CN104532367B - A kind of method that solvent-free electrostatic spinning prepares polyurethane micro nanometer fiber - Google Patents
A kind of method that solvent-free electrostatic spinning prepares polyurethane micro nanometer fiber Download PDFInfo
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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
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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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
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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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
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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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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- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
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Abstract
The invention belongs to electrostatic spinning technique field, relate to a kind of method that solvent-free electrostatic spinning prepares polyurethane micro nanometer fiber, in flask, first add isocyanates, polyhydric alcohol, modifying agent and catalyst carry out reacting to obtain polyurethane prepolymer；Measure the content of remaining isocyanate again, add chain extender to stir, gained solution is loaded in the syringe of solvent-free electrostatic spinning apparatus and stand, every 13 hours, measure the viscosity of polyurethane prepolymer, the viscosity of polyurethane prepolymer carries out electrospinning after reaching 5,000 10000 centipoises, i.e. prepares polyurethane micro nanometer fiber；Its preparation technology is simple, easy to operate, and efficiency is high, uses solvent-free electrostatic spinning apparatus, non-volatility organic compound VOC emission, environmental friendliness, is beneficial to realize industrialization.
Description
Technical field:
The invention belongs to electrostatic spinning technique field, relating to a kind of solvent-free electrostatic spinning, to prepare polyurethane micro-nano
The method of fiber, a kind of utilizes novel solvent-free electrostatic spinning apparatus, prepares under condition of no solvent
Polyurethane prepolymer presoma carry out electrostatic spinning after, under heat radiation, rapidly reaction is fully cured into micro-nano
The method of rice fiber.
Background technology:
Electrostatic spinning technique is considered as a kind of side simply effectively preparing the one-dimensional micro/nano-fibre of uniformly continuous
Method.But, along with developing rapidly of nanotechnology, environmental pollution and production cost increasingly cause the weight of people
Depending on.Although people are prepared for the micro/nano-fibre of various pattern and architectural feature by electrostatic spinning, but molten
It is generally required to use a large amount of organic solvent in the presoma of liquid spinning, these organic solvent usage amounts often beyond
80%, and when electrostatic spinning, organic solvent is difficult to reclaim, and pollutes, and makes solution electrostatic spinning prepare
The industrialization of micro/nano-fibre is restricted.Solvent-free electrostatic spinning it is crucial that spinning precursor solution can
All it is solidified into fibrous body, and needs quickly to solidify while electrospinning.Currently, with respect to solvent-free electrostatic
The report of spining technology is less, and one is to utilize the fast wet of cyanoacrylate (502 glue class) curing, electricity
It is spun into micro nanometer fiber (Polym.Chem.2013,4,5696)；Two be Chinese patent (patent publication No.:
CN101021017A) disclose under the initiation of ultraviolet light irradiation and initiator, make containing activity double key official
The precursor liquid that can roll into a ball is solidified into micro nanometer fiber.
Polyurethane elastomeric fiber, also known as spandex, is to prepare through dry spinning or wet spinning with polyurethane for raw material
Synthetic fibers, there is the elastic recovery rate of rubber like silk and high extension at break, the electrostatic spinning of polyurethane
It is usually to dissolve and carries out (synthetic fiber industry, 2008,5:44) in a solvent.Heat cure refers at heat radiation
Effect under, make electrospinning precursor liquid jet all be solidified into fiber, thus realize solvent-free purpose, at present this
One method prepares micro nanometer fiber, and there is not been reported, especially to use heat cure electrospinning to prepare polyurethane micro nanometer fiber
It is not reported so far.
Summary of the invention:
It is an object of the invention to the shortcoming overcoming prior art to exist, seeking design provides a kind of solvent-free electrostatic
Spin processes prepares the method for polyurethane fiber, and under thermal-radiating effect, electrospinning liquid is all solidified into micro-/ nano
Fiber.
