CN110359119A - A method of circulation acid-base method prepares ureaformaldehyde fiber - Google Patents
A method of circulation acid-base method prepares ureaformaldehyde fiber Download PDFInfo
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- CN110359119A CN110359119A CN201910694099.2A CN201910694099A CN110359119A CN 110359119 A CN110359119 A CN 110359119A CN 201910694099 A CN201910694099 A CN 201910694099A CN 110359119 A CN110359119 A CN 110359119A
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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
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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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
Abstract
The invention discloses a kind of methods of circulation acid-base method preparation ureaformaldehyde fiber, after urea, aldehydes and basic catalyst reaction are added in water-soluble polymers, sequentially add aldehydes, acidic catalyst, add basic catalyst and remaining aldehyde compound, finally being adjusted to acid reaction terminates, and ureaformaldehyde fiber is obtained after solution-polymerized SBR, heat cure.The present invention increases molecular weight and structural controllability, improves spinnability, the stability of spinning solution by rationally designing reaction process, the fiber is as three-dimensional cross-linked fiber type, have many advantages, such as that at low cost, flame-retardant fiber, heat-insulated, nothing melt drop, burns nontoxic, have broad application prospects.
Description
Technical field
The invention belongs to the preparation fields of special fibre, and in particular to one kind is molten by circulation acid-base method preparation ureaformaldehyde spinning
The method of liquid, wet spinning and heat cure to obtain functional ureaformaldehyde fiber.
Background technique
Three-dimensional cross-linked fiber type have the characteristics that it is fire-retardant, heat-insulated and carbonization yield it is high functional textile, carbon fiber and
Activated carbon fibre field has potential application.But since cross-linked fiber has different preparation methods from orientation fiber
And design feature, so that the development of cross-linked fiber is extremely slow, existing cross-linked fiber only has phenolic fibre and melamine is fine
Dimension etc. is several.
Phenolic fibre is the first three-dimensional cross-linked organic fiber, and 1968 by U.S.'s diamond dust (Carborundum)
The J.Economy of company applies for related patents [ Economy J, Clark R A for the first time.US patent, 3650102 ], the fibre
Three-dimensional cross-linked resin has been broken in the appearance of dimension can not be at fine intrinsic notion.As general chemistry fiber is in household, decoration
It is growing day by day using the harm in, chemical fibre indoors fire, the properties such as the high limit oxygen index (OI) of phenolic fibre, low-smoke
It is of concern, and has pushed further research and development [ Zeng Hanmin, the functional fibre [ M ] of phenolic fibre.Beijing: chemical industry
Publishing house, 2005:537-621 ].
The tridimensional network imparting melamine resin fiber that melamine and formaldehyde are formed by condensation reaction is good
Fire-retardant, acid and alkali-resistance, the performances such as high temperature resistant.Melamine resin (MF) fiber is also known as melamine fiber, is after phenolic fibre
There is a kind of cross filament.With good anti-flammability, limit oxygen index up to 32, burning or with when flame contact without toxic gas
It generates；It is not melted in combustion process, without dripping off, can avoid spot fire；Melamine fiber can make for a long time under the conditions of 200 DEG C simultaneously
With, and the almost unchanged [Luo Yifeng of size, tensile strength.New developments in hi-tech synthetic fibers [J].Tec fiber and application,
2000 (4): 1-8], melamine fiber can be carbonized at a higher temperature, activate, and prepare carbon fiber or porous carbon fiber material.Melamine
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.
Summary of the invention
The present invention provide it is a kind of circulation acid-base method preparation ureaformaldehyde fiber method, in water-soluble polymers be added urea,
Aldehyde compound is adjusted to alkaline condition after undergoing alkali-acid solution reaction process again, is added after adjusting soda acid every time
Aldehyde compound reaction；It is finally adjusted to acidity and obtains spinning solution, it is fine that wet spinning, heat cure prepare three-dimensional cross-linked ureaformaldehyde
Dimension.This method provides a kind of methods of circulation acid-base method preparation ureaformaldehyde fiber.
