CN110373737A - A kind of method that multiple addition prepares melamine modified urea-formaldehyde fiber - Google Patents
A kind of method that multiple addition prepares melamine modified urea-formaldehyde fiber Download PDFInfo
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- CN110373737A CN110373737A CN201910694107.3A CN201910694107A CN110373737A CN 110373737 A CN110373737 A CN 110373737A CN 201910694107 A CN201910694107 A CN 201910694107A CN 110373737 A CN110373737 A CN 110373737A
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
- C08G12/36—Ureas; Thioureas
- C08G12/38—Ureas; Thioureas and melamines
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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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
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Abstract
The invention discloses a kind of methods that multiple addition prepares melamine modified urea-formaldehyde fiber, and melamine and aldehydes (first solution), urea and aldehydes (second solution) are separately added into two parts of water-soluble polymers, are separately added into basic catalyst reaction different time；Acidic catalyst and a certain amount of urea is added in the mixing of first, second solution, and the reaction was continued, then plus basic catalyst and remaining aldehyde compound reaction after, spinning is heating and curing to obtain modified urea-formaldehyde fiber.The present invention is improved by rationally designing reaction process, ureaformaldehyde molecule spinnability, and the degree of cross linking increases, 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 multiple addition prepares melamine modified urea-formaldehyde
The method of spinning solution, wet spinning and heat cure to obtain 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.Melamine passes through with formaldehyde
The tridimensional network that condensation reaction is formed assigns the performances such as the good fire-retardant, acid and alkali-resistance of melamine resin fiber, high temperature resistant.
Melamine resin (MF) fiber is also known as melamine fiber, is to have a kind of cross filament after phenolic fibre.With good resistance
Combustion property, limit oxygen index burn or generate with when flame contact without toxic gas up to 32；It is not melted in combustion process, without drop
It falls, can avoid spot fire；Melamine fiber can be used for a long time under the conditions of 200 DEG C simultaneously, and size, tensile strength are almost without change
Change [Luo Yifeng.New developments in hi-tech synthetic fibers [J].Tec fiber and application, 2000 (4): 1-8], melamine fiber can be
It is carbonized, activates under higher temperature, prepare carbon fiber or porous carbon fiber material.Melamine fiber can be widely applied to fire-retardant weaving
The fields such as product, 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.It the advantages of both present invention combination ureaformaldehyde, melamine, is prepared for by multiaddition method cyanurotriamide modified
Ureaformaldehyde fiber.
Summary of the invention
The present invention provides a kind of method that multiple addition prepares melamine modified urea-formaldehyde fiber, in water-soluble polymers
It is blended after melamine, urea, aldehyde compound reaction is added, after undergoing acid reaction process, is adjusted to alkaline condition again,
Remaining aldehyde compound is added to react to obtain spinning solution, it is fine that wet spinning, heat cure prepare three-dimensional cross-linked modified urea-formaldehyde
Dimension.This method provides a kind of methods that multiple addition prepares melamine modified urea-formaldehyde fiber.
In order to solve the above technical problems, the technical scheme is that
A kind of method that multiple addition prepares melamine modified urea-formaldehyde fiber, steps are as follows:
(1) water soluble polymer aqueous solution is obtained by water soluble polymer is soluble in water, then by water soluble polymer aqueous solution
It is divided into A, B two parts solution, melamine, aldehydes and basic catalyst are added into part A solution, in 50-95 DEG C of condition
Lower reaction 0.4-10h, obtains first solution；Urea and aldehyde compound and basic catalyst are added into part B solution, so
0.5-8h is reacted under the conditions of 45-95 DEG C afterwards, obtains second solution；Acidic catalyst tune is added after first solution, second solution are mixed
PH value is saved to acidity, urea is added under the conditions of 40-95 DEG C the reaction was continued 0.1-7h, obtain 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, modified urea-formaldehyde spinning solution is obtained, using wet spinning technology, ureaformaldehyde is obtained after coagulating bath
As-spun fibre；
(3) then as-spun fibre is heating and curing in an oven according to certain heating rate, obtains by washing, drying
Modified urea-formaldehyde 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- in the water soluble polymer aqueous solution
30%。
Further, the aldehyde compound is one of formaldehyde, glutaraldehyde, acetaldehyde or paraformaldehyde；Basic catalyst
For one of sodium hydroxide, potassium hydroxide, triethanolamine, sodium bicarbonate, magnesium hydroxide or calcium hydroxide；Acidic catalyst is
One of hydrochloric acid, sulfuric acid, phosphoric acid or oxalic acid.
