CN110359118A - A kind of preparation method of phenol-modified ureaformaldehyde fiber - Google Patents
A kind of preparation method of phenol-modified ureaformaldehyde fiber Download PDFInfo
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- CN110359118A CN110359118A CN201910694098.8A CN201910694098A CN110359118A CN 110359118 A CN110359118 A CN 110359118A CN 201910694098 A CN201910694098 A CN 201910694098A CN 110359118 A CN110359118 A CN 110359118A
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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 kind of preparation method of phenol-modified ureaformaldehyde fiber, in the water-soluble polymers being divided into two parts, it is separately added into phenols, aldehydes and basic catalyst reaction (first solution), urea, aldehydes and basic catalyst reaction (second solution)；Acidic catalyst is added in the mixing of first, second solution, and the reaction was continued, again plus basic catalyst and the reaction of remaining aldehyde compound, after using wet-spinning frame carry out spinning, by coagulating bath wind as-spun fibre be heating and curing in an oven, after Temperature fall take out obtain phenol-modified ureaformaldehyde fiber.The present invention is prepared for phenol-modified ureaformaldehyde fiber by rationally designing reaction process, wet spinning, which has many advantages, such as that at low cost, flame-retardant fiber, heat-insulated, nothing melt drop, burn nontoxic, have broad application prospects as three-dimensional cross-linked fiber type.
Description
Technical field
The invention belongs to the preparation fields of special fibre, and in particular to a kind of phenol-modified ureaformaldehyde spinning solution preparation, wet
Method spinning and heat cure are to obtain the preparation method of functional modification ureaformaldehyde fiber.
Background technique
Three-dimensional cross-linked fiber type have the characteristics that it is intrinsic it is fire-retardant, it is heat-insulated and carbonization yield it is high in functional textile, carbon fiber
Dimension and activated carbon fibre field have potential application.But since cross-linked fiber has different preparations from orientation fiber
Method and structure feature, so that the development of cross-linked fiber is extremely slow.
Phenolic fibre is the first three-dimensional cross-linked organic fiber [ Economy J, Clark R A.US patent,
3650102 ], the appearance of the fiber broken three-dimensional cross-linked resin can not be at fine intrinsic notion.Phenols and formaldehyde pass through condensation
The tridimensional network that reaction is formed assigns the performances such as the good fire-retardant, acid and alkali-resistance of phenolic fiber, high temperature resistant.With good
Anti-flammability, limit oxygen index burning or generates with when flame contact without toxic gas up to 32；Do not melted in combustion process,
Without dripping off, it can avoid spot fire；It can be carbonized, activate at a higher temperature, prepare carbon fiber or porous carbon fiber material.Phenolic aldehyde
Fiber can be widely applied to the fields such as flame retardant textiles, high temperature filtration, purification absorption.
Lauxite is widely used in manufacture furniture appliance, machine components, electrically as urea-formaldehyde plastics, wood adhesive etc.
Accessory, various button and cover board etc. are rapidly progressed due to cheap, good flame resistance, but answering in terms of fiber
With having no relevant report.The advantages of both present invention combination ureaformaldehyde, phenolic aldehyde, is prepared for phenol-modified ureaformaldehyde fiber.
Summary of the invention
The present invention provides a kind of preparation method of phenol-modified ureaformaldehyde fiber, is separately added into two parts of water-soluble polymers
It is blended after the reaction such as phenols, aldehyde compound and urea, aldehyde compound, after undergoing acid reaction process, is adjusted to alkali again
Property condition, and remaining aldehyde compound is added and reacts to obtain spinning solution, wet spinning, heat cure prepare three-dimensional cross-linked change
Property ureaformaldehyde fiber.This method provides a kind of preparation methods of phenol-modified ureaformaldehyde fiber.
