CN110359118B - Preparation method of phenol modified urea-formaldehyde fiber - Google Patents
Preparation method of phenol modified urea-formaldehyde fiber Download PDFInfo
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- CN110359118B CN110359118B CN201910694098.8A CN201910694098A CN110359118B CN 110359118 B CN110359118 B CN 110359118B CN 201910694098 A CN201910694098 A CN 201910694098A CN 110359118 B CN110359118 B CN 110359118B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/08—Ureas; Thioureas
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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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
Abstract
The invention discloses a preparation method of phenolic modified urea-formaldehyde fiber, which comprises the steps of adding phenols, aldehydes and alkaline catalysts into two parts of macromolecular aqueous solution respectively for reaction (solution A), and adding urea, aldehydes and alkaline catalysts for reaction (solution B); and mixing the solution A and the solution B, adding an acid catalyst for continuous reaction, adding a basic catalyst and the rest aldehyde compound for reaction, spinning by using a wet spinning machine after the reaction is finished, heating and curing the primary fiber wound by a coagulating bath in an oven, naturally cooling, and taking out the primary fiber to obtain the phenolic modified urea-formaldehyde fiber. The phenolic modified urea-formaldehyde fiber is prepared by reasonably designing a reaction process and wet spinning, and the fiber serving as the three-dimensional crosslinking fiber has the advantages of low cost, flame retardance, heat insulation, no molten drop, no toxicity during combustion and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of preparation of special fibers, and particularly relates to a preparation method of a functional modified urea-formaldehyde fiber obtained by preparation of a phenolic modified urea-formaldehyde spinning solution, wet spinning and thermosetting.
Background
The three-dimensional cross-linked fiber has the characteristics of intrinsic flame retardance, heat insulation, high carbonization yield and the like, and has potential application value in the fields of functional textiles, carbon fibers and activated carbon fibers. However, the development of the crosslinked fiber is very slow because the crosslinked fiber and the oriented fiber have different preparation methods and structural characteristics.
Phenolic fibers were the first three-dimensionally crosslinked organic fibers [ Economy J, Clark R A. US patent, 3650102 ], the advent of the fiber broke through the inherent concept that three-dimensional crosslinked resins could not be formed into fibers. The phenolic resin fiber has good flame retardance, acid and alkali resistance, high temperature resistance and other properties due to the three-dimensional network structure formed by condensation reaction of phenols and formaldehyde. The flame-retardant polyester has good flame retardance, the limit oxygen index of the flame-retardant polyester reaches 32, and no toxic gas is generated during combustion or contact with flame; the fuel is not melted and does not drop in the combustion process, so that secondary fire can be avoided; can be carbonized and activated at higher temperature to prepare carbon fiber or porous carbon fiber materials. The phenolic fiber can be widely applied to the fields of flame-retardant textiles, high-temperature filtration, purification and adsorption and the like.
The urea-formaldehyde resin is widely used for manufacturing furniture and household appliances, mechanical parts, electrical fittings, various buttons, cover plates and the like as urea-formaldehyde plastic, wood adhesive and the like, is rapidly developed due to low price and good flame retardance, but has no related report on the application of the urea-formaldehyde resin in the aspect of fibers. The invention combines the advantages of urea formaldehyde and phenol formaldehyde to prepare the phenolic modified urea formaldehyde fiber.