In order to solve the above technical problems, the technical scheme is that
A method of circulation acid-base method prepares ureaformaldehyde fiber, and steps are as follows:
(1) water-soluble polymers are obtained by water soluble polymer is soluble in water, urea, aldehydes is added into water-soluble polymers
It closes object and basic catalyst obtains the solution under alkaline condition, a period of time is then reacted under the conditions of 45-95 DEG C；
(2) acidic catalyst adjusting pH value to acidity is added and obtains the solution under acid condition, a certain amount of aldehydes chemical combination is added
Object obtains urea-formaldehyde resin solution after the reaction was continued under the conditions of 40-95 DEG C a period of time；
(3) basic catalyst is added and adjusts urea-formaldehyde resin solution to alkalinity, is slowly added to aldehyde compound under the conditions of 35-95 DEG C
Reaction a period of time, it is that 3-6 obtains ureaformaldehyde after reacting a period of time under the conditions of 40-85 DEG C that last Plus acidic catalyst, which is adjusted to pH,
Spinning solution obtains ureaformaldehyde as-spun fibre using wet spinning technology after coagulating bath；
(4) then as-spun fibre is heating and curing in an oven according to certain heating rate, obtains by washing, drying
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.
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.
Further, in the step (1) in water-soluble polymer solution high molecular mass content be 1-30%, urea and
The molar ratio of aldehyde compound is 1:(0.4-1.5), the mass ratio of macromolecule and urea is 1:(0.2-10).
Further, the solution ph range under the conditions of step (1) neutral and alkali is 7.5-10.5, reaction time 0.5-
8h.The additional amount of aldehyde compound is urea and aldehyde compound on the basis of the urea in step (1) in the step (2)
Molar ratio be 1:(0.4-1.5), the solution ph range under acid condition is 4.0-6.9, reaction time 0.1-7h.
Further, it is 7.4-10.5 that basic catalyst is added in the step (3) and adjusts urea-formaldehyde resin solution pH value range
Reaction time is 0.4-8h；It is 3-6 that Plus acidic catalyst, which is adjusted to pH, reacts 1-5h.
Further, the additional amount of aldehyde compound is the urea on the basis of the urea in step (1) in the step (3)
Molar ratio with aldehyde compound is 1:(0.2-2).
Further, the coagulating bath of wet spinning is saturated aqueous sodium sulfate in the step (3), 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 (4)
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 ureaformaldehyde 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 is mild, and ureaformaldehyde molecule is the linear structure of high molecular weight in gained spinning solution；Aldehydes is added by several times
Compound is conducive to control reaction process, is conducive to Molecular Design；Circulation soda acid is conducive to the control of linearity molecular structure,
Spinnability is improved, the content of free aldehyde in spinning solution is reduced, improves resin solution viscosity, improves spinnability, further letter
Change spinning condition；Spinning condition is mild, and spinning speed is fast, gained as-spun fibre only need to by heat cure can ureaformaldehyde fiber, Gu
It is simple and easy to change crosslinking；Gained ureaformaldehyde fiber is a kind of three-dimensional cross-linked fiber, without adding fire retardant, excellent flame retardancy, pole
Limited oxygen index is high, release toxic and harmful gas is considerably less when putting out, burn from flame, flame-retarding height, and heat-proof quality is excellent.
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 of the circulation acid-base method preparation ureaformaldehyde fiber of the present embodiment, steps are as follows:
(1) by the PVA PVA aqueous solution soluble in water for obtaining 1wt%, urea and formaldehyde (molar ratio 1:0.4), PVA and urine is added
Plain mass ratio is 1:0.2, and sodium hydrate aqueous solution is then added, and adjusts pH value to 7.5, in 45 DEG C of reaction 0.5h；Then it is added
Second batch formaldehyde (molar ratio is 1:0.4 to urea therewith), 40 DEG C of reaction 0.1h are added to 4.0 in salt acid for adjusting pH value；
(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 1:0.2), 35 DEG C of reaction 0.4h；Hydrochloric acid tune pH value is eventually adding to react to 3,40 DEG C
1h obtains spinning solution；
(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 ureaformaldehyde fiber.
The ureaformaldehyde fibre diameter of preparation is 16 microns, tensile strength 370MPa, elongation at break 40%, the LOI of fiber
Value is 32.
Embodiment 2
A method of circulation acid-base method prepares ureaformaldehyde fiber, and its steps is as follows:
(1) by the PEG PEG aqueous solution soluble in water for obtaining 30wt%, urea and paraformaldehyde (molar ratio 1:1.5) is added,
PEG and urea quality ratio are 1:10, and potassium hydroxide aqueous solution is then added, and adjust pH value to 10.5, in 95 DEG C of reaction 8h；Then
Sulphur acid for adjusting pH value is added to 6.9, second batch formaldehyde (molar ratio is 1:1.5 to urea therewith), 95 DEG C of reaction 7h are added；
(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；It is eventually adding sulfuric acid tune pH value and obtains spinning solution to 6,85 DEG C of reaction 5h；
(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 34 microns, tensile strength 73MPa, elongation at break 12%, the LOI of fiber
Value is 32.