To achieve these goals, the present invention realizes in solvent-free electrostatic spinning apparatus, prepares polyurethane micro-nano
The concrete technology step of rice fiber is:
(1), in flask, isocyanates and polyhydric alcohol, wherein NCO (NCO): hydroxyl are added
(OH) mol ratio is 1.1～2.1, adds the modifying agent of gross weight 0.05%～10%, adds gross weight
0.01～the catalyst of 0.1%, it is warming up to 80 DEG C of stirring reactions 2～8 hours, obtains polyurethane (PU) prepolymer；
(2), using di-n-butylamine-toluene method to measure the content of remaining isocyanate, the addition of equimolar amounts is expanded
Chain agent (ripple hydrogen of living: NCO (NCO)=1:1), is uniformly mixing to obtain solution, is filled by gained solution
Enter in the syringe of solvent-free electrostatic spinning apparatus, at room temperature to 80 DEG C, stand 2-48 hour, make polyurethane
(PU) the further chain extension of prepolymer；
(3), every 1-3 hour, measuring the viscosity of polyurethane prepolymer, the viscosity of polyurethane prepolymer reaches
Carrying out electrospinning after 5000-10000 centipoise, the distance of regulation spinning head to receiving pole is 5～50 centimetres, receives
Pole temperature is 50～200 DEG C, and the voltage of high voltage power supply is 10～30 kilovolts, electrospinning 1～after 30 minutes, is receiving
Obtain electrospinning fibre on extremely, i.e. prepare polyurethane micro nanometer fiber.
Modifying agent described in step of the present invention (1) includes dihydromethyl propionic acid (DMPA) and polyurethane catalysis
Agent, catalysts for polyurethanes includes organic tin catalyst and Tertiary organic amine catalysts, wherein organic tin catalyst
Including T-12 dibutyl tin laurate, Tertiary organic amine catalysts includes its quaternary ammonium salt, such as triethylamine, N, N-
Dimethyl benzylamine, N-methylmorpholine and pyridine.
Isocyanates of the present invention is alkyl and the aromatic radical isocyanates of polyfunctionality, including hydrogenation
MDI, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene
Diisocyanate (XDI), hydrogenation of benzene dimethylene diisocyanate (H6XDI), durol dimethyl two
Isocyanates (TMXDI) series, methyl diphenylene diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI)
And the trimer condensation substance of these isocyanates and closure.
Polyhydric alcohol of the present invention is polyether polyol, including Polyethylene Glycol PEG, polypropylene glycol PPG,
Polytetrahydrofuran diol PTMG and PEPA.
Chain extender of the present invention is glycol or the diamidogen of low-molecular-weight, including ethylene glycol, diethylene glycol,
Tirethylene glycol, Polyethylene Glycol (PEG200), 1,4-butanediol, ethylenediamine and hexamethylene diamine.
The present invention prepares the scope that is preferable to carry out of polyurethane nanofiber, polyisocyanates used in step (1)
It is 1.2～2.0 with polyhydric alcohol (NCO:OH) ratio, reacts 2～6 hours at 50～80 DEG C；Then chain extension is added
Agent and modifying agent DMPA if desired, load syringe after stirring, stands 2～48 at room temperature to 50 DEG C
Hour, make the further chain extension of PU prepolymer；Then loading onto internal diameter is that 0.35～1.0 millimeter of spinning head carries out electrospinning,
Shower nozzle is 5～30 centimetres to the distance of receiving pole, and receiving pole temperature is 50～180 DEG C, and the voltage of high voltage power supply is
10～25 kilovolts, after 1～20 minute, receiving pole obtains micro nanometer fiber.