Disclosure of Invention
The invention provides a preparation method of phenol modified urea-formaldehyde fiber, which comprises the steps of respectively adding phenol, aldehyde compounds, urea, aldehyde compounds and the like into two parts of high molecular water solution, mixing after reaction, adjusting to alkaline condition again after acid reaction process, adding the rest aldehyde compounds, reacting to obtain spinning solution, and preparing the three-dimensional cross-linked modified urea-formaldehyde fiber by wet spinning and thermosetting. The method provides a preparation method of the phenolic modified urea-formaldehyde fiber.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of phenol modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving water-soluble polymer in water to obtain water-soluble polymer aqueous solution, equally dividing into A, B parts of solution, adding phenols, aldehydes and alkaline catalyst into the part A of solution, and reacting at 50-95 deg.C for 0.4-10h to obtain solution A; adding urea, an aldehyde compound and an alkaline catalyst into the solution B, and reacting for 0.5-8h at 45-95 ℃ to obtain a solution B; mixing the solution A and the solution B, adjusting the pH value to acidity, and continuously reacting for 0.1-7h at the temperature of 40-95 ℃ to obtain a phenol modified urea-formaldehyde resin solution;
(2) adding an alkaline catalyst to adjust the urea-formaldehyde resin solution to be alkaline, slowly adding an aldehyde compound, reacting for a period of time at 35-95 ℃ to obtain a phenolic modified urea-formaldehyde spinning solution, and carrying out coagulation bath by using a wet spinning process to obtain the urea-formaldehyde nascent fiber.
(3) And washing and drying the nascent fiber, and then heating and curing the nascent fiber in an oven according to a certain heating rate to obtain the phenolic modified urea-formaldehyde fiber.
Further, the water-soluble polymer in the step (1) is one of PVA, PEG, polyvinyl formal, PVP, water-soluble modified starch or water-soluble modified cellulose; the water soluble polymer solution contains polymer 1-30 wt%.
Further, the aldehyde compound is one of formaldehyde, glutaraldehyde, acetaldehyde and paraformaldehyde; the alkaline catalyst is one of sodium hydroxide, potassium hydroxide, triethanolamine, sodium bicarbonate, magnesium hydroxide or calcium hydroxide, and the acidic catalyst is one of hydrochloric acid, sulfuric acid, phosphoric acid or oxalic acid; the phenolic compound is one of phenol and p-cresol.
Furthermore, in the step (1), the molar ratio of the phenols to the aldehydes in the solution of the part A is 1 (0.7-1.9), and the mass ratio of the polymer to the phenols is 1 (0.1-4); the molar ratio of urea to aldehydes in the solution of the part B is 1 (0.7-1.9), and the mass ratio of the polymer to the urea is 1 (0.2-10).
Further, in the step (1), the pH value range of the solution A is 7.4-11, and the pH value range of the solution B is 7.5-10.5; the first solution and the second solution are mixed and then the pH value is adjusted to be 4.0-6.9.
Further, adding an alkaline catalyst in the step (2) to adjust the pH value of the urea-formaldehyde resin solution to 7.4-10.5, wherein the reaction time is 0.4-8 h.
Furthermore, the addition amount of the aldehyde compound in the step (2) is based on the urea in the step (1), and the amount ratio of the urea to the aldehyde compound is 1 (0.3-2).
Further, the coagulating bath for wet spinning in the step (2) is a saturated sodium sulfate aqueous solution, and boric acid with the weight content of 0.1-5% is added, the temperature is 10-60 ℃, and the winding speed is 10-500 m/min.
Further, in the step (3), the drying temperature of the nascent fiber in the vacuum oven is 20-40 ℃, the heating rate is 1-30 ℃/min, the temperature is increased to 150-.
The invention has the following beneficial effects: the raw materials of the urea and the aldehyde compound are cheap and easy to obtain, strong acid, strong alkali or corrosive conditions are not needed, and the reaction conditions are mild; the addition of phenols changes the functionality of molecules, is beneficial to spinning and mechanical property improvement, is beneficial to reaction with aldehyde, and reduces the content of free aldehyde; the urea-formaldehyde molecules in the obtained spinning solution are of a high-molecular-weight linear structure, the obtained spinning solution has high viscosity and excellent spinnability, can be directly spun without further treatment, has mild spinning conditions and high spinning speed, the obtained nascent fiber only needs to be thermally cured to obtain the modified urea-formaldehyde fiber, and the curing and crosslinking are simple and easy; the obtained modified urea-formaldehyde fiber is a three-dimensional cross-linked fiber, does not need to be added with a flame retardant, has excellent flame retardant performance, high limit oxygen index, can be extinguished after leaving flame, releases very little toxic and harmful gas during combustion, has high flame retardant safety, excellent heat insulation performance and increased mechanical property of the fiber.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to be illustrative only and not to be limiting of the invention in any way, and any person skilled in the art can modify the present invention by applying the teachings disclosed above and applying them to equivalent embodiments with equivalent modifications. Any simple modification or equivalent changes made to the following embodiments according to the technical essence of the present invention, without departing from the technical spirit of the present invention, fall within the scope of the present invention.