In order to solve the above technical problems, the technical scheme is that
A kind of preparation method of phenol-modified ureaformaldehyde fiber, its steps are as follows:
(1) water soluble polymer aqueous solution is obtained by water soluble polymer is soluble in water, A, B two parts solution are divided into, to the portion A
Divide and phenols, aldehydes and basic catalyst are added in solution, reacts 0.4-10h under the conditions of 50-95 DEG C, obtain first solution；To the portion B
Divide and urea and aldehyde compound and basic catalyst are added in solution, then reacts 0.5-8h under the conditions of 45-95 DEG C, obtain
To second solution；PH value is adjusted after the mixing of first, second solution to acidity, the reaction was continued under the conditions of 40-95 DEG C 0.1-7h obtains phenols
Modified urea-formaldehyde resin solution；
(2) basic catalyst is added and adjusts urea-formaldehyde resin solution to alkalinity, and is slowly added to aldehyde compound, in 35-95 DEG C of item
After reacting a period of time under part, obtains phenol-modified ureaformaldehyde spinning solution and obtained after coagulating bath using wet spinning technology
Ureaformaldehyde as-spun fibre.
(3) then as-spun fibre is heating and curing according to certain heating rate in an oven by washing, drying,
Obtain phenol-modified ureaformaldehyde fiber.
Further, water soluble polymer is PVA, PEG in the step (1), polyvinyl formal, PVP, water solubility change
Property one of starch or water-soluble modified cellulose；High molecular mass content is 1-30% in water soluble polymer aqueous solution.
Further, the aldehyde compound is one of formaldehyde, glutaraldehyde, acetaldehyde, paraformaldehyde；Basic catalyst is
One of sodium hydroxide, potassium hydroxide, triethanolamine, sodium bicarbonate, magnesium hydroxide or calcium hydroxide, acidic catalyst are salt
One of acid, sulfuric acid, phosphoric acid or oxalic acid；Phenolic compound is one of phenol, paracresol.
Further, in the step (1), the molar ratio of phenols and aldehydes is 1:(0.7-1.9 in part A solution), high score
The mass ratio of son and phenols is 1:(0.1-4)；The molar ratio of urea and aldehydes is 1:(0.7-1.9 in part B solution), macromolecule
Mass ratio with urea is 1:(0.2-10).
Further, the pH value range of first solution is 7.4-11 in the step (1), and the pH value range of second solution is 7.5-
10.5,；It is 4.0-6.9 that pH value range is adjusted after the mixing of first, second solution.
Further, it is 7.4- that basic catalyst is added in the step (2) and adjusts the pH value range of urea-formaldehyde resin solution
10.5 reaction time were 0.4-8h.
Further, in the step (2) additional amount of aldehyde compound on the basis of the urea in step (1), urea and
The mass ratio of the material of aldehyde compound is 1:(0.3-2).
Further, the coagulating bath of wet spinning is saturated aqueous sodium sulfate in the step (2), and adds weight content
For the boric acid of 0.1-5%, temperature is 10-60 DEG C, winding speed 10-500m/min.
Further, 20-40 DEG C of drying temperature in vacuum drying oven of as-spun fibre, heating rate 1- in the step (3)
30 DEG C/min, it is warming up to 150-230 DEG C, constant temperature 0.1-2h, is taken out after Temperature fall up to modified urea-formaldehyde fiber.
The invention has the following advantages: urea and aldehyde compound raw material are cheap and easy to get, it is not necessarily to strong acid, highly basic or corruption
Corrosion condition, reaction condition are mild；The addition of phenols changes the degree of functionality of molecule, is conducive to the progress and mechanical property of spinning
Raising, while being conducive to and aldehyde reaction, reduce content of free aldehyde；Ureaformaldehyde molecule is the line of high molecular weight in gained spinning solution
Property structure, have viscosity higher, excellent spinnability, without be further processed can direct fabrics, spinning condition is mild, spinning speed
Degree is fast, and gained as-spun fibre only need to be by heat cure up to modified urea-formaldehyde fiber, and solidification crosslinking is simple and easy；Gained modified urea-formaldehyde
Fiber is a kind of three-dimensional cross-linked fiber, and without adding fire retardant, excellent flame retardancy, limit oxygen index is high, puts out, burns from flame
When release toxic and harmful gas it is considerably less, flame-retarding is high, and heat-proof quality is excellent, and fibrous mechanical property increases.