The agent structure of solvent-free electrostatic spinning apparatus of the present invention includes that syringe, high-voltage power cathode are led
Line, spinning head, electrospinning fibre, receiving pole, conduction oil, oil bath pan, oil bath pan heater switch, high voltage power supply
Voltage knob, high voltage power supply electricity adjusted by switch, oil bath pan thermoregulation knob, oil bath pan temperature display, high voltage power supply
Pressure display screen, oil bath pan heating control system, high voltage power supply, fixed support and base；The base of case structure
Inside it is provided with oil bath pan heating control system and the high voltage power supply of electrical information connection, on the leading flank of base from the right side extremely
A left side is shaped with oil bath pan heater switch successively, high-voltage electric switch, oil bath pan thermoregulation knob, oil bath pan temperature show
Screen, high voltage power supply adjust voltage knob and high-voltage power voltage display screen, wherein oil bath pan heater switch, oil bath pan
Thermoregulation knob and oil bath pan temperature display electrically connect with oil bath pan heating control system respectively according to electrical principles,
High-voltage electric switch, high voltage power supply adjust voltage knob and high-voltage power voltage display screen according to electrical principles respectively with
High voltage power supply electrically connects, and high voltage power supply uses electrostatic generator, and its voltage is 10～30 kilovolts；Γ shape structure
Fixed support is arranged on base, and high-voltage power cathode wire is drawn by fixed support；Syringe fixedly mounts
On fixed support, the lower end of syringe connects and is shaped with the spinning head that internal diameter is 0.35～2.0 millimeter, spinning head with
High-voltage power cathode wire electrically connects；Electrospinning fibre is sprayed by spinning head；Oil bath pan, oil bath it is provided with on base
Filling conduction oil in Guo, receiving pole is placed in oil bath pan, by the temperature of oil bath pan thermoregulation knob regulation receiving pole
Degree is 50～200 DEG C, and receiving pole is placed on the underface of spinning head, collects the electrospinning fibre of spinning head ejection；
Spinning head is 5～50 centimetres to the distance of receiving pole.
The operation principle of the present invention is: diisocyanate and polyhydric alcohol prepolymerization, and NCO:OH ratio is more than 1,
Guarantee that the end group of prepolymer is still for NCO group；It is subsequently adding the glycol of the little molecule of chain extender, both for expanding
Chain agent, simultaneously works as the effect of diluent；Then, room temperature or stand a period of time in relatively low temperature, make chain
Increasing, then carry out electrospinning, receiving pole is owing to having higher temperature, so that still having neither part nor lot in having of reaction
The NCO (NCO) of relatively high reaction activity is fully cured into main body with hydroxyl (OH) fast reaction
Fiber, solvent-free, non-volatility organic compound VOC emission.
Compared with prior art, its preparation technology is simple, easy to operate for the present invention, and efficiency is high, use without molten
Agent electrostatic spinning apparatus, non-volatility organic compound VOC emission, environmental friendliness, it is beneficial to realize industrialization.
Accompanying drawing illustrates:
Fig. 1 is the agent structure principle schematic of the solvent-free electrostatic spinning apparatus that the present invention uses, including
Syringe 1, high-voltage power cathode wire 2, spinning head 3, electrospinning fibre 4, receiving pole 5, conduction oil 6,
Oil bath pan 7, oil bath pan heater switch 8, high-voltage electric switch 9, oil bath pan thermoregulation knob 10, oil bath pan temperature
Degree display screen 11, high voltage power supply adjust voltage knob 12, high-voltage power voltage display screen 13, fixed support 16
With base 17.
Fig. 2 is the cross-section structure principle schematic of solvent-free electrostatic spinning apparatus used in the present invention, wherein wraps
Include emitter 1, high-voltage power cathode wire 2, spinning head 3, electrospinning fibre 4, receiving pole 5, conduction oil 6,
Oil bath pan 7, oil bath pan heating control system 14 and high voltage power supply 15.
Fig. 3 is the polymer micro-nanometer fiber optical microscope photograph of the embodiment of the present invention 1 preparation.
Fig. 4 is the polymer micro-nanometer fiber optical microscope photograph of the embodiment of the present invention 2 preparation.
Fig. 5 is the polymer micro-nanometer fiber optical microscope photograph of the embodiment of the present invention 3 preparation.
Fig. 6 is the polymer micro-nanometer fiber optical microscope photograph of the embodiment of the present invention 4 preparation.