Embodiment 3
A method of circulation acid-base method prepares ureaformaldehyde fiber, and its steps is as follows:
(1) by the polyvinyl formal polyvinyl formal solution soluble in water for obtaining 20wt%, urea and penta 2 is added
Aldehyde (molar ratio 1:1.1), polyvinyl formal and urea quality ratio are 1:3, and triethanolamine is then added, and adjust pH value and arrive
8.5, in 90 DEG C of reaction 3h；Then phosphorus acid for adjusting pH value is added to 5, be added second batch formaldehyde (molar ratio is 1 to urea therewith:
0.9), 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；Being eventually adding phosphoric acid tune pH value, to 4,80 DEG C of reaction 5h to obtain spinning molten
Liquid；
(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 ureaformaldehyde fiber.
The ureaformaldehyde fibre diameter of preparation is 16 microns, tensile strength 244MPa, elongation at break 14%, the LOI of fiber
Value is 33.
Embodiment 4
A method of circulation acid-base method prepares ureaformaldehyde fiber, and its steps is as follows:
(1) urea and acetaldehyde (molar ratio 1:1.1) are added by the PVP PVP aqueous solution soluble in water for obtaining 10wt%, PVP with
Urea quality ratio is 1:2, and sodium bicarbonate is then added, and adjusts pH value to 8.5, in 90 DEG C of reaction 2h；Then oxalic acid is added to adjust
Second batch formaldehyde (molar ratio is 1:1.2 to urea therewith), 85 DEG C of reaction 2h are added to 5.5 in pH value；
(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 1:0.7), 75 DEG C of reaction 4h；It is eventually adding oxalic acid tune pH value and obtains spinning to 4,40 DEG C of reaction 3h
Solution；
(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 ureaformaldehyde fiber.
The ureaformaldehyde fibre diameter of preparation is 22 microns, tensile strength 245MPa, elongation at break 11%, the LOI of fiber
Value is 34.
Embodiment 5
A method of circulation acid-base method prepares ureaformaldehyde fiber, and its steps is as follows:
(1) by the water soluble starch water soluble starch aqueous solution soluble in water for obtaining 10wt%, urea is added and paraformaldehyde (rubs
You are than being 1:1.1), water soluble starch and urea quality ratio are 1:1, and magnesium hydroxide is then added, and adjust pH value to 8.5,90
DEG C reaction 2h；Then sulphur acid for adjusting pH value is added to 5.5, is added second batch formaldehyde (molar ratio is 1:0.8 to urea therewith), 85 DEG C
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 1:0.6), 75 DEG C of reaction 4h；It is eventually adding hydrochloric acid tune pH value and obtains spinning solution to 5,40 DEG C of reaction 3h；
(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 ureaformaldehyde fiber.
The ureaformaldehyde fibre diameter of preparation is 24 microns, tensile strength 261MPa, elongation at break 16%, the LOI of fiber
Value is 33.
Embodiment 6
A method of circulation acid-base method prepares ureaformaldehyde fiber, and its steps is as follows:
(1) by the water-soluble cellulose water-soluble cellulose aqueous solution soluble in water for obtaining 18wt%, urea and glutaraldehyde is added
(molar ratio 1:1.2), water-soluble cellulose and urea quality ratio are 1:3, and calcium hydroxide is then added, and adjust pH value to 8.5,
In 90 DEG C of reaction 2h；Then sulphur acid for adjusting pH value is added to 5.5, second batch formaldehyde (molar ratio is 1:1.4 to urea therewith) is added,
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；It is eventually adding hydrochloric acid tune pH value and obtains spinning solution to 5,50 DEG C of reaction 2h；
(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 ureaformaldehyde fiber.
The ureaformaldehyde fibre diameter of preparation is 33 microns, tensile strength 134MPa, elongation at break 9.1%, fiber
LOI value is 33.
Embodiment 7
A method of circulation acid-base method prepares ureaformaldehyde fiber, and its steps is as follows:
(1) by the water-soluble cellulose water-soluble cellulose aqueous solution soluble in water for obtaining 18wt%, urea is added and formaldehyde (rubs
You are than being 1:1.2), water-soluble cellulose and urea quality ratio are 1:3, and sodium hydroxide is then added, adjust pH value to 8.5,
90 DEG C of reaction 2h；Then careless acid for adjusting pH value is added to 5.5, is added second batch formaldehyde (molar ratio is 1:1.4 to urea therewith), 85
DEG C 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 1:1.6), 75 DEG C of reaction 4h；It is eventually adding sulfuric acid tune pH value and obtains spinning solution to 5,70 DEG C of reaction 1h；
(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 22 microns, tensile strength 263MPa, elongation at break 18.6%, fiber
LOI value is 33.
