CN105220244B - A kind of method of the standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning - Google Patents
A kind of method of the standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning Download PDFInfo
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Abstract
The invention discloses a kind of method that scale no-solvent electrically spins standby photo-curing material micro nanometer fiber, comprise the following steps：(1) the spinning precursor liquid of photo-curing material is configured；(2) electrospinning micro nanometer fiber：The spinning precursor solution that step (1) is matched somebody with somebody is placed in the liquid storage mechanism of electrostatic spinning apparatus connection spinning nozzle, and the spinning nozzle of the electrostatic spinning apparatus and collector are placed under few oxygen environment and carry out electrospinning, the jet stream sprayed in electro-spinning process with ultraviolet source to spinning nozzle is irradiated, you can photo-curing material micro nanometer fiber is collected on the collector of electrostatic spinning apparatus.This method is easy to operate, environmental pollution caused by effectively prevent organic solvent volatilization, safety and environmental protection, suitable for the large-scale production of photo-curing material micro nanometer fiber, the technical barrier that current electrospinning photo-curing material micro nanometer fiber precursor liquid arrangement step is complicated, gained fiber is generally shorter and irregular, curing is incomplete, can not mass produce is overcome.
Description
Technical field
The present invention relates to a kind of method that scale no-solvent electrically spins standby photo-curing material micro nanometer fiber, belong to nanometer
Field of material preparation.
Background technology
Electrostatic spinning technique is as a kind of easy and effective method for preparing micro/nano-fibre.It can not only prepare and uniformly connect
Continuous one dimension fibre, and various patterns and the micro/nano-fibre of architectural feature are prepared, but with the rapid hair of nanometer technology
Exhibition, people increasingly pay attention to environmental protection and large-scale production.Conventional electrostatic spinning is preparing the presoma of micro/nano-fibre
Generally required in solution using a large amount of organic solvents, and in electrostatic spinning, can have more than 80% organic solvent volatilization and
It is difficult to recycle, so as to pollute, is restricted the industrialization that solution electrostatic spinning prepares micro/nano-fibre.
In order to solve solvent volatilization problems, no-solvent electrically is spun into as one of current research hotspot.Solvent-free electrostatic spinning
Key be that spinning precursor solution can be participated in into fibre as the main body of spinning fibre, and need while electrospinning quick
Cure.Domestic and foreign scholars have done some explorations in terms of solvent-free electrostatic spinning, and at present, having for having reported utilizes alpha-cyano propylene
The quick moisture-curable of acid esters (medical adhesive, the main component of 502 glue), electrospinning is into micro nanometer fiber (Polymer Chemistry
4:5696(2013))；Chinese patent (patent publication No.：CN104532367A) disclose a kind of solvent-free electrostatic spinning and prepare and gather
The method of urethane micro nanometer fiber, mainly by heating collector, solvent-free electrostatic spinning is realized in the method for heat cure；China
Patent (patent publication No.：CN104213207A a kind of packaged type air pressure gun melt heating electrostatic spinning apparatus, the dress) are disclosed
Put easy to assembling, easily operated, polymer that can be relatively low to fusing point realizes that mobile electrostatic spinning prepares its micro nanometer fiber.