Example 1
The preparation method of the phenolic modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving PVA in water to obtain 1wt% PVA solution, equally dividing into two parts, adding phenol, acetaldehyde and potassium hydroxide into one part, reacting for 0.4h at 50 ℃ and pH of 7.4, wherein the molar ratio of phenol to acetaldehyde is 1: 0.7; the mass ratio of PVA to phenol is 1: 0.1; adding urea and formaldehyde (the molar ratio is 1: 0.7) into the other part, wherein the mass ratio of PVA to urea is 1: 0.2; then adding sodium hydroxide aqueous solution, adjusting the pH value to 7.5, and reacting for 0.5h at 45 ℃; after the two parts of solution are blended, hydrochloric acid is added to adjust the pH value to 4.0, and the reaction lasts for 0.1h at 40 ℃;
(2) adding the calcium hydroxide aqueous solution again, adjusting the pH value to 7.4, then adding paraformaldehyde (the mass ratio of the urea to the paraformaldehyde added in the step (1) is 1: 0.3), and reacting at 35 ℃ for 0.4h to obtain a modified urea-formaldehyde solution with the aldehyde content of 0.09%;
(3) and (3) carrying out wet spinning on the obtained spinning solution, using a saturated sodium sulfate aqueous solution with the weight content of 0.1% boric acid as a coagulating bath, obtaining a nascent fiber at the winding speed of 10m/min at the temperature of 10 ℃, drying at the temperature of 20 ℃, heating to 150 ℃ at the speed of 1 ℃/min, keeping the temperature for 0.1h, naturally cooling, and taking out to obtain the modified urea-formaldehyde fiber.
The diameter of the prepared modified urea-formaldehyde fiber is 11 microns, the tensile strength is 380MPa, the elongation at break is 30%, and the LOI value of the fiber is 33.
Example 2
The preparation method of the phenolic modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving PEG in water to obtain 30wt% PEG aqueous solution, equally dividing into two parts, adding p-cresol, formaldehyde and sodium hydroxide into one part, and reacting at pH of 11 and 95 deg.C for 10h, wherein the molar ratio of p-cresol to formaldehyde is 1: 1.9; the mass ratio of PEG to p-cresol is 1: 4; adding urea and paraformaldehyde (the molar ratio is 1: 1.9) into the other part, wherein the mass ratio of PEG to urea is 1: 10; then adding a potassium hydroxide aqueous solution, adjusting the pH value to 10.5, and reacting for 8 hours at 95 ℃; after the two parts of solution are blended, adding sulfuric acid to adjust the pH value to 6.9, and reacting for 7 hours at 95 ℃;
(2) adding the sodium hydroxide aqueous solution again, adjusting the pH value to 10.5, then adding formaldehyde (the mass ratio of the urea to the formaldehyde added in the step (1) is 1: 2), and reacting for 8 hours at 95 ℃ to obtain a modified urea-formaldehyde solution with the aldehyde content of 0.08%;
(3) and (3) carrying out wet spinning on the obtained spinning solution, using a saturated sodium sulfate aqueous solution with the weight content of 5% boric acid as a coagulating bath, obtaining a nascent fiber at the winding speed of 500m/min at the temperature of 60 ℃, drying at the temperature of 40 ℃, heating at the temperature of 30 ℃/min to 230 ℃, keeping the temperature for 2h, naturally cooling, and taking out to obtain the urea-formaldehyde fiber.
The diameter of the prepared urea-formaldehyde fiber is 20 microns, the tensile strength is 350MPa, the elongation at break is 15%, and the LOI value of the fiber is 31.