Embodiment 8
A method of circulation acid-base method prepares ureaformaldehyde fiber, and its steps is as follows:
(1) by the PVA PVA aqueous solution soluble in water for obtaining 8wt%, urea and formaldehyde (molar ratio 1:1.2), PVA and urine is added
Plain mass ratio is 1:3, and sodium hydroxide is then added, and adjusts pH value to 8.5, in 90 DEG C of reaction 2h；Then salt acid for adjusting pH is added
Second batch formaldehyde (molar ratio is 1:1.2 to urea therewith), 85 DEG C of reaction 3h are added to 5.5 in value；
(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；It is eventually adding hydrochloric acid tune pH value and obtains spinning solution to 4,40 DEG C of reaction 3h；
(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 24 microns, tensile strength 227MPa, elongation at break 24%, 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 of circulation acid-base method preparation ureaformaldehyde fiber, it is characterised in that steps are as follows:
(1) water-soluble polymers are obtained by water soluble polymer is soluble in water, urea, aldehydes is added into water-soluble polymers
It closes object and basic catalyst obtains the solution under alkaline condition, a period of time is then reacted under the conditions of 45-95 DEG C；
(2) acidic catalyst adjusting pH value to acidity is added and obtains the solution under acid condition, a certain amount of aldehydes chemical combination is added
Object obtains urea-formaldehyde resin solution after the reaction was continued under the conditions of 40-95 DEG C a period of time；
(3) basic catalyst is added and adjusts urea-formaldehyde resin solution to alkalinity, is slowly added to aldehyde compound under the conditions of 35-95 DEG C
Reaction a period of time, it is that 3-6 obtains ureaformaldehyde after reacting a period of time under the conditions of 40-85 DEG C that last Plus acidic catalyst, which is adjusted to pH,
Spinning solution obtains ureaformaldehyde as-spun fibre using wet spinning technology after coagulating bath；
(4) then as-spun fibre is heating and curing in an oven according to certain heating rate, obtains by washing, drying
Ureaformaldehyde fiber.
2. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the step (1)
Middle water soluble polymer is in PVA, PEG, polyvinyl formal, PVP, water-soluble modified starch or water-soluble modified cellulose
One kind.
3. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the aldehydes
Conjunction object is one of formaldehyde, glutaraldehyde, acetaldehyde, paraformaldehyde；Basic catalyst is sodium hydroxide, potassium hydroxide, three ethyl alcohol
One of amine, sodium bicarbonate, magnesium hydroxide or calcium hydroxide, acidic catalyst are one in hydrochloric acid, sulfuric acid, phosphoric acid or oxalic acid
Kind.
4. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the step (1)
High molecular mass content is 1-30% in middle water-soluble polymer solution, and the molar ratio of urea and aldehyde compound is 1:(0.4-
1.5), the mass ratio of macromolecule and urea is 1:(0.2-10).
5. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the step (1)
Solution ph range under the conditions of neutral and alkali is 7.5-10.5, reaction time 0.5-8h.
6. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the step (2)
The additional amount of middle aldehyde compound is on the basis of the urea in step (1), and the molar ratio of urea and aldehyde compound is 1:
(0.4-1.5), the solution ph range under acid condition are 4.0-6.9, reaction time 0.1-7h.
7. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the step (3)
It is 0.4-8h that middle addition basic catalyst adjusting urea-formaldehyde resin solution pH value range, which is the 7.4-10.5 reaction time,；Plus acidic catalysis
It is 3-6 that agent, which is adjusted to pH, reacts 1-5h.
8. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the step (3)
The additional amount of middle aldehyde compound is on the basis of the urea in step (1), and the molar ratio of urea and aldehyde compound is 1:
(0.2-2).
9. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the step (3)
The coagulating bath of middle 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.
10. the method for the circulation acid-base method preparation ureaformaldehyde fiber according to claim 1, it is characterised in that: the step
(4) 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, is warming up to 150-230
DEG C, constant temperature 0.1-2h takes out after Temperature fall up to ureaformaldehyde fiber.