Photo-curing material (UV curing materials) is a kind of special high molecular material, and the prepolymer addition of its liquid is light-initiated
Agent, after absorbing high-intensity ultraviolet light (UV), produces living radical or cation, so as to trigger polymerization, crosslinking and grafting
Reaction, can be converted into solid-state by liquid within a certain period of time.In theory can as the presoma of solvent-free electrospinning, still, on
The report of the solvent-free electrostatic spinning technique of ultraviolet light is very rare, Chinese patent (patent publication No.：CN101021017A it is) open
The method of no-solvent electrically spinning process for preparing micron and nanometer fiber, mainly under the initiation of ultraviolet light irradiation and initiator, makes
The precursor liquid of the functional group containing activity double key is solidified into micro nanometer fiber, but its needs mixes according to a certain percentage with reactive diluent
Close and use, precursor liquid prepares cumbersome, and the fiber prepared is generally shorter and irregular, it is incomplete to cure, length maximum
It is worth for 1 centimetre.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of scale no-solvent electrically to spin standby photocuring
The method of material micro-nano rice fiber, this method is easy to operate, effectively prevent environmental pollution caused by organic solvent volatilization, safety
Environmental protection, is particularly suitable for the large-scale commercial production of photo-curing material micro nanometer fiber, meanwhile, overcome current electrospinning photocuring
Material micro-nano rice fiber precursor liquid arrangement step is complicated, gained fiber is generally shorter and irregular, it is incomplete to cure, can not advise greatly
The technical barrier of mould production, can largely be made the photo-curing material micro nanometer fiber that completion of cure, form are regular and continuity is good,
It is suitable for scale production.
To achieve these goals, technical solution provided by the invention is as follows：
A kind of method of the standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning, comprises the following steps：
(1) spinning precursor liquid is configured：The liquid prepolymer of photo-curing material is mixed with photoinitiator under light protected environment
Uniformly, then being stood under natural light environment makes its pre-polymerization, obtains spinning precursor liquid；
(2) electrospinning micro nanometer fiber：The spinning precursor solution that step (1) is matched somebody with somebody is placed in electrostatic spinning apparatus connection to spin
In the liquid storage mechanism of silk nozzle, and the spinning nozzle of the electrostatic spinning apparatus and collector are placed under few oxygen environment and carry out electricity
Spin, the jet stream sprayed in electro-spinning process with ultraviolet source to spinning nozzle is irradiated, you can in the collection of electrostatic spinning apparatus
Photo-curing material micro nanometer fiber is collected on extremely.
Inventor summarizes by many experiments and finds, it is endless that method of electrostatic spinning prepares the curing of UV curing materials micro nanometer fiber
Entirely, fiber is generally shorter and irregular reason is：Electrostatic spinning is used as a kind of method for preparing micro nanometer fiber
In preparing photo-curing material micro nanometer fiber, the big feature of specific surface area of its obtained micro nanometer fiber, this fibre morphology increases
The big contact area of prepolymer and oxygen, makes it be contacted with the oxygen in air more abundant, is exaggerated UV curing materials and exists
The effect of oxygen inhibition phenomenon in solidification process, hinders the polymerizing curable of prepolymer, so as to cause obtained photocuring material
Expect that micro nanometer fiber curing is incomplete, fiber is generally shorter and irregular, have impact on large-scale production and the application prospect of fiber.
In order to solve the problems, such as this, preparation method of the invention, selects to carry out electricity under the low few oxygen environment of oxygen concentration
Spinning process prepares photo-curing material micro nanometer fiber, and in spinning process, pre-polymer solution is under action of high voltage, from spinneret
Ejection forms jet stream, and the photoinitiator in jet stream absorbs the energy of ultraviolet light and produces living radical, and living radical triggers
Prepolymer occur polymerisation, jet stream fall during with fiber splitting, finally on collector formed polymer it is micro-
Nanofiber, so as to fulfill solvent-free electrostatic spinning.The spinning environment of few oxygen, the oxygen inhibition that effectively prevent in electrostatic spinning show
As so that completion of cure, form rule and continuous photo-curing material micro nanometer fiber largely be made, and making in spinning process
Precursor liquid is made of the prepolymer of photoinitiator and photo-curing material, without other organic solvents, effectively prevent organic
Environmental pollution caused by solvent volatilizees, safety and environmental protection, this method are suitable for the large-scale industrial of photo-curing material micro nanometer fiber
Production.
Further, the photo-curing material of the step (1) is urethane acrylate, epoxy acrylate, polyethers third
One or more in olefin(e) acid ester, polyester acrylate, acrylic resin.