Specific embodiment
The present invention will be further explained with reference to the examples below, as described below, is only to preferable implementation of the invention
Example, not limits the present invention, any person skilled in the art is possibly also with the disclosure above
Technology contents be changed to the equivalent embodiment changed on an equal basis.Without departing from the concept of the present invention, according to the present invention
Technical spirit any simple modification or equivalent variations that following embodiment is made, fall within the scope of protection of the present invention.
Embodiment 1
The preparation method of the phenol-modified ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) by the PVA PVA aqueous solution soluble in water for obtaining 1wt%, two parts are divided into, phenol, acetaldehyde and hydrogen is added in a part
Potassium oxide reacts 0.4h under the conditions of pH is 7.4,50 DEG C, and the molar ratio of phenol and acetaldehyde is 1:0.7；The matter of PVA and phenol
Amount is than being 1:0.1；Urea and formaldehyde (molar ratio 1:0.7) is added in another part, and wherein the mass ratio of PVA and urea is 1:
0.2；Then sodium hydrate aqueous solution is added, adjusts pH value to 7.5, in 45 DEG C of reaction 0.5h；It is added after two parts solution blending
Salt acid for adjusting pH value is to 4.0,40 DEG C of reaction 0.1h；
(2) calcium hydroxide aqueous solution is added again, adjusts pH value to 7.4, paraformaldehyde is then added and (urine is added in step (1)
The mass ratio of the material of element and paraformaldehyde is 1:0.3), it is molten to obtain the modified urea-formaldehyde that aldehyde is 0.09% by 35 DEG C of reaction 0.4h
Liquid；
(3) gained spinning solution is by wet spinning, use saturated aqueous sodium sulfate that weight content is 0.1% boric acid as
Coagulating bath, winding speed is that 10m/min obtains as-spun fibre at 10 DEG C of temperature, then after 20 DEG C of drying, is heated up with 1 DEG C/min
It 150 DEG C, constant temperature 0.1h, takes out after Temperature fall up to modified urea-formaldehyde fiber.
The modified urea-formaldehyde fibre diameter of preparation is 11 microns, tensile strength 380MPa, elongation at break 30%, fiber
LOI value be 33.
Embodiment 2
The preparation method of the phenol-modified ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) two parts are divided by the PEG PEG aqueous solution soluble in water for obtaining 30wt%, a part be added paracresol, formaldehyde and
Sodium hydroxide reacts 10h under the conditions of pH is 11,95 DEG C, and the molar ratio of paracresol and formaldehyde is 1:1.9；PEG and paracresol
Mass ratio be 1:4；Urea and paraformaldehyde (molar ratio 1:1.9) is added in another part, wherein the mass ratio of PEG and urea
For 1:10；Then potassium hydroxide aqueous solution is added, adjusts pH value to 10.5, in 95 DEG C of reaction 8h；Add after two parts solution blending
Enter sulphur acid for adjusting pH value to 6.9,95 DEG C of reaction 7h；
(2) be added sodium hydrate aqueous solution again, adjust pH value to 10.5, be then added formaldehyde (be added in step (1) urea and
The mass ratio of the material of formaldehyde is 1:2), 95 DEG C of reaction 8h obtain the modified urea-formaldehyde solution that aldehyde is 0.08%；
(3) gained spinning solution is by wet spinning, uses saturated aqueous sodium sulfate that weight content is 5% boric acid as coagulating
Gu bathing, winding speed is that 500m/min obtains as-spun fibre under temperature 60 C, then after 40 DEG C of dryings, with 30 DEG C/min heating
It 230 DEG C, constant temperature 2h, takes out after Temperature fall up to ureaformaldehyde fiber.