Fig. 7 is the polymer micro-nanometer fiber optical microscope photograph of the embodiment of the present invention 5 preparation.
Fig. 8 is the polymer micro-nanometer fiber optical microscope photograph of the embodiment of the present invention 6 preparation.
Detailed description of the invention:
Below by embodiment and combine accompanying drawing and be described further.
The present embodiment realizes in solvent-free electrostatic spinning apparatus, prepares the concrete technology of polyurethane micro nanometer fiber
Step is:
(1), in flask, isocyanates and polyhydric alcohol, wherein NCO (NCO): hydroxyl are added
(OH) mol ratio is 1.1～2.1, adds the modifying agent of gross weight 0.05%～10%, adds gross weight
0.01～the catalyst of 0.1%, it is warming up to 80 DEG C of stirring reactions 2～8 hours, obtains polyurethane (PU) prepolymer；
(2), di-n-butylamine-toluene method is used to measure the content of remnants-NCO, the addition chain extension of equimolar amounts
Agent (ripple hydrogen of living: NCO (NCO)=1:1), is uniformly mixing to obtain solution, is loaded by gained solution
In the syringe 1 of solvent-free electrostatic spinning apparatus, at room temperature to 80 DEG C, stand 2-48 hour, make polyurethane
(PU) the further chain extension of prepolymer；
(3), every 1-3 hour, measuring the viscosity of polyurethane prepolymer, the viscosity of polyurethane prepolymer reaches
Carrying out electrospinning after 5000-10000 centipoise, the distance of regulation spinning head 3 to receiving pole 5 is 5～50 centimetres,
Receiving pole temperature is 50～200 DEG C, and the voltage of high voltage power supply 15 is 10～30 kilovolts, electrospinning 1～after 30 minutes,
Receiving pole 5 obtains electrospinning fibre 4, i.e. prepares polyurethane micro nanometer fiber.
Described in the present embodiment, the agent structure of solvent-free electrostatic spinning apparatus includes syringe 1, high-voltage power cathode
The heating of wire 2, spinning head 3, electrospinning fibre 4, receiving pole 5, conduction oil 6, oil bath pan 7, oil bath pan is opened
Pass 8, high-voltage electric switch 9, oil bath pan thermoregulation knob 10, oil bath pan temperature display 11, high voltage power supply are adjusted
Voltage knob 12, high-voltage power voltage display screen 13, oil bath pan heating control system 14, high voltage power supply 15,
Fixed support 16 and base 17；The oil bath pan heating of electrical information connection it is provided with in the base 17 of case structure
Control system 14 and high voltage power supply 15, the leading flank of base 17 is shaped with successively oil bath pan heating from right-to-left
Switch 8, high-voltage electric switch 9, oil bath pan thermoregulation knob 10, oil bath pan temperature display 11, high voltage power supply
Adjust voltage knob 12 and high-voltage power voltage display screen 13, wherein oil bath pan heater switch 8, oil bath pan homoiothermic
Knob 10 and oil bath pan temperature display 11 are electric with oil bath pan heating control system 14 respectively according to electrical principles
Connect, high-voltage electric switch 9, high voltage power supply adjust voltage knob 12 and high-voltage power voltage display screen 13 according to
Electrical principles electrically connects with high voltage power supply 15 respectively, and high voltage power supply 15 uses electrostatic generator, and its voltage is
10～30 kilovolts；The fixed support 16 of Γ shape structure is arranged on base 17, and high-voltage power cathode wire 2 leads to
Cross fixed support 16 to draw；Syringe 1 is fixedly mounted on fixed support 16, and the lower end of syringe 1 connects
Being shaped with the spinning head 3 that internal diameter is 0.35～2.0 millimeter, spinning head 3 electrically connects with high-voltage power cathode wire 2；
Electrospinning fibre 4 is sprayed by spinning head 3；It is provided with oil bath pan 7 on base 17, in oil bath pan 7, fills heat conduction
Oil 6, receiving pole 5 is placed in oil bath pan 7, is regulated the temperature of receiving pole 5 by oil bath pan thermoregulation knob 10
Degree is 50～200 DEG C, and receiving pole 5 is placed on the underface of spinning head 3, collects the electrospinning of spinning head 3 ejection
Fiber 4；Spinning head 3 is 5～50 centimetres to the distance of receiving pole 5.