Further, the photo-curing material of the step (1) is urethane acrylate, the photoinitiator and polyurethane
The mass ratio of acrylate is 1:10~1:30.
In numerous photo-curing materials, urethane acrylate (PUA) is a kind of ideal UV-cured resin,
Be usually used in coating and adhesive area, its film or fiber after curing have high-wearing feature of polyurethane, adhesion, pliability,
The optical property and weatherability of high-peeling strength and excellent resistance to low temperature and polyacrylate brilliance, are a kind of comprehensive
The excellent radiation curing material of energy.The various acrylates used as coating and adhesive, are easy to carry out polymerisation in bulk,
Oxygen inhibition phenomenon is easier to overcome.
Further, the standing pre-polymerization time of the step (1) is 1~2 day.
Further, few oxygen environment of the step (2) is less than 5% spinning environment for oxygen concentration.
Further, the spinning voltage of the electro-spinning process of the step (2) is 10~30 kilovolts, and spinning distance is 5~50
Centimetre, the power of ultraviolet source is 300~500 watts, and ultraviolet source is 10~20 centimetres with the spacing for collecting interpolar.
Further, the electrostatic spinning apparatus in the step (2) include high voltage power supply, liquid storage mechanism, spinning nozzle, every
Oxygen mechanism, ultraviolet source and collector, the high-voltage power cathode connect spinning nozzle, spinning nozzle connection storage spinning forerunner
The liquid storage mechanism of liquid, collector connection high voltage power supply anode or is directly grounded, the oxygen barrier mechanism include internal anaerobic or
The seal box of few oxygen, the spinning nozzle and collector be located in seal box, and ultraviolet source be located at that seal box is interior or it is launched
Ultraviolet light can be injected in seal box, and ultraviolet source can irradiate spinning nozzle and collect interelectrode space.
The device is provided with oxygen barrier mechanism, and when device use need to first open oxygen barrier mechanism, and the oxygen in seal box is complete
Portion discharges or the concentration for reducing oxygen in seal box as far as possible, to build the spinning environment of few oxygen, then again by solvent-free spinning
Silk precursor liquid injection liquid storage mechanism, opens ultraviolet source and high voltage power supply, carries out electrostatic spinning under few oxygen oxygen atmosphere, can have
Effect overcomes influence of the oxygen inhibition phenomenon to photo-curing material micro nanometer fiber forming process.
Further, the seal box of the oxygen barrier mechanism is vacuum desiccator, and the vacuum desiccator connects vacuum pump.
Vacuum pump can exclude the air in seal box, so as to be provided for the electrostatic spinning process carried out in seal box
The environment of anaerobic or few oxygen, the influence for avoiding oxygen inhibition phenomenon from forming photo-curing material micro nanometer fiber.
Further, air inlet and gas outlet are provided with the seal box of the oxygen barrier mechanism, the air inlet connects gas
Body source, the gas source are source nitrogen, carbon dioxide source or inert gas source, are additionally provided with the seal box and hinder gas straight
The baffle being blown into case is connect, for the baffle between air inlet and collector, being provided with the seal box prevents ultraviolet light
The shadow shield of jet stream at line direct irradiation spinning nozzle ejection end, the shadow shield are located at ultraviolet source and spinning nozzle injection
Between end, set close to spinning nozzle ejection end, the collection extremely roller collector, the collection cylinder of the roller collector
Linkage is docked with the output shaft of DC brushless motor, collection cylinder is mutually overlapping with the central axis of the output shaft of DC brushless motor
Close, the electric machine controller of DC brushless motor electric connection of power supply and control motor speed.