Further, the molar ratio of melamine and aldehyde compound is 1:(0.7- in step (1) the part A solution
1.9), the mass ratio of macromolecule and melamine is 1:(0.1-4)；The molar ratio of urea and aldehyde compound in part B solution
For 1:(0.7-1.9), the mass ratio of macromolecule and urea is 1:(0.2-10).
Further, the amount that urea is added after step (1) the first solution, the mixing of second solution, which accounts for, is added urine in part B solution
The 5%-50% of the amount of plain substance.
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 acidic catalyst is added after first solution, second solution are mixed and adjusts pH value range.
Further, it is 7.4-10.5 that basic catalyst is added in the step (2) and adjusts urea-formaldehyde resin solution pH value range,
Reaction time is 0.4-8h.
Further, in the step (2) additive 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；Urea, aldehydes repeatedly add, and are conducive to the control of the extent of reaction, and molecular structure has obtained excellent
Change；The addition of melamine improves the degree of functionality of molecule, is conducive to the increase of the degree of cross linking, while being conducive to and aldehyde reaction, drop
Low content of free aldehyde；Ureaformaldehyde molecule is the linear structure of high molecular weight in gained spinning solution, has viscosity higher, and excellent can
Spin property, without be further processed can direct fabrics, spinning condition is mild, and spinning speed is fast, and gained as-spun fibre need to only pass through heat
Solidify up to modified urea-formaldehyde fiber, solidification crosslinking is simple and easy；Gained modified urea-formaldehyde fiber is a kind of three-dimensional cross-linked fiber, is not necessarily to
Fire retardant, excellent flame retardancy are added, limit oxygen index is high, release toxic and harmful gas is considerably less when putting out, burn from flame, hinders
Fire highly-safe, 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 method that the multiple addition of the present embodiment prepares melamine modified urea-formaldehyde fiber, steps are as follows:
(1) by the PVA PVA aqueous solution soluble in water for obtaining 1wt%, two parts are divided into, melamine, acetaldehyde is added in a part
And potassium hydroxide, 0.4h is reacted under the conditions of pH is 7.4,50 DEG C, and the molar ratio of melamine and acetaldehyde is 1:0.7, PVA and three
The mass ratio of poly cyanamid is 1:0.1；Urea and formaldehyde (molar ratio 1:0.7) is added in another part, wherein the matter of PVA and urea
Then amount is added sodium hydrate aqueous solution, adjusts pH value to 7.5, in 45 DEG C of reaction 0.5h than being 1:0.2；Two parts solution is total
Salt acid for adjusting pH value is added after mixed to 4.0,40 DEG C of addition urea (account for the amount of alkaline condition addition urea substance 5%), 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 14 microns, tensile strength 341MPa, elongation at break 33%, fiber
LOI value be 33.
Embodiment 2
The method that the multiple addition of the present embodiment prepares melamine modified urea-formaldehyde fiber, steps are as follows:
(1) by the PEG PEG aqueous solution soluble in water for obtaining 30wt%, two parts are divided into, melamine, formaldehyde is added in a part
And sodium hydroxide, 10h is reacted under the conditions of pH is 11,95 DEG C, and the molar ratio of melamine and formaldehyde is 1:1.9, PEG and three
The mass ratio of poly cyanamid is 1:4；Urea and paraformaldehyde (molar ratio 1:1.9) is added in another part, wherein PEG and urea
Mass ratio is 1:10；Then potassium hydroxide aqueous solution is added, adjusts pH value to 10.5, in 95 DEG C of reaction 8h；Two parts solution is total
Sulphur acid for adjusting pH value is added after mixed to 6.9,95 DEG C of addition urea (account for the amount of alkaline condition addition urea substance 50%), 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 22 microns, tensile strength 346MPa, elongation at break 19%, the LOI of fiber
Value is 31.