Embodiment 1:
The present embodiment first adds the 4,4-dicyclohexyl methyl hydride diisocyanate of 3.67 grams in 50 milliliters of flasks
(H12MDI) and 20 grams of Polyethylene Glycol (PEG-2000 uses initial vacuum moisture removal), wherein NCO:OH
Mol ratio be 1.4:1, the T-12 (dibutyl tin laurate) adding 0.01 gram is catalyst, heat up
React 5 hours to 80 DEG C of stirrings, obtain PU prepolymer；Then chain extender diglycol 1.06 grams is added,
After stirring, load with in the syringe 1 that internal diameter is 0.41 millimeter of spinning head 3, at room temperature (25 DEG C)
Lower standing 24 hours, makes the further chain extension of PU prepolymer；Chain extending reaction carries out electrospinning, spinning head 3 after completing
Distance to receiving pole 5 is 15 centimetres, and receiving pole 5 temperature is 100 DEG C, and the voltage of high voltage power supply 15 is 18
Kilovolt, electrospinning, after 2 minutes, collects polymer micro-nanometer fiber on receiving pole 5, and its optical microscope shines
Sheet is as shown in Figure 3.
Embodiment 2:
The present embodiment adds the 4,4-dicyclohexyl methyl hydride diisocyanate of 4.19 grams in 50 milliliters of flasks
(H12MDI) PEG-2000 of and 20 grams (uses initial vacuum moisture removal), wherein NCO:OH mole
Ratio is 1.6:1, adds T-12 (dibutyl tin laurate) catalyst of 0.01 gram, is warming up to 80 DEG C and stirs
Mix reaction 8 hours, obtain PU prepolymer；It is subsequently adding chain extender Polyethylene Glycol (PEG200) 2.00 grams,
Load with in the syringe 1 that internal diameter is 0.41 millimeter of spinning head 3 after stirring, under room temperature (～25 DEG C)
Stand 48 hours, make the further chain extension of PU prepolymer；Chain extending reaction carries out electrospinning, spinning head 3 after completing
Distance to receiving pole 5 is 15 centimetres, and the temperature of receiving pole 5 is 100 DEG C, and the voltage of high voltage power supply 15 is
18 kilovolts, electrospinning, after 2 minutes, collects polymer micro-nanometer fiber on receiving pole 5, its optical microphotograph
Mirror photo is as shown in Figure 4.
Embodiment 3:
The present embodiment adds the isophorone diisocyanate (IPDI) and 20 of 3.11 grams in 50 millimeters of flasks
Gram Polyethylene Glycol (PEG-2000 uses initial vacuum moisture removal), wherein the mol ratio of NCO:OH is 1.4:1,
The T-12 (dibutyl tin laurate) adding 0.01 gram is catalyst, is warming up to 80 DEG C of stirring reactions 5
Hour, obtain PU prepolymer；Then add chain extender diglycol 1.06 grams, load after stirring with
Interior through the syringe 1 for 0.41 millimeter of spinning head 3, under room temperature, (～25 DEG C) stand 24 hours, make PU pre-
The further chain extension of polymers；Chain extending reaction carries out electrospinning after completing, the distance of spinning head 3 to receiving pole 5 is 15
Centimetre, the temperature of receiving pole 5 is 100 DEG C, and the voltage of high voltage power supply 15 is 18 kilovolts, and electrospinning is after 2 minutes,
Collecting polymer micro-nanometer fiber on receiving pole 5, its optical microscope photograph is as shown in Figure 5.