Gas source can persistently be filled with nitrogen, carbon dioxide or inert gas into seal box from air inlet, by seal box
Air from gas outlet exclude so that the electrostatic spinning process to be carried out in seal box provides lack oxygen environment, avoid oxygen from hindering
The influence that poly- phenomenon forms photo-curing material micro nanometer fiber.Baffle in seal box effectively can prevent from being passed through direct during air-flow
Blow on fiber, influence the collection of fiber, in addition, the gas that baffle can also make to be passed through be not it is straight directly go out, reach gas
Circulate purpose.Shadow shield can prevent spinning solution jet stream from just having gone out spinneret and just having cured under the irradiation of ultraviolet light, influence the drawing of jet stream
Stretch and cleave, and then influence the effect of continuous spinning.Using roller collector, by adjusting spinning parameter (spinning voltage, spinning
Distance, drum rotation speed etc.), orderly electrospinning photo-curing material micro nanometer fiber can be made.
Further, the step (2) first opens gas source and gas is passed through into seal box before electro-spinning process starts,
3~9 milliliters/second of gas flow rate, is passed through after reaching within 3~5 minutes few oxygen environment and is then turned on electrostatic spinning apparatus unlatching spinning, spinning
The spacing of nozzle to collection cylinder is 5~50 centimetres, 3~8 centimetres of collection cylinder radius, and DC brushless motor drives roller rotation
Rotating speed be 30~90 revs/min.
Beneficial effects of the present invention are：The present invention provides a kind of scale no-solvent electrically to spin standby photo-curing material micro-nano
Rice fiber method, this method is easy to operate, effectively prevent organic solvent volatilization caused by environmental pollution, safety and environmental protection, especially
It is suitable for the large-scale commercial production of photo-curing material micro nanometer fiber, meanwhile, it is micro- to overcome current electrospinning photo-curing material
Nanofiber precursor liquid arrangement step is complicated, gained fiber is generally shorter and irregular, it is incomplete to cure, can not mass produce
Technical barrier, completion of cure, form rule and the good photo-curing material micro nanometer fiber of continuity, suitable rule can largely be made
Modelling produces.Specifically：
(1) it is micro-nano to prepare photo-curing material for this method selection progress electro-spinning process under the low few oxygen environment of oxygen concentration
Fiber, in spinning process, pre-polymer solution sprays to form jet stream under action of high voltage from spinneret, and the light in jet stream draws
Hair agent absorbs the energy of ultraviolet light and produces living radical, living radical initiation prepolymer generation polymerisation, under jet stream
With the splitting of fiber during falling, polymer micro-nanometer fiber is finally formed on collector, so as to fulfill solvent-free quiet
Electrospun.The spinning environment of few oxygen, effectively prevent the oxygen inhibition phenomenon in electrostatic spinning, thus be largely made completion of cure,
Form rule and continuous photo-curing material micro nanometer fiber, scale of this method suitable for photo-curing material micro nanometer fiber
Industrial production.
(2) precursor liquid used in spinning process is made of the prepolymer of photoinitiator and photo-curing material, without other
Organic solvent, effectively prevent environmental pollution caused by organic solvent volatilization, safety and environmental protection.
(3) in preferred solution, the device that uses in step (2) is provided with oxygen barrier mechanism, and when device use need to first open
Oxygen barrier mechanism, the concentration for reducing oxygen in seal box that the oxygen in seal box is all discharged or tried one's best, to build few oxygen
Spinning environment, then injects liquid storage mechanism by solvent-free spinning precursor liquid again, ultraviolet source and high voltage power supply is opened, in few oxygen
Electrostatic spinning is carried out under oxygen atmosphere, can effectively overcome shadow of the oxygen inhibition phenomenon to photo-curing material micro nanometer fiber forming process
Ring.Gas source, which is employed, in further prioritization scheme is persistently filled with nitrogen, carbon dioxide or lazy into seal box from air inlet
Property gas, by the air in seal box from gas outlet exclude so that the electrostatic spinning process to be carried out in seal box provides lack
The environment of oxygen, the influence formed to avoid oxygen inhibition phenomenon to photo-curing material micro nanometer fiber.Baffle in seal box can have
Effect is directly blown on fiber when preventing from being passed through air-flow, the collection of fiber is influenced, in addition, the gas that baffle can also make to be passed through is not
It is straight directly to go out, reach the circulation purpose of gas.Shadow shield can prevent spinning solution jet stream from just having gone out spinneret just in the irradiation of ultraviolet light
Lower curing, influences the stretching and splitting of jet stream, and then influences the effect of continuous spinning.Using roller collector, spun by adjusting
Orderly electrospinning photo-curing material micro nanometer fiber can be made in silk parameter, make the performance of gained micro nanometer fiber membrane material in spy
Determine that there is specificity on direction, to extend the application range of photo-curing material micro nanometer fiber material.