Embodiment 3
The method that the multiple addition of the present embodiment prepares melamine modified urea-formaldehyde fiber, steps are as follows:
(1) by the polyvinyl formal polyvinyl formal solution soluble in water for obtaining 20wt%, two parts are divided into,
Melamine, glutaraldehyde and calcium hydroxide is added in a part, reacts 4h, melamine and penta 2 under the conditions of pH is 8.5,65 DEG C
The molar ratio of aldehyde is 1:1.3；The mass ratio of polyvinyl formal and melamine is 1:3；Urea and penta is added in another part
Dialdehyde (molar ratio 1:1.1), wherein the mass ratio of polyvinyl formal and urea is 1:5；Then triethanolamine is added, adjusts
PH value is saved to 8.5, in 90 DEG C of reaction 3h；Phosphorus acid for adjusting pH value to 5,55 DEG C of addition urea are added after two parts solution blending (to account for
The 25% of the amount of urea substance is added in alkaline condition), react 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 33 microns, tensile strength 284MPa, elongation at break 21%, fiber
LOI value be 32.
Embodiment 4
The method that the multiple addition of the present embodiment prepares melamine modified urea-formaldehyde fiber, steps are as follows:
(1) by the PVP PVP aqueous solution soluble in water for obtaining 10wt%, two parts are divided into, melamine, poly is added in a part
Formaldehyde and magnesium hydroxide react 3h under the conditions of pH is 9,55 DEG C, and the molar ratio of melamine and paraformaldehyde is 1:1.1；
The mass ratio of PVP and melamine is 1:0.2；Urea and acetaldehyde (molar ratio 1:1.1) is added in another part, wherein PVP with
The mass ratio of urea is 1:3；Then sodium bicarbonate is added, adjusts pH value to 8.5, in 90 DEG C of reaction 2h；Two parts solution blending
Careless acid for adjusting pH value is added afterwards to 5.5,75 DEG C of addition urea (account for the amount of alkaline condition addition urea substance 15%), reacts 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 17 microns, tensile strength 320MPa, elongation at break 13%, fiber
LOI value be 34.
Embodiment 5
The method that the multiple addition of the present embodiment prepares melamine modified urea-formaldehyde fiber, 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 melamine, formaldehyde and sodium bicarbonate, react 5h under the conditions of pH is 9.1,75 DEG C, the molar ratio of melamine and formaldehyde is
1:0.9；Wherein the mass ratio of water soluble starch and melamine is 1:0.2；Another part be added urea and paraformaldehyde (mole
Than for 1:1.1), wherein the mass ratio of water soluble starch and urea is 1:0.5；Then magnesium hydroxide is added, adjusts pH value and arrives
8.5, in 90 DEG C of reaction 2h；Sulphur acid for adjusting pH value to 5.5,55 DEG C of addition urea are added after two parts solution blending and (account for alkaline item
The 19% of the amount of urea substance is added in part), react 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 22 microns, tensile strength 236MPa, elongation at break 17%, fiber
LOI value be 33.
Embodiment 6
The method that the multiple addition of the present embodiment prepares melamine modified urea-formaldehyde fiber, 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
Divide and melamine, paraformaldehyde and triethanolamine is added, reacts 0.9h, melamine and aldehydes under the conditions of pH is 8.0,85 DEG C
Molar ratio be 1:1.2；The mass ratio of water-soluble cellulose and melamine is 1:1；Urea and glutaraldehyde is added in another part
(molar ratio 1:1.2), wherein the mass ratio of water-soluble cellulose and urea is 1:2；Then calcium hydroxide is added, adjusts pH value
To 8.5, in 90 DEG C of reaction 2h；Sulphur acid for adjusting pH value to 5.5,76 DEG C of addition urea are added after two parts solution blending and (account for alkalinity
The 45% of the amount of urea substance is added in condition), react 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 27 microns, tensile strength 230MPa, elongation at break 40%, fiber
LOI value be 31.
Embodiment 7
The method that the multiple addition of the present embodiment prepares melamine modified urea-formaldehyde fiber, 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 melamine, acetaldehyde and potassium hydroxide is added, reacts 4.5h under the conditions of pH is 10,80 DEG C, melamine and aldehydes rub
You are than being 1:1；Wherein the mass ratio of water-soluble cellulose and melamine is 1:0.4；Urea is added in another part and formaldehyde (rubs
You are than being 1:1.2), wherein the mass ratio of water-soluble cellulose and urea is 1:3；Then sodium hydroxide is added, adjusts pH value and arrives
8.5, in 90 DEG C of reaction 2h；Careless acid for adjusting pH value to 5.5,76 DEG C of addition urea are added after two parts solution blending and (account for alkaline item
The 49% of the amount of urea substance is added in part), react 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 24 microns, tensile strength 310MPa, elongation at break 29%, the LOI of fiber
Value is 32.