The ureaformaldehyde fibre diameter of preparation is 20 microns, tensile strength 350MPa, elongation at break 15%, the LOI of fiber
Value is 31.
Embodiment 3
The preparation method of the phenol-modified ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) by the polyvinyl formal polyvinyl formal solution soluble in water for obtaining 20wt%, two parts are divided into,
Paracresol, glutaraldehyde and calcium hydroxide is added in a part, reacts 4h under the conditions of pH is 8.5,65 DEG C, paracresol and glutaraldehyde
Molar ratio is 1:1.3；The mass ratio of polyvinyl formal and paracresol is 1:3；Urea is added in another part and glutaraldehyde (rubs
You are than being 1:1.1), wherein the mass ratio of polyvinyl formal and urea is 1:5；Then triethanolamine is added, adjusts pH value
To 8.5, in 90 DEG C of reaction 3h；Phosphorus acid for adjusting pH value is added after two parts solution blending to 5,85 DEG C of reaction 2h；
(2) be added potassium hydroxide aqueous solution again, adjust pH value to 8.5, be then added acetaldehyde (be added in step (1) urea and
The mass ratio of the material of acetaldehyde is 1:0.5), 75 DEG C of reaction 4h obtain the modified urea-formaldehyde solution that aldehyde is 0.1%；
(3) gained spinning solution is by wet spinning, uses saturated aqueous sodium sulfate that weight content is 3% boric acid as coagulating
Gu bathing, winding speed is that 300m/min obtains as-spun fibre under temperature 50 C, then after 30 DEG C of dryings, with 20 DEG C/min heating
It 210 DEG C, constant temperature 1h, takes out after Temperature fall up to modified urea-formaldehyde fiber.
The modified urea-formaldehyde fibre diameter of preparation is 20 microns, tensile strength 280MPa, elongation at break 25%, fiber
LOI value be 34.
Embodiment 4
The preparation method of the phenol-modified ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) by the PVP PVP aqueous solution soluble in water for obtaining 10wt%, two parts are divided into, paracresol, poly first is added in a part
Aldehyde and magnesium hydroxide react 3h under the conditions of pH is 9,55 DEG C, and the molar ratio of paracresol and paraformaldehyde is 1:1.1；PVP with it is right
The mass ratio of cresols is 1:0.2；Urea and acetaldehyde (molar ratio 1:1.1) is added in another part, wherein the quality of PVP and urea
Than for 1:3；Then sodium bicarbonate is added, adjusts pH value to 8.5, in 90 DEG C of reaction 2h；Oxalic acid is added after two parts solution blending
PH value is adjusted to 5.5,85 DEG C of reaction 2h；
(2) it is added triethanolamine again, adjusts pH value to 8.5, paraformaldehyde is then added and (urea and more is added in step (1)
The mass ratio of the material of polyformaldehyde is 1:0.5), 75 DEG C of reaction 4h obtain the modified urea-formaldehyde solution that aldehyde is 0.12%；
(3) gained spinning solution is by wet spinning, uses saturated aqueous sodium sulfate that weight content is 3% boric acid as coagulating
Gu bathing, winding speed is that 200m/min obtains as-spun fibre under temperature 50 C, then after 30 DEG C of dryings, with 20 DEG C/min heating
It 180 DEG C, constant temperature 1h, takes out after Temperature fall up to modified urea-formaldehyde fiber.
The modified urea-formaldehyde fibre diameter of preparation is 19 microns, tensile strength 310MPa, elongation at break 19%, fiber
LOI value be 32.