Brief description of the drawings
Fig. 1 is the structure diagram for the electrostatic spinning apparatus that embodiment 1 to 5 uses.
The optical microscope photograph of orderly urethane acrylate micro nanometer fiber prepared by Fig. 2 embodiments 1.
The optical microscope photograph of orderly urethane acrylate micro nanometer fiber prepared by Fig. 3 comparative examples.
The optical microscope photograph of distorted-structure urethane acrylate micro nanometer fiber prepared by Fig. 4 embodiments 1.
In Fig. 1,1- high voltage power supplies, 2- ultraviolet sources, 3- gas cylinders, 31- gas cylinder pressure reducing valves, 4- DC brushless motors, 41- electricity
Machine controller, 5- air inlets, 6- gas outlets, 7- collection cylinders, 8- spinning nozzles, 9- baffles, 10- shadow shields, 11- gas-guide tubes,
12- liquid storage mechanisms, 13- conducting wires, 14- seal boxs.
Embodiment
According to following embodiments, the present invention may be better understood.It is however, as it will be easily appreciated by one skilled in the art that real
Apply example described specific material proportion, process conditions and its result and be merely to illustrate the present invention without that will not should limit
The present invention described in detail in claims.
Embodiment 1
A kind of method that scale no-solvent electrically spinning has sequence urethane acrylate micro nanometer fiber, this method use
Electrostatic spinning apparatus as shown in Figure 1, including high voltage power supply 1, liquid storage mechanism 12, spinning nozzle 8, oxygen barrier mechanism, ultraviolet source 2
And collector, 1 cathode of high voltage power supply connect spinning nozzle 8, the liquid storage mechanism of the connection storage spinning precursor liquid of spinning nozzle 8
12, the liquid storage mechanism 12 is plastic injector needle tubing, and the collector connects 1 anode of high voltage power supply, oxygen barrier mechanism bag
The seal box 14 of internal anaerobic or few oxygen is included, the spinning nozzle 8 and collector are located in seal box 14, and ultraviolet source 2 is located at
Outside seal box 14, its ultraviolet light launched can be injected in seal box 14, and ultraviolet source 2 can irradiate spinning nozzle 8 and collector
Between；Air inlet 5 and gas outlet 6 are provided with the seal box 14 of the oxygen barrier mechanism, the seal box 14 is organic glass case,
Air inlet 5 and gas outlet 6 are separately positioned in the opposite two side walls of seal box 14, and the air inlet 5 connects gas source, described
Gas source is gas cylinder 3, filled with nitrogen in the gas cylinder 3 of embodiment 1, is additionally provided with the seal box 14 and hinders nitrogen to be directly blown into
Baffle 9 in case, the baffle 9 is between air inlet 5 and collector, the collection extremely roller collector, the roller
The collection cylinder 7 of collector docks linkage with the output shaft of DC brushless motor 4, collection cylinder 7 and DC brushless motor 4 it is defeated
The central axis of shaft coincides, the electric machine controller 41 of 4 electric connection of power supply of DC brushless motor and control motor speed, described
Being provided with seal box 14 prevents the shadow shield 10 of the jet stream at 8 ejection end of ultraviolet light direct irradiation spinning nozzle, the screening
Tabula rasa 10 is located between 8 ejection end of ultraviolet source 2 and spinning nozzle, is set close to 8 ejection end of spinning nozzle.