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| PCT/CN2020/118742 WO2021018319A1 (en) | 2019-07-30 | 2020-09-29 | Method for preparing urea formaldehyde fibers via cyclic acid-alkali process |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4828007B1 (en) * | 1970-06-30 | 1973-08-28 | ||
| JPS52154893A (en) * | 1976-06-17 | 1977-12-22 | Matsushita Electric Works Ltd | Preparation of urea resin syrup |
| US4172057A (en) * | 1977-05-06 | 1979-10-23 | Imperial Chemical Industries Limited | Amino-resin compositions |
| CN101265314A (en) * | 2008-04-30 | 2008-09-17 | 北京化工大学 | Environmental protection urea-formaldehyde resin and preparation method thereof |
| CN101858045A (en) * | 2010-04-30 | 2010-10-13 | 华中师范大学 | Epoxy modified urea resin wet strength agent and preparation method thereof |
| CN102408855A (en) * | 2011-07-18 | 2012-04-11 | 广西大学 | Urea formaldehyde resin adhesive for moisture-proof environment-friendly medium density fiberboard and production method as well as composite additives thereof |
| CN104388022A (en) * | 2014-11-02 | 2015-03-04 | 北京化工大学 | Cyclic polyamine modified urea-formaldehyde resin adhesive and preparation method thereof |
| CN104788633A (en) * | 2015-04-29 | 2015-07-22 | 武汉工程大学 | Phenolic-resin-modified urea formaldehyde resin and preparation method thereof |
| CN109851735A (en) * | 2018-12-29 | 2019-06-07 | 大亚人造板集团有限公司 | A kind of manufacturing method of low melamine amount modified urea-formaldehyde resin and its application in MDF production |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034417C (en) * | 1992-12-04 | 1997-04-02 | 福州人造板厂 | Urea-formaldehyde resin for middle density fibre board use and preparing process |
| CN103333651B (en) * | 2013-07-02 | 2014-11-05 | 西南林业大学 | Hyperbranched resin adhesive with low formaldehyde release rate as well as preparation method and application of hyperbranched resin adhesive |
| CN104558464A (en) * | 2013-10-12 | 2015-04-29 | 许昌花都地板有限公司 | New synthesis technology of urea-formaldehyde resin |
| CN103804619B (en) * | 2014-02-20 | 2016-01-20 | 北京林业大学 | Xylogen-phenol-urea-formaldehyde condensation copolymerization resin tackiness agent and preparation method |
| CN104311767B (en) * | 2014-10-10 | 2016-09-07 | 湖北省宏源药业科技股份有限公司 | A kind of modified urea-formaldehyde resin adhesive and preparation method thereof |
| CN110359117B (en) * | 2019-07-30 | 2022-01-21 | 中原工学院 | Preparation method of urea-formaldehyde fiber |
| CN110359116B (en) * | 2019-07-30 | 2022-01-21 | 中原工学院 | Method for preparing urea-formaldehyde fiber by adding urea-formaldehyde fiber in multiple times |
| CN110359119B (en) * | 2019-07-30 | 2021-03-02 | 中原工学院 | Method for preparing urea-formaldehyde fiber by circulating acid-base method |
-
2019
- 2019-07-30 CN CN201910694099.2A patent/CN110359119B/en active Active
-
2020
- 2020-09-29 WO PCT/CN2020/118742 patent/WO2021018319A1/en active Application Filing
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4828007B1 (en) * | 1970-06-30 | 1973-08-28 | ||
| JPS52154893A (en) * | 1976-06-17 | 1977-12-22 | Matsushita Electric Works Ltd | Preparation of urea resin syrup |
| US4172057A (en) * | 1977-05-06 | 1979-10-23 | Imperial Chemical Industries Limited | Amino-resin compositions |
| CN101265314A (en) * | 2008-04-30 | 2008-09-17 | 北京化工大学 | Environmental protection urea-formaldehyde resin and preparation method thereof |
| CN101519483A (en) * | 2008-04-30 | 2009-09-02 | 北京化工大学 | Novel environment-friendly urea-formaldehyde resin and preparation method thereof |
| CN101858045A (en) * | 2010-04-30 | 2010-10-13 | 华中师范大学 | Epoxy modified urea resin wet strength agent and preparation method thereof |
| CN102408855A (en) * | 2011-07-18 | 2012-04-11 | 广西大学 | Urea formaldehyde resin adhesive for moisture-proof environment-friendly medium density fiberboard and production method as well as composite additives thereof |
| CN104388022A (en) * | 2014-11-02 | 2015-03-04 | 北京化工大学 | Cyclic polyamine modified urea-formaldehyde resin adhesive and preparation method thereof |
| CN104788633A (en) * | 2015-04-29 | 2015-07-22 | 武汉工程大学 | Phenolic-resin-modified urea formaldehyde resin and preparation method thereof |
| CN109851735A (en) * | 2018-12-29 | 2019-06-07 | 大亚人造板集团有限公司 | A kind of manufacturing method of low melamine amount modified urea-formaldehyde resin and its application in MDF production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021018319A1 (en) * | 2019-07-30 | 2021-02-04 | 中原工学院 | Method for preparing urea formaldehyde fibers via cyclic acid-alkali process |
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