Embodiment 5
The preparation method of the phenol-modified ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) by the water soluble starch water soluble starch aqueous solution soluble in water for obtaining 10wt%, two parts are divided into, a part adds
Enter phenol, formaldehyde and sodium bicarbonate, react 5h under the conditions of pH is 9.1,75 DEG C, the molar ratio of phenol and formaldehyde is 1:0.9；Water
The mass ratio of soluble starch and phenol is 1:0.2；Urea and paraformaldehyde (molar ratio 1:1.1) is added in another part, wherein
The mass ratio of water soluble starch and urea is 1:0.5；Then magnesium hydroxide is added, adjusts pH value to 8.5, in 90 DEG C of reaction 2h；
Sulphur acid for adjusting pH value is added after two parts solution blending to 5.5,85 DEG C of reaction 2h；
(2) sodium bicarbonate is added again, adjusts pH value to 8.5, glutaraldehyde is then added and (urea and penta 2 is added in step (1)
The mass ratio of the material of aldehyde is 1:0.5), 75 DEG C of reaction 4h obtain the modified urea-formaldehyde solution that aldehyde is 0.06%；
(3) gained spinning solution is by wet spinning, uses saturated aqueous sodium sulfate that weight content is 2% boric acid as coagulating
Gu bathing, winding speed is that 180m/min obtains as-spun fibre at 40 DEG C of temperature, then after 30 DEG C of dryings, with 20 DEG C/min heating
It 190 DEG C, constant temperature 1h, takes out after Temperature fall up to modified urea-formaldehyde fiber.
The modified urea-formaldehyde fibre diameter of preparation is 28 microns, tensile strength 230MPa, elongation at break 19%, fiber
LOI value be 33.
Embodiment 6
The preparation method of the phenol-modified ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) two parts are divided by the water-soluble cellulose water-soluble cellulose aqueous solution soluble in water for obtaining 18wt%, one
Point phenol, paraformaldehyde and triethanolamine is added, reacts 0.9h under the conditions of pH is 8.0,85 DEG C, phenol and paraformaldehyde rub
You are than being 1:1.2；The mass ratio of water-soluble cellulose and phenol is 1:1；Urea and glutaraldehyde is added in another part, and (molar ratio is
1:1.2), wherein the mass ratio of water-soluble cellulose and urea is 1:2；Then it is added calcium hydroxide, adjusts pH value to 8.5,
90 DEG C of reaction 2h；Sulphur acid for adjusting pH value is added after two parts solution blending to 5.5,85 DEG C of reaction 3h；
(2) it is added magnesium hydroxide again, adjusts pH value to 8.5, formaldehyde is then added and (urea and formaldehyde are added in step (1)
The mass ratio of the material is 1:0.8), 75 DEG C of reaction 4h obtain the modified urea-formaldehyde solution that aldehyde is 0.1%；
(3) gained spinning solution is by wet spinning, use saturated aqueous sodium sulfate that weight content is 0.9% boric acid as
Coagulating bath, winding speed is that 50m/min obtains as-spun fibre at 40 DEG C of temperature, then after 30 DEG C of drying, is heated up with 20 DEG C/min
It 190 DEG C, constant temperature 1h, takes out after Temperature fall up to modified urea-formaldehyde fiber.
The modified urea-formaldehyde fibre diameter of preparation is 28 microns, tensile strength 280MPa, elongation at break 30%, fiber
LOI value be 32.
Embodiment 7
The preparation method of the phenol-modified ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) two parts are divided by the water-soluble cellulose water-soluble cellulose aqueous solution soluble in water for obtaining 18wt%, one
Point phenol, acetaldehyde and potassium hydroxide is added, reacts 4.5h under the conditions of pH is 10,80 DEG C, the molar ratio of phenol and acetaldehyde is 1:
1；The mass ratio of water-soluble cellulose and phenol is 1:0.4；Urea and formaldehyde (molar ratio 1:1.2) is added in another part,
The mass ratio of middle water-soluble cellulose and urea is 1:3；Then sodium hydroxide is added, adjusts pH value to 8.5, is reacted at 90 DEG C
2h；Careless acid for adjusting pH value is added after two parts solution blending to 5.5,85 DEG C of reaction 3h；
(2) it is added magnesium hydroxide again, adjusts pH value to 8.5, acetaldehyde is then added and (urea and acetaldehyde are added in step (1)
The mass ratio of the material is 1:0.8), 75 DEG C of reaction 4h obtain the modified urea-formaldehyde solution that aldehyde is 0.08%；
(3) gained spinning solution is by wet spinning, use saturated aqueous sodium sulfate that weight content is 1.9% boric acid as
Coagulating bath, winding speed is that 50m/min obtains as-spun fibre at 40 DEG C of temperature, then after 30 DEG C of drying, is heated up with 20 DEG C/min
It 190 DEG C, constant temperature 1h, takes out after Temperature fall up to ureaformaldehyde fiber.