This method comprises the following steps：
(1) spinning precursor liquid is configured：0.4 gram of Liquid photoinitiators (photoinitiator is added in conical flask
1173,2- hydroxy-2-methyl -1- phenyl -1- acetone, Aldrich), add 8 grams urethane acrylate (DR-U301,
Changxing chemical engineering industry joint-stock company (Taiwan)), shading stirring is carried out with magnetic stirring apparatus, it is small using 45 degree of heating water baths, stirring 2
When, photoinitiator is uniformly mixed with urethane acrylate；2 days are stood under room temperature available light, makes polyurethane acroleic acid
The pre-polymerization that ester occurs to a certain extent obtains precursor solution；
(2) electrospinning micro nanometer fiber：By the liquid storage of the device of the prepared precursor solution injection embodiment 1 of step (1)
In mechanism, spinning nozzle is 3 millimeters of aluminum nozzles of ejection end internal diameter, is passed through nitrogen into seal box, 3 milliliters/second of nitrogen flow rate,
It is passed through and reaches few oxygen environment of the oxygen concentration less than 5% in seal box after five minutes, then carries out electrostatic spinning, spinning nozzle injection
The spacing of mouth and collection cylinder is 10 centimetres, 22 kilovolts of spinning voltage, 70 revs/min of motor speed, with ultraviolet source power 300
Watt, the fiber sprayed to spinneret is irradiated, and the spacing of ultraviolet source and collection cylinder is 15 centimetres, by 10 minutes,
The continuous micro nanometer fiber of aligned orderly is collected on roller collector, the results are shown in Figure 2 for observation under an optical microscope.It is logical
The rotating speed of adjustment roller collector is crossed, the different continuous micro nanometer fiber of degree of crook can be collected into, by drum rotation speed tune
To 30 revs/min, the results are shown in Figure 4 in optical fiber Microscopic observation for gained fiber.
Embodiment 2
A kind of method that scale no-solvent electrically spinning has sequence urethane acrylate micro nanometer fiber, this method use
Device it is similar to Example 1, filled with carbon dioxide in the gas cylinder 3 used difference lies in embodiment 2.This method include with
Lower step：
(1) spinning precursor liquid is configured：0.5 gram of solid-state photoinitiator (184,1- hydroxy-cyclohexans are added in conical flask
Base-phenyl ketone, Aldrich), add 9 grams of urethane acrylate (DR-U301, Changxing chemical engineering industry joint-stock company
(Taiwan)), carry out shading stirring with magnetic stirring apparatus, using 50 degree of heating water baths, when stirring 1 is small, make solid-state photoinitiator with
Urethane acrylate mixed dissolution is uniform；1 day is stood under room temperature available light, makes urethane acrylate that certain journey occur
Pre-polymerization on degree obtains precursor solution；
(2) electrospinning micro nanometer fiber：By the liquid storage machine of the prepared precursor solution injection electrostatic spinning apparatus of step (1)
In structure, spinning nozzle is 2 millimeters of aluminum nozzles of ejection end internal diameter, using dioxide bottle as gas source, is led into seal box
Enter carbon dioxide, 9 milliliters/second of gas flow rate, is passed through and reaches within 3 minutes few oxygen that oxygen concentration is less than 5% in back sealed box
Environment, then electrostatic spinning is carried out, the spacing of spinning nozzle jet port and collection cylinder is 12 centimetres, 24 kilovolts of spinning voltage, electricity
90 revs/min of machine rotating speed, with 500 watts of ultraviolet source power, the fiber sprayed to spinneret is irradiated, and ultraviolet source is rolled with collecting
The spacing of cylinder is 10 centimetres, and by 5 minutes, the continuous micro nanometer fiber of aligned orderly is collected on roller collector.