Embodiment 4:
The present embodiment adds the hexamethylene diisocyanate (HDI) and 20 of 2.35 grams in 50 milliliters of flasks
Gram Polyethylene Glycol (PEG-2000 uses initial vacuum moisture removal), wherein the mol ratio of NCO:OH is 1.4:1,
The T-12 (dibutyl tin laurate) adding 0.01 gram is catalyst, is warming up to 80 DEG C of stirring reactions 5
Hour, obtain PU prepolymer；Then chain extender Polyethylene Glycol (PEG400) 4.00 grams is added, after stirring
Loading with in the syringe 1 that internal diameter is 0.35 millimeter of spinning head 3, under room temperature, (～25 DEG C) standing 24 is little
Time, make the further chain extension of PU prepolymer；Chain extending reaction carries out electrospinning, spinning head 3 to receiving pole 5 after completing
Distance be 15 centimetres, the temperature of receiving pole 5 is 100 DEG C, and the voltage of high voltage power supply 15 is 18 kilovolts,
After electrospinning 2 minutes, receiving pole 5 collects polymer micro-nanometer fiber, its optical microscope photograph such as figure
Shown in 6.
Embodiment 5:
The present embodiment adds the hexamethylene diisocyanate (HDI) and 20 of 2.35 grams in 50 milliliters of flasks
Gram Polyethylene Glycol (PEG-2000 uses initial vacuum moisture removal), wherein the mol ratio of NCO:OH is 1.4:1,
The T-12 (dibutyl tin laurate) adding 0.01 gram is catalyst, is warming up to 80 DEG C of stirring reactions 5
Hour, obtain PU prepolymer；Then chain extender Polyethylene Glycol (PEG400) 4.00 grams is added, after stirring
Loading with in the syringe 1 that internal diameter is 0.35 millimeter of spinning head 3, under room temperature, (～25 DEG C) standing 24 is little
Time, make the further chain extension of PU prepolymer；Chain extending reaction carries out electrospinning, spinning head 3 to receiving pole 5 after completing
Distance be 15 centimetres, receiving pole 5 temperature is 80 DEG C, and the voltage of high voltage power supply 15 is 18 kilovolts, pass through
After 3 minutes, receiving pole 5 collects polymer micro-nanometer fiber, its optical microscope photograph such as Fig. 7 institute
Show.
Embodiment 6:
The present embodiment adds the hexamethylene diisocyanate (HDI) and 20 of 3.13 grams in 50 milliliters of flasks
Gram polytetrahydrofuran diol (PTMG-2000 uses initial vacuum moisture removal), wherein NCO:OH mole
Ratio is 1.8:1, and the T-12 (dibutyl tin laurate) adding 0.01 gram is catalyst, is warming up to 50 DEG C
Stirring reaction 5 hours, obtains PU prepolymer；Then chain extender Polyethylene Glycol (PEG600) 6.00 grams is added,
After stirring, load with the syringe 1 that internal diameter is 0.35 millimeter of spinning head 3, under room temperature (～25 DEG C)
Stand 2 hours, make the further chain extension of PU prepolymer；After chain extending reaction completes, proceed by electrospinning, spray webbing
3 is 15 centimetres to the distance of receiving pole 5, and the temperature of receiving pole 5 is 80 DEG C, the electricity of high voltage power supply 15
Pressure is 18 kilovolts, after 2 minutes, collects polymer micro-nanometer fiber on receiving pole 5, its optics
Microphotograph is as shown in Figure 8.