Example 3
The preparation method of the phenolic modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving polyvinyl formal in water to obtain 20wt% of polyvinyl formal aqueous solution, equally dividing the polyvinyl formal aqueous solution into two parts, adding p-cresol, glutaraldehyde and calcium hydroxide into one part, and reacting for 4 hours at the conditions of pH of 8.5 and 65 ℃, wherein the molar ratio of the p-cresol to the glutaraldehyde is 1: 1.3; the mass ratio of the polyvinyl formal to the p-cresol is 1: 3; adding urea and glutaraldehyde (the molar ratio is 1: 1.1) into the other part, wherein the mass ratio of the polyvinyl formal to the urea is 1: 5; then adding triethanolamine, adjusting the pH value to 8.5, and reacting for 3h at 90 ℃; mixing the two solutions, adding phosphoric acid to adjust the pH value to 5, and reacting for 2 hours at 85 ℃;
(2) adding the potassium hydroxide aqueous solution again, adjusting the pH value to 8.5, then adding acetaldehyde (the mass ratio of the urea to the acetaldehyde added in the step (1) is 1: 0.5), and reacting for 4 hours at 75 ℃ to obtain a modified urea-formaldehyde solution with the aldehyde content of 0.1%;
(3) and (3) carrying out wet spinning on the obtained spinning solution, using a saturated sodium sulfate aqueous solution with the weight content of 3% boric acid as a coagulating bath, obtaining a nascent fiber at the winding speed of 300m/min at the temperature of 50 ℃, drying at the temperature of 30 ℃, heating at the temperature of 20 ℃/min to 210 ℃, keeping the temperature for 1h, naturally cooling, and taking out to obtain the modified urea-formaldehyde fiber.
The diameter of the prepared modified urea-formaldehyde fiber is 20 microns, the tensile strength is 280MPa, the elongation at break is 25%, and the LOI value of the fiber is 34.
Example 4
The preparation method of the phenolic modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving PVP in water to obtain 10wt% PVP aqueous solution, equally dividing into two parts, adding p-cresol, paraformaldehyde and magnesium hydroxide into one part, reacting for 3h at the conditions of pH 9 and 55 ℃, wherein the molar ratio of the p-cresol to the paraformaldehyde is 1: 1.1; the mass ratio of PVP to p-cresol is 1: 0.2; adding urea and acetaldehyde (the molar ratio is 1: 1.1) into the other part, wherein the mass ratio of PVP to urea is 1: 3; then adding sodium bicarbonate, adjusting the pH value to 8.5, and reacting for 2h at 90 ℃; after the two parts of solution are blended, adding oxalic acid to adjust the pH value to 5.5, and reacting for 2h at 85 ℃;
(2) adding triethanolamine again, adjusting the pH value to 8.5, then adding paraformaldehyde (the mass ratio of the urea to the paraformaldehyde added in the step (1) is 1: 0.5), and reacting for 4 hours at 75 ℃ to obtain a modified urea-formaldehyde solution with the aldehyde content of 0.12%;
(3) and (3) carrying out wet spinning on the obtained spinning solution, using a saturated sodium sulfate aqueous solution with the weight content of 3% boric acid as a coagulating bath, obtaining a nascent fiber at the winding speed of 200m/min at the temperature of 50 ℃, drying at the temperature of 30 ℃, heating to 180 ℃ at the speed of 20 ℃/min, keeping the temperature for 1h, naturally cooling, and taking out to obtain the modified urea-formaldehyde fiber.
The diameter of the prepared modified urea-formaldehyde fiber is 19 microns, the tensile strength is 310MPa, the elongation at break is 19%, and the LOI value of the fiber is 32.