Embodiment 3
A kind of method that scale no-solvent electrically spinning has sequence urethane acrylate micro nanometer fiber, this method use
Device it is similar to Example 1, filled with helium in the gas cylinder 3 used difference lies in embodiment 2.This method comprises the following steps：
(1) spinning precursor liquid is configured：0.1 gram of Liquid photoinitiators (photoinitiator is added in conical flask
1173,2- hydroxy-2-methyl -1- phenyl -1- acetone, Aldrich), add 2 grams of urethane acrylate
(Sartomer704, Sartomer (Guangzhou) Chemical Co., Ltd.), carries out shading stirring, using 40 degree of water-baths with magnetic stirring apparatus
Heating, when stirring 1.5 is small, makes photoinitiator and urethane acrylate mixed dissolution uniform, is stood under room temperature available light
1.5 days, the pre-polymerization that urethane acrylate occurs to a certain extent is set to obtain precursor solution；
(2) electrospinning micro nanometer fiber：By the liquid storage machine of the prepared precursor solution injection electrostatic spinning apparatus of step (1)
In structure, spinning nozzle is 1 millimeter of aluminum nozzle of ejection end internal diameter, and using helium gas cylinder as gas source, helium is passed through into seal box
Gas, 5 milliliters/second of gas flow rate, is passed through and reaches within 4 minutes few oxygen environment of the oxygen concentration less than 5% in back sealed box, then carries out quiet
The spacing of Electrospun, spinning nozzle jet port and collection cylinder is 8 centimetres, 22 kilovolts of spinning voltage, 75 revs/min of motor speed,
With 350 watts of ultraviolet source power, the fiber sprayed to spinneret is irradiated, and the spacing of ultraviolet source and collection cylinder is 12 lis
Rice, by 8 minutes, is collected into the continuous micro nanometer fiber of aligned orderly on roller collector.
Embodiment 4
A kind of method that scale no-solvent electrically spinning has sequence urethane acrylate micro nanometer fiber, this method use
Device it is same as Example 1.This method comprises the following steps：
(1) spinning precursor liquid is configured：0.2 gram of solid-state photoinitiator (184,1- hydroxy-cyclohexans are added in conical flask
Base-phenyl ketone, Aldrich), adding 2 grams of urethane acrylate, (Sartomer704, Sartomer (Guangzhou) chemistry have
Limit company), shading stirring is carried out with magnetic stirring apparatus, using 30~40 degree of heating water baths, when stirring 1~1.5 is small, makes solid-state light
Initiator is uniformly mixed with urethane acrylate, and 1 day is stood under room temperature available light, urethane acrylate is occurred one
The pre-polymerization determined in degree obtains precursor solution；
(2) electrospinning micro nanometer fiber：By the liquid storage machine of the prepared precursor solution injection electrostatic spinning apparatus of step (1)
In structure, spinning nozzle is 1.5 millimeters of aluminum nozzles of ejection end internal diameter, using nitrogen gas cylinder as gas source, is passed through into seal box
Nitrogen, 8 milliliters/second of gas flow rate, is passed through and reaches few oxygen environment of the oxygen concentration less than 5% in seal box after five minutes, then carries out
The spacing of electrostatic spinning, spinning nozzle jet port and collection cylinder is 9 centimetres, 23 kilovolts of spinning voltage, 60 turns of motor speed/
Point, with 400 watts of ultraviolet source power, the fiber sprayed to spinneret is irradiated, and the spacing of ultraviolet source and collection cylinder is
13 centimetres, by 10 minutes, the continuous micro nanometer fiber of aligned orderly is collected on roller collector.
