non-woven fabric is prepared by the following steps: step S1: weighing the following raw materials in parts by weight: 30 parts of commercially available Sidian 500 cellulose pulp, 4 parts of modified cellulose of example 2, 180 parts of N-methylmorpholine-N-oxide solution, 2 parts of 1010 antioxidant, 15 parts of cross-linking impregnating compound of example 5, 2 parts of sodium phosphate, 150 parts of ethanol and 40 parts of water, wherein the mass fraction of the N-methylmorpholine-N-oxide solution is 50%;
Step S2: mixing cellulose pulp, modified cellulose, an antioxidant and an N-methylmorpholine-N-oxide solution to prepare a spinning solution, adding the spinning solution into a spinning melt-blowing device, spinning, melt-blowing, forming a net, and leaching to prepare non-infiltrated non-woven fabrics;
Step S3: mixing the cross-linking impregnating compound, sodium phosphate, ethanol and water to prepare a cross-linking impregnating solution, soaking non-impregnated non-woven fabrics in the cross-linking impregnating solution for 30min at the temperature of 70 ℃, performing secondary soaking and secondary bundling by using a padder, controlling the rolling surplus rate to be 80%, taking out, washing with water, pre-drying at 80 ℃, and baking at 140 ℃ to prepare the lyocell fiber non-woven fabrics.
Example 9
The lyocell fiber non-woven fabric is prepared by the following steps: step S1: weighing the following raw materials in parts by weight: 30 parts of commercially available Sidian 500 cellulose pulp, 6 parts of modified cellulose of example 3, 180 parts of N-methylmorpholine-N-oxide solution, 2 parts of 1010 antioxidant, 15 parts of cross-linking impregnating compound of example 6, 4 parts of sodium phosphate, 150 parts of ethanol and 40 parts of water, wherein the mass fraction of the N-methylmorpholine-N-oxide solution is 50%;
Step S2: mixing cellulose pulp, modified cellulose, an antioxidant and an N-methylmorpholine-N-oxide solution to prepare a spinning solution, adding the spinning solution into a spinning melt-blowing device, spinning, melt-blowing, forming a net, and leaching to prepare non-infiltrated non-woven fabrics;
Step S3: mixing a cross-linking impregnating compound, sodium phosphate, ethanol and water to prepare a cross-linking impregnating solution, soaking non-impregnated non-woven fabrics in the cross-linking impregnating solution at the temperature of 70 ℃ for 40min, performing two-soaking and two-bundling by using a padder, controlling the rolling surplus rate to be 80%, taking out, washing with water, pre-drying at 80 ℃, and baking at 140 ℃ to prepare the lyocell fiber non-woven fabrics.
Comparative example 1
This comparative example was compared to example 9, except that the modified cellulose was replaced with 30 μm cellulose, which is commercially available in a constant state of the art, and the procedure was the same.
Comparative example 2
Compared with the example 9, the modified cellulose is prepared by replacing the grafted graphene oxide with a mixture of commercially available Xintai 20 polyacrylamide and commercially available Shuobang 10 mu m graphene oxide, wherein the weight ratio of the polyacrylamide to the graphene oxide is 5g:1g, the other steps are the same.
Comparative example 3
In this comparative example, the cross-linking impregnating compound was replaced with intermediate 5 of example 6, and the procedure was the same as in example 9.
Comparative example 4
This comparative example was compared with example 9, except that the cross-linking impregnating compound was replaced with 1,3, 5-triacryloyl-hexahydrotriazine.
Taking one of the lyocell fiber nonwoven fabrics prepared in examples 7, 8, 9,1, 2,3 and 4, preparing a 5mm×200mm sample by referring to T/CCFA 01026-2016 and FZ/T52019-2018, immersing the sample in water for 30min, measuring the wet friction time by using a rotary steam wet friction device, and judging the fibrillation resistance of the sample by the length of the wet friction time, wherein the contact angle is 45 °, the friction shaft rotation speed is 500rpm, and the weight is 10g; the mechanical properties of the steel are tested by using a universal mechanical testing machine, the stretching rate is 10mm/min, and the clamping distance is 10mm; with reference to GB/T5454-1997, the limiting oxygen index was tested using an oxygen index meter and the test results are shown in the following table:
As can be seen from the test results of the table, comparing example 7, example 8 and example 9 with comparative example 1, comparative example 2, comparative example 3 and comparative example 4, the comparative example 1 replaces the modified cellulose with 30 μm cellulose with a constant market reputation, and the cellulose and the graphene oxide are obviously reduced in antigen fibrillation performance and tensile strength due to the lack of grafted graphene oxide, which indicates that the acetylated cellulose and graphene oxide can improve the antigen fibrillation performance and tensile strength of the lyocell fiber nonwoven fabric; in comparative example 2, the grafted graphene oxide is replaced by a mixture of commercially available Xintai 20 polyacrylamide and commercially available Shuobang 10 mu m graphene oxide, and the graphene oxide and cellulose are not uniformly dispersed in a base material due to the lack of chemical bond connection, so that the elongation at break and the tensile strength of the graphene oxide are reduced to a certain extent; in the comparative example 3, the cross-linking impregnating compound is replaced by the intermediate 5 in the example 6, and the intermediate 5 lacks double bonds compared with the cross-linking impregnating compound, so that the non-woven fabric cannot be cross-linked, and the antigen fibrillation performance of the non-woven fabric is poor; comparative example 4 the cross-linking impregnating compound was replaced with 1,3, 5-triacryloyl-hexahydrotriazine, and the flame retardant properties of the nonwoven fabric were significantly reduced due to the imperfections of the flame retardant system.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
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