Example 5
The preparation method of the phenolic modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving water-soluble starch in water to obtain 10wt% water-soluble starch aqueous solution, equally dividing into two parts, adding phenol, formaldehyde and sodium bicarbonate into one part, reacting at 75 deg.C and pH of 9.1 for 5 hr, wherein the molar ratio of phenol to formaldehyde is 1: 0.9; the mass ratio of the water-soluble starch to the phenol is 1: 0.2; adding urea and paraformaldehyde (the molar ratio is 1: 1.1) into the other part, wherein the mass ratio of the water-soluble starch to the urea is 1: 0.5; then adding magnesium hydroxide, adjusting the pH value to 8.5, and reacting for 2h at 90 ℃; after the two parts of solution are blended, adding sulfuric acid to adjust the pH value to 5.5, and reacting for 2h at 85 ℃;
(2) adding sodium bicarbonate again, adjusting the pH value to 8.5, then adding glutaraldehyde (the mass ratio of the urea to the glutaraldehyde added in the step (1) is 1: 0.5), and reacting for 4 hours at 75 ℃ to obtain a modified urea-formaldehyde solution with the aldehyde content of 0.06%;
(3) and (3) carrying out wet spinning on the obtained spinning solution, using a saturated sodium sulfate aqueous solution with the weight content of 2% boric acid as a coagulating bath, obtaining a nascent fiber at the winding speed of 180m/min at the temperature of 40 ℃, drying at the temperature of 30 ℃, heating to 190 ℃ at the speed of 20 ℃/min, keeping the temperature for 1h, naturally cooling, and taking out to obtain the modified urea-formaldehyde fiber.
The diameter of the prepared modified urea-formaldehyde fiber is 28 microns, the tensile strength is 230MPa, the elongation at break is 19%, and the LOI value of the fiber is 33.
Example 6
The preparation method of the phenolic modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving water-soluble cellulose in water to obtain 18wt% water-soluble cellulose aqueous solution, equally dividing into two parts, adding phenol, paraformaldehyde and triethanolamine into one part, and reacting at 85 deg.C and pH of 8.0 for 0.9h, wherein the molar ratio of phenol to paraformaldehyde is 1: 1.2; the mass ratio of the water-soluble cellulose to the phenol is 1: 1; adding urea and glutaraldehyde (molar ratio is 1: 1.2) into the other part, wherein the mass ratio of the water-soluble cellulose to the urea is 1: 2; then adding calcium hydroxide, adjusting the pH value to 8.5, and reacting for 2h at 90 ℃; after the two parts of solution are blended, adding sulfuric acid to adjust the pH value to 5.5, and reacting for 3 hours at 85 ℃;
(2) adding magnesium hydroxide again, adjusting the pH value to 8.5, then adding formaldehyde (the mass ratio of the urea to the formaldehyde added in the step (1) is 1: 0.8), and reacting for 4 hours at 75 ℃ to obtain a modified urea-formaldehyde solution with the aldehyde content of 0.1%;
(3) and (3) carrying out wet spinning on the obtained spinning solution, using a saturated sodium sulfate aqueous solution containing 0.9 wt% of boric acid as a coagulating bath, obtaining a nascent fiber at the winding speed of 50m/min at the temperature of 40 ℃, drying at the temperature of 30 ℃, heating to 190 ℃ at the speed of 20 ℃/min, keeping the temperature for 1h, naturally cooling, and taking out to obtain the modified urea-formaldehyde fiber.
The diameter of the prepared modified urea-formaldehyde fiber is 28 microns, the tensile strength is 280MPa, the elongation at break is 30 percent, and the LOI value of the fiber is 32.