Claims (6)
1. the method that a solvent-free electrostatic spinning prepares polyurethane micro nanometer fiber, it is characterised in that without molten
Realizing in agent electrostatic spinning apparatus, the concrete technology step preparing polyurethane micro nanometer fiber is:
(1), in flask, isocyanates and polyhydric alcohol, wherein NCO: the mol ratio of hydroxyl are added
It is 1.1～2.1, adds the modifying agent of gross weight 0.05%～10%, add gross weight 0.01～the catalysis of 0.1%
Agent, is warming up to 80 DEG C of stirring reactions 2～8 hours, obtains polyurethane prepolymer；
(2), using di-n-butylamine-toluene method to measure the content of remaining isocyanate, the addition of equimolar amounts is expanded
Chain agent, is uniformly mixing to obtain solution, is loaded by gained solution in the syringe of solvent-free electrostatic spinning apparatus,
Stand 2-48 hour at room temperature to 80 DEG C, make the further chain extension of polyurethane prepolymer；
(3), every 1-3 hour, measuring the viscosity of polyurethane prepolymer, the viscosity of polyurethane prepolymer reaches
Carrying out electrospinning after 5000-10000 centipoise, the distance of regulation spinning head to receiving pole is 5～50 centimetres, receives
Pole temperature is 50～200 DEG C, and the voltage of high voltage power supply is 10～30 kilovolts, electrospinning 1～after 30 minutes, is receiving
Obtain electrospinning fibre on extremely, i.e. prepare polyurethane micro nanometer fiber.
The most solvent-free electrostatic spinning prepares the method for polyurethane micro nanometer fiber, its
The modifying agent being characterised by described includes that dihydromethyl propionic acid, described catalyst include organic tin catalyst and have
Machine tertiary amine catalyst, wherein organic tin catalyst includes T-12 dibutyl tin laurate, and trimethylamine is urged
Agent includes triethylamine, N, N-dimethyl benzylamine, N-methylmorpholine and pyridine.
The most solvent-free electrostatic spinning prepares the method for polyurethane micro nanometer fiber, its
Be characterised by the described alkyl that isocyanates is polyfunctionality and aromatic radical isocyanates, including hydrogenation MDI,
Hexamethylene diisocyanate, isophorone diisocyanate, eylylene diisocyanate, hydrogenation of benzene two
Methylene diisocyanate, durol dimethyl diphenylmethane series, methyl diphenylene diisocyanate,
The trimer condensation substance of toluene di-isocyanate(TDI) and these isocyanates and closure.
The most solvent-free electrostatic spinning prepares the method for polyurethane micro nanometer fiber, its
The polyhydric alcohol being characterised by described includes Polyethylene Glycol, polypropylene glycol, polytetrahydrofuran diol and PEPA.
The most solvent-free electrostatic spinning prepares the method for polyurethane micro nanometer fiber, its
It is characterised by the described glycol that chain extender is low-molecular-weight or diamidogen, including ethylene glycol, diethylene glycol, two
Condensed ethandiol, Polyethylene Glycol PEG200,1,4-butanediol, ethylenediamine and hexamethylene diamine.
The most solvent-free electrostatic spinning prepares the method for polyurethane micro nanometer fiber, its
Be characterised by the agent structure of described solvent-free electrostatic spinning apparatus include syringe, high-voltage power cathode wire,
Spinning head, electrospinning fibre, receiving pole, conduction oil, oil bath pan, oil bath pan heater switch, high-voltage electric switch,
Oil bath pan thermoregulation knob, oil bath pan temperature display, high voltage power supply adjust voltage knob, high-voltage power voltage to show
Screen, oil bath pan heating control system, high voltage power supply, fixed support and base；Arrange in the base of case structure
There are oil bath pan heating control system and high voltage power supply that electrical information connects, on the leading flank of base from right-to-left successively
It is shaped with oil bath pan heater switch, high-voltage electric switch, oil bath pan thermoregulation knob, oil bath pan temperature display, height
Voltage source adjusts voltage knob and high-voltage power voltage display screen, wherein oil bath pan heater switch, oil bath pan homoiothermic rotation