The ureaformaldehyde fibre diameter of preparation is 21 microns, tensile strength 390MPa, elongation at break 29%, the LOI of fiber
Value is 33.
Embodiment 8
The preparation method of the phenol-modified ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) by the PVA PVA aqueous solution soluble in water for obtaining 8wt%, two parts are divided into, phenol, acetaldehyde and hydrogen is added in a part
Potassium oxide reacts 3.8h under the conditions of pH is 7.8,60 DEG C, and the molar ratio of phenol and acetaldehyde is 1:0.9；The quality of PVA and phenol
Than for 1:0.9；Urea and formaldehyde (molar ratio 1:1.2) is added in another part, and wherein the mass ratio of PVA and urea is 1:3.6；
Then sodium hydroxide is added, adjusts pH value to 8.5, in 90 DEG C of reaction 2h；Salt acid for adjusting pH value is added after two parts solution blending
To 5.5,85 DEG C of reaction 3h；
(2) it is added sodium hydroxide again, adjusts pH value to 8.5, formaldehyde is then added and (urea and formaldehyde are added in step (1)
The mass ratio of the material is 1:0.8), 75 DEG C of reaction 2h obtain the modified urea-formaldehyde solution that aldehyde is 0.11%；
(3) gained spinning solution is by wet spinning, uses saturated aqueous sodium sulfate that weight content is 2% boric acid as coagulating
Gu bathing, winding speed is that 20m/min obtains as-spun fibre at 40 DEG C of temperature, then after 30 DEG C of dryings, with 20 DEG C/min heating 190
DEG C, constant temperature 1.5h takes out after Temperature fall up to ureaformaldehyde fiber.
The ureaformaldehyde fibre diameter of preparation is 28 microns, tensile strength 380MPa, elongation at break 31%, the LOI of fiber
Value is 32.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (9)
1. a kind of preparation method of phenol-modified ureaformaldehyde fiber, which is characterized in that steps are as follows:
(1) water soluble polymer aqueous solution is obtained by water soluble polymer is soluble in water, A, B two parts solution are divided into, to the portion A
Divide and phenols, aldehydes and basic catalyst are added in solution, reacts 0.4-10h under the conditions of 50-95 DEG C, obtain first solution；To the portion B
Divide and urea and aldehyde compound and basic catalyst are added in solution, then reacts 0.5-8h under the conditions of 45-95 DEG C, obtain
To second solution；PH value is adjusted after the mixing of first, second solution to acidity, the reaction was continued under the conditions of 40-95 DEG C 0.1-7h obtains phenols
Modified urea-formaldehyde resin solution；
(2) basic catalyst is added and adjusts urea-formaldehyde resin solution to alkalinity, and is slowly added to aldehyde compound, in 35-95 DEG C of item
After reacting a period of time under part, obtains phenol-modified ureaformaldehyde spinning solution and obtained after coagulating bath using wet spinning technology
Ureaformaldehyde as-spun fibre；
(3) then as-spun fibre is heating and curing in an oven according to certain heating rate, obtains by washing, drying
Phenol-modified ureaformaldehyde fiber.
2. the preparation method of the phenol-modified ureaformaldehyde fiber according to claim 1, it is characterised in that: in the step (1)
Water soluble polymer is in PVA, PEG, polyvinyl formal, PVP, water-soluble modified starch or water-soluble modified cellulose
It is a kind of；High molecular mass content is 1-30% in water soluble polymer aqueous solution.