Example 7
The preparation method of the phenolic modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving water-soluble cellulose in water to obtain 18wt% water-soluble cellulose aqueous solution, equally dividing into two parts, adding phenol, acetaldehyde and potassium hydroxide into one part, reacting for 4.5h at pH 10 and 80 deg.C, wherein the molar ratio of phenol to acetaldehyde is 1: 1; the mass ratio of the water-soluble cellulose to the phenol is 1: 0.4; adding urea and formaldehyde (the molar ratio is 1: 1.2) into the other part, wherein the mass ratio of the water-soluble cellulose to the urea is 1: 3; then adding sodium hydroxide, adjusting the pH value to 8.5, and reacting for 2h at 90 ℃; after the two parts of solution are blended, adding oxalic acid to adjust the pH value to 5.5, and reacting for 3 hours at 85 ℃;
(2) adding magnesium hydroxide again, adjusting the pH value to 8.5, then adding acetaldehyde (the mass ratio of the urea to the acetaldehyde added in the step (1) is 1: 0.8), and reacting for 4 hours at 75 ℃ to obtain a modified urea-formaldehyde solution with the aldehyde content of 0.08%;
(3) and (3) carrying out wet spinning on the obtained spinning solution, using a saturated sodium sulfate aqueous solution containing 1.9 wt% of boric acid as a coagulating bath, obtaining a nascent fiber at the winding speed of 50m/min at the temperature of 40 ℃, drying at the temperature of 30 ℃, heating to 190 ℃ at the speed of 20 ℃/min, keeping the temperature for 1h, naturally cooling, and taking out to obtain the urea-formaldehyde fiber.
The diameter of the prepared urea-formaldehyde fiber is 21 microns, the tensile strength is 390MPa, the elongation at break is 29 percent, and the LOI value of the fiber is 33.
Example 8
The preparation method of the phenolic modified urea-formaldehyde fiber comprises the following steps:
(1) dissolving PVA in water to obtain an 8wt% PVA aqueous solution, equally dividing the PVA aqueous solution into two parts, adding phenol, acetaldehyde and potassium hydroxide into one part, and reacting for 3.8h at the pH of 7.8 and the temperature of 60 ℃, wherein the molar ratio of the phenol to the acetaldehyde is 1: 0.9; the mass ratio of PVA to phenol is 1: 0.9; adding urea and formaldehyde (the molar ratio is 1: 1.2) into the other part, wherein the mass ratio of PVA to urea is 1: 3.6; then adding sodium hydroxide, adjusting the pH value to 8.5, and reacting for 2h at 90 ℃; after the two parts of solution are blended, hydrochloric acid is added to adjust the pH value to 5.5, and the reaction is carried out for 3 hours at 85 ℃;
(2) adding sodium hydroxide again, adjusting the pH value to 8.5, then adding formaldehyde (the mass ratio of the urea to the formaldehyde added in the step (1) is 1: 0.8), and reacting for 2h at 75 ℃ to obtain a modified urea-formaldehyde solution with the aldehyde content of 0.11%;
(3) and (3) carrying out wet spinning on the obtained spinning solution, using a saturated sodium sulfate aqueous solution with the weight content of 2% boric acid as a coagulating bath, obtaining a nascent fiber at the winding speed of 20m/min at the temperature of 40 ℃, drying at the temperature of 30 ℃, heating to 190 ℃ at the temperature of 20 ℃/min, keeping the temperature for 1.5h, naturally cooling, and taking out to obtain the urea-formaldehyde fiber.
The diameter of the prepared urea-formaldehyde fiber is 28 microns, the tensile strength is 380MPa, the elongation at break is 31 percent, and the LOI value of the fiber is 32.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The preparation method of the phenolic modified urea-formaldehyde fiber is characterized by comprising the following steps:
(1) dissolving water-soluble polymer in water to obtain water-soluble polymer aqueous solution, equally dividing into A, B parts of solution, adding phenols, aldehydes and alkaline catalyst into the part A of solution, and reacting at 50-95 deg.C for 0.4-10h to obtain solution A; adding urea, an aldehyde compound and an alkaline catalyst into the solution B, and reacting for 0.5-8h at 45-95 ℃ to obtain a solution B; mixing the solution A and the solution B, adjusting the pH value to acidity, and continuously reacting for 0.1-7h at the temperature of 40-95 ℃ to obtain a phenol modified urea-formaldehyde resin solution;
(2) adding an alkaline catalyst to adjust the urea-formaldehyde resin solution to be alkaline, slowly adding an aldehyde compound, reacting for a period of time at 35-95 ℃ to obtain a phenolic modified urea-formaldehyde spinning solution, and performing coagulation bath by using a wet spinning process to obtain urea-formaldehyde nascent fiber;
(3) washing and drying the nascent fiber, and then heating and curing the nascent fiber in an oven according to a certain heating rate to obtain the phenolic modified urea-formaldehyde fiber;
in the step (1), the molar ratio of the phenols to the aldehydes in the solution of the part A is 1 (0.7-1.9), and the mass ratio of the high polymer to the phenols is 1 (0.1-4); the molar ratio of urea to aldehydes in the solution of the part B is 1 (0.7-1.9), and the mass ratio of macromolecules to urea is 1 (0.2-10);
in the step (1), the pH value range of the solution A is 7.4-11, and the pH value range of the solution B is 7.5-10.5; mixing the solution A and the solution B, and adjusting the pH value to be 4.0-6.9;
adding an alkaline catalyst in the step (2) to adjust the pH value range of the urea-formaldehyde resin solution to 7.4-10.5, wherein the reaction time is 0.4-8 h;
the addition amount of the aldehyde compound in the step (2) is based on the urea in the step (1), and the mass ratio of the urea to the aldehyde compound is 1 (0.3-2).