Button and oil bath pan temperature display electrically connect with oil bath pan heating control system respectively according to electrical principles, high-tension electricity
Source switch, high voltage power supply adjust voltage knob and high-voltage power voltage display screen according to electrical principles respectively with high-tension electricity
Source electrically connects, and high voltage power supply uses electrostatic generator, and its voltage is 10～30 kilovolts；Fixing of Γ shape structure
Frame is arranged on base, and high-voltage power cathode wire is drawn by fixed support；Syringe is fixedly mounted on fixing
On support, the lower end connection of syringe is shaped with the spinning head that internal diameter is 0.35～2.0 millimeter, spinning head and high-tension electricity
Source positive wire electrical connection；Electrospinning fibre is sprayed by spinning head；It is provided with oil bath pan on base, contains in oil bath pan
There are conduction oil, receiving pole to be placed in oil bath pan, by the temperature of oil bath pan thermoregulation knob regulation receiving pole are
50～200 DEG C, receiving pole is placed on the underface of spinning head, collects the electrospinning fibre of spinning head ejection；Spinning head
Distance to receiving pole is 5～50 centimetres.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105088367B (en) * | 2015-08-25 | 2017-12-22 | 青岛大学 | A kind of solvent-free electrostatic spinning apparatus based on UV solidifications |
| CN105332136A (en) * | 2015-11-27 | 2016-02-17 | 青岛大学 | Conductive micro-nanometer fiber stranded wire based on solvent-free electrospinning and preparing method thereof |
| CN105332092B (en) * | 2015-11-27 | 2017-11-24 | 青岛大学 | A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance and preparation method thereof |
| CN105702479B (en) * | 2016-04-12 | 2019-04-02 | 齐鲁工业大学 | A kind of preparation method and application of polyurethane porous carbon electrode material for super capacitor |
| CN108690181A (en) * | 2017-04-05 | 2018-10-23 | 高鼎精密材料股份有限公司 | Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof |
| KR101937697B1 (en) * | 2017-11-23 | 2019-01-14 | 태광산업주식회사 | Preparation Method of Colored Polyurethaneurea Elastic Fiber |
| KR101943894B1 (en) * | 2017-11-23 | 2019-01-30 | 태광산업주식회사 | Preparation Method of Black Polyurethaneurea Fiber |
| CN110241467B (en) * | 2019-05-23 | 2021-10-26 | 东华大学 | Inner cone angle type electrostatic spinning device and using method thereof |
| CN110644238B (en) * | 2019-09-18 | 2022-04-19 | 界首市双鑫纺织有限公司 | Preparation process of wear-resistant fireproof cloth |
| CN111945243B (en) * | 2020-07-31 | 2022-11-22 | 哈尔滨理工大学 | Method for quickly preparing polyurethane fiber through coaxial electrostatic spinning |
| CN115323521B (en) * | 2022-08-04 | 2024-01-09 | 中国民用航空飞行学院 | Preparation method of intelligent temperature-regulating body type phase change fiber |
| CN115491818A (en) * | 2022-09-27 | 2022-12-20 | 扬州工业职业技术学院 | Chemically modified electrostatic spinning membrane and preparation method thereof |
| CN117385554B (en) * | 2023-12-07 | 2024-03-22 | 苏州中科纳威新材料有限公司 | Polyurethane nanofiber membrane, preparation system and preparation method |
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| DE4414327A1 (en) * | 1994-04-25 | 1995-10-26 | Bayer Ag | Process for the production of elastane threads |
| US5616675A (en) * | 1995-02-08 | 1997-04-01 | Kenneth Wilkinson | Process of preparing elastomeric thread |
| CN100526524C (en) * | 2007-02-02 | 2009-08-12 | 吉林大学 | No-solvent electrically spinning process for preparing micron and nanometer fiber |
| JP2010518273A (en) * | 2007-02-14 | 2010-05-27 | ダウ グローバル テクノロジーズ インコーポレイティド | Polymer or oligomer fibers by solventless electrospinning |
| CN102787447B (en) * | 2011-05-20 | 2014-12-10 | 中国科学院化学研究所 | Shape memory material with fiber structure and preparation method of shape memory material |
| CN103194820B (en) * | 2013-04-27 | 2014-08-27 | 青岛大学 | Method for preparing micro-nanofiber through solvent curing type electrostatic spinning |
| CN103992458A (en) * | 2014-06-11 | 2014-08-20 | 苏州大学 | Ultra-high strength polyurethane urea supermolecule hydrogel and preparation method thereof |
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