3. the preparation method of the phenol-modified ureaformaldehyde fiber according to claim 1, it is characterised in that: the aldehydes chemical combination
Object is one of formaldehyde, glutaraldehyde, acetaldehyde, paraformaldehyde；Basic catalyst be sodium hydroxide, potassium hydroxide, triethanolamine,
One of sodium bicarbonate, magnesium hydroxide or calcium hydroxide, acidic catalyst are one of hydrochloric acid, sulfuric acid, phosphoric acid or oxalic acid；
Phenolic compound is one of phenol, paracresol.
4. the preparation method of the phenol-modified ureaformaldehyde fiber according to claim 1, it is characterised in that: the step (1)
In, the molar ratio of phenols and aldehydes is 1:(0.7-1.9 in part A solution), the mass ratio of macromolecule and phenols is 1:(0.1-
4)；The molar ratio of urea and aldehydes is 1:(0.7-1.9 in part B solution), the mass ratio of macromolecule and urea is 1:(0.2-
10).
5. the preparation method of the phenol-modified ureaformaldehyde fiber according to claim 1, it is characterised in that: in the step (1)
The pH value range of first solution is 7.4-11, and the pH value range of second solution is 7.5-10.5；PH value model is adjusted after the mixing of first, second solution
It encloses for 4.0-6.9.
6. the preparation method of the phenol-modified ureaformaldehyde fiber according to claim 1, it is characterised in that: in the step (2)
It is 0.4-8h that the pH value range that basic catalyst adjusting urea-formaldehyde resin solution is added, which is the 7.4-10.5 reaction time,.
7. the preparation method of the phenol-modified ureaformaldehyde fiber according to claim 1, it is characterised in that: in the step (2)
For the additional amount of aldehyde compound on the basis of the urea in step (1), the mass ratio of the material of urea and aldehyde compound is 1:
(0.3-2).
8. the preparation method of the phenol-modified ureaformaldehyde fiber according to claim 1, it is characterised in that: in the step (2)
The coagulating bath of wet spinning is saturated aqueous sodium sulfate, and adds the boric acid that weight content is 0.1-5%, temperature 10-60
DEG C, winding speed 10-500m/min.
9. the preparation method of the phenol-modified ureaformaldehyde fiber according to claim 1, it is characterised in that: in the step (3)
For as-spun fibre at 20-40 DEG C of drying temperature of vacuum drying oven, heating rate is 1-30 DEG C/min, is warming up to 150-230 DEG C, constant temperature
0.1-2h takes out after Temperature fall up to modified urea-formaldehyde fiber.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110714233A (en) * | 2019-11-27 | 2020-01-21 | 中原工学院 | Method for producing phenolic/melamine fibres by copolymerization |
| CN110846737A (en) * | 2019-11-27 | 2020-02-28 | 中原工学院 | Method for preparing phenolic modified melamine fiber by one-step method |
| CN110846740A (en) * | 2019-11-27 | 2020-02-28 | 中原工学院 | Method for preparing phenol modified melamine fiber by single-kettle method |
| CN112522805A (en) * | 2020-12-10 | 2021-03-19 | 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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| 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 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110714233A (en) * | 2019-11-27 | 2020-01-21 | 中原工学院 | Method for producing phenolic/melamine fibres by copolymerization |
| CN110846737A (en) * | 2019-11-27 | 2020-02-28 | 中原工学院 | Method for preparing phenolic modified melamine fiber by one-step method |
| CN110846740A (en) * | 2019-11-27 | 2020-02-28 | 中原工学院 | Method for preparing phenol modified melamine fiber by single-kettle method |
| CN112522805A (en) * | 2020-12-10 | 2021-03-19 | 河南本征新材料科技有限公司 | Preparation method of intrinsic flame-retardant fiber wet spinning |
| 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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