Embodiment 5
A kind of method that scale no-solvent electrically spinning has sequence urethane acrylate micro nanometer fiber, this method use
Device it is same as Example 1.This method comprises the following steps：
(1) spinning precursor liquid is configured：0.1 gram of solid-state photoinitiator (184,1- hydroxy-cyclohexans are added in conical flask
Base-phenyl ketone, Aldrich), 3 grams of urethane acrylate (Sheng Mao new materials Co., Ltd of Foshan City) is added, then add
0.2 gram of hydroxy-ethyl acrylate, shading stirring is carried out with magnetic stirring apparatus, using 40 degree of heating water baths, when stirring 1.5 is small, is made
Solid-state photoinitiator is uniformly mixed with urethane acrylate, is stood 1 day under room temperature available light, is made urethane acrylate
The pre-polymerization occurred to a certain extent obtains precursor solution；
(2) electrospinning micro nanometer fiber：By the liquid storage machine of the prepared precursor solution injection electrostatic spinning apparatus of step (1)
In structure, spinning nozzle is 1 millimeter of aluminum nozzle of ejection end internal diameter, and using nitrogen gas cylinder as gas source, nitrogen is passed through into seal box
Gas, 9 milliliters/second of gas flow rate, is passed through and reaches within 4 minutes few oxygen environment of the oxygen concentration less than 5% in back sealed box, then carries out quiet
The spacing of Electrospun, spinning nozzle jet port and collection cylinder is 6 centimetres, 20 kilovolts of spinning voltage, 40 revs/min of motor speed,
With 450 watts of ultraviolet source power, the fiber sprayed to spinneret is irradiated, and the spacing of ultraviolet source and collection cylinder is 10 lis
Rice, by 3 minutes, is collected into the continuous micro nanometer fiber of aligned orderly on roller collector.
Reference examples
The electrostatic spinning apparatus that comparative example uses is similar to Example 1, difference lies in：The device for spinning of comparative example is not provided with
Oxygen barrier mechanism, i.e., carry out spinning in air atmosphere, and it is micro- to have sequence urethane acrylate using device no-solvent electrically spinning
The method of nanofiber, comprises the following steps：
(1) spinning precursor liquid is configured：0.4 gram of Liquid photoinitiators (photoinitiator is added in conical flask
1173,2- hydroxy-2-methyl -1- phenyl -1- acetone, Aldrich), add 8 grams urethane acrylate (DR-U301,
Changxing chemical engineering industry joint-stock company (Taiwan)), shading stirring is carried out with magnetic stirring apparatus, it is small using 45 degree of heating water baths, stirring 2
When, photoinitiator is uniformly mixed with urethane acrylate；2 days are stood under room temperature available light, makes polyurethane acroleic acid
The pre-polymerization that ester occurs to a certain extent obtains precursor solution；
(2) electrospinning micro nanometer fiber：By the liquid storage machine of the device of the prepared precursor solution injection comparative example of step (1)
In structure, spinning nozzle is 3 millimeters of aluminum nozzles of ejection end internal diameter, and the spacing of spinning nozzle jet port and collection cylinder is 10 lis
Rice, 22 kilovolts of spinning voltage, 70 revs/min of motor speed, with 300 watts of ultraviolet source power, carries out the fiber that spinneret sprays
The spacing of irradiation, ultraviolet source and collection cylinder is 15 centimetres, and by 10 minutes, aligned orderly is collected on roller collector
Continuous micro nanometer fiber, under an optical microscope observation the results are shown in Figure 3.
By reference examples compared with embodiment 1 as can be seen that in the case where other spinning parameters are identical, in air
The fiber of obtained reference examples is generally shorter and irregular in atmosphere, it is incomplete to cure, and by the preparation method of the present invention few
The diameter smaller that micro nanometer fiber made from electrospinning is tieed up under oxygen environment, fiber morphology is more regular, and continuity is more preferable, i.e. this hair
The method of the bright standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning effectively prevent the oxygen resistance in electrostatic spinning
Poly- phenomenon, so that completion of cure, form rule and continuous photo-curing material micro nanometer fiber be made