Embodiment 8
The method that the multiple addition of the present embodiment prepares melamine modified urea-formaldehyde fiber, steps are as follows:
(1) by the PVA PVA aqueous solution soluble in water for obtaining 8wt%, two parts are divided into, melamine, acetaldehyde is added in a part
And potassium hydroxide, 3.8h is reacted under the conditions of pH is 7.8,60 DEG C, and the molar ratio of melamine and aldehydes is 1:0.9；Wherein PVA
Mass ratio with melamine is 1:0.9；Urea and formaldehyde (molar ratio 1:1.2) is added in another part, wherein PVA and urine
The mass ratio of element is 1:3.6；Then sodium hydroxide is added, adjusts pH value to 8.5, in 90 DEG C of reaction 2h；Two parts solution blending
Salt acid for adjusting pH value is added afterwards to 5.5,83 DEG C of addition urea (account for the amount of alkaline condition addition urea substance 33%), reacts 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 22 microns, tensile strength 280MPa, elongation at break 31%, the LOI of fiber
Value is 33.
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 (10)
1. a kind of method that multiple addition prepares melamine modified urea-formaldehyde fiber, it is characterised in that steps are as follows:
(1) water soluble polymer aqueous solution is obtained by water soluble polymer is soluble in water, then by water soluble polymer aqueous solution
It is divided into A, B two parts solution, melamine, aldehydes and basic catalyst are added into part A solution, in 50-95 DEG C of condition
Lower reaction 0.4-10h, obtains first solution；Urea and aldehyde compound and basic catalyst are added into part B solution, so
0.5-8h is reacted under the conditions of 45-95 DEG C afterwards, obtains second solution；Acidic catalyst tune is added after first solution, second solution are mixed
PH value is saved to acidity, urea is added under the conditions of 40-95 DEG C the reaction was continued 0.1-7h, obtain 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, modified urea-formaldehyde spinning solution is obtained, using wet spinning technology, ureaformaldehyde is obtained after coagulating bath
As-spun fibre；
(3) then as-spun fibre is heating and curing in an oven according to certain heating rate, obtains by washing, drying
Modified urea-formaldehyde fiber.
2. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that: institute
Stating water soluble polymer in step (1) is that PVA, PEG, polyvinyl formal, PVP, water-soluble modified starch or water solubility change
Property one of cellulose, high molecular mass content is 1-30% in the water soluble polymer aqueous solution.
3. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that: institute
Stating aldehyde compound is one of formaldehyde, glutaraldehyde, acetaldehyde or paraformaldehyde；Basic catalyst is sodium hydroxide, hydroxide
One of potassium, triethanolamine, sodium bicarbonate, magnesium hydroxide or calcium hydroxide；Acidic catalyst be hydrochloric acid, sulfuric acid, phosphoric acid or
One of oxalic acid.
4. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that: institute
Stating the molar ratio of melamine and aldehyde compound in step (1) part A solution is 1:(0.7-1.9), macromolecule and melamine
The mass ratio of amine is 1:(0.1-4)；The molar ratio of urea and aldehyde compound is 1:(0.7-1.9 in part B solution), macromolecule
Mass ratio with urea is 1:(0.2-10).
5. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that: institute
State step (1) first solution, second solution mixing after be added urea amount account in part B solution be added urea substance amount 5%-
50%。
6. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that: institute
The pH value range for stating first solution in step (1) is 7.4-11, and the pH value range of second solution is 7.5-10.5, and first solution, second is molten
It is 4.0-6.9 that acidic catalyst is added after liquid mixing and adjusts pH value range.
7. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that: institute
Stating and basic catalyst adjusting urea-formaldehyde resin solution pH value range is added in step (2) is 7.4-10.5, reaction time 0.4-8h.
8. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that: institute
The additive amount of aldehyde compound in step (2) is stated on the basis of the urea in step (1), the substance of urea and aldehyde compound
Amount is than being 1:(0.3-2).
9. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that: institute
The coagulating bath for stating wet spinning in step (2) is saturated aqueous sodium sulfate, and adds the boric acid that weight content is 0.1-5%, temperature
Degree is 10-60 DEG C, winding speed 10-500m/min.
10. the method that multiple addition according to claim 1 prepares melamine modified urea-formaldehyde fiber, it is characterised in that:
For as-spun fibre at 20-40 DEG C of drying temperature of vacuum drying oven, heating rate is 1-30 DEG C/min in the step (3), is warming up to
It 150-230 DEG C, constant temperature 0.1-2h, takes out after Temperature fall up to modified urea-formaldehyde fiber.
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