2. The method of preparing a phenolic-modified urea formaldehyde fiber as claimed in claim 1, wherein: the water-soluble polymer in the step (1) is one of PVA, PEG, polyvinyl formal, PVP, water-soluble modified starch or water-soluble modified cellulose; the water soluble polymer solution contains polymer 1-30 wt%.
3. The method of preparing a phenolic-modified urea formaldehyde fiber as claimed in claim 1, wherein: the aldehyde compound is one of formaldehyde, glutaraldehyde, acetaldehyde and paraformaldehyde; the alkaline catalyst is one of sodium hydroxide, potassium hydroxide, triethanolamine, sodium bicarbonate, magnesium hydroxide or calcium hydroxide, and the acidic catalyst is one of hydrochloric acid, sulfuric acid, phosphoric acid or oxalic acid; the phenolic compound is one of phenol and p-cresol.
4. The method of preparing a phenolic-modified urea formaldehyde fiber as claimed in claim 1, wherein: and (3) the coagulating bath for wet spinning in the step (2) is a saturated sodium sulfate aqueous solution, and boric acid with the weight content of 0.1-5% is added, the temperature is 10-60 ℃, and the winding speed is 10-500 m/min.
5. The method of preparing a phenolic-modified urea formaldehyde fiber as claimed in claim 1, wherein: and (3) drying the nascent fiber in the vacuum oven at the temperature of 20-40 ℃, heating at the rate of 1-30 ℃/min to the temperature of 150-.
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| CN110846737A (en) * | 2019-11-27 | 2020-02-28 | 中原工学院 | Method for preparing phenolic modified melamine fiber by one-step method |
| CN112522805B (en) * | 2020-12-10 | 2023-03-21 | 河南本征新材料科技有限公司 | Preparation method of intrinsic flame-retardant fiber wet spinning |
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| US4202959A (en) * | 1976-12-08 | 1980-05-13 | Imperial Chemical Industries Limited | Sulfite-modified fibrous resinous material |
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2019
- 2019-07-30 CN CN201910694098.8A patent/CN110359118B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB305468A (en) * | 1928-02-04 | 1930-04-29 | Alais & Froges & Camarque Cie | Process for the preparation of artificial silk |
| JPS4912116A (en) * | 1972-05-17 | 1974-02-02 | ||
| GB1420838A (en) * | 1973-05-22 | 1976-01-14 | Teijin Ltd | Fibres and their production |
| US4138445A (en) * | 1974-05-21 | 1979-02-06 | Toray Industries, Inc. | Flame retardant fiber |
| JPS5274015A (en) * | 1975-12-15 | 1977-06-21 | Asahi Chem Ind Co Ltd | Filament yarns of urea resins modified with alcohols |
| US4202959A (en) * | 1976-12-08 | 1980-05-13 | Imperial Chemical Industries Limited | Sulfite-modified fibrous resinous material |
| US4178336A (en) * | 1977-03-11 | 1979-12-11 | Imperial Chemical Industries Limited | Production of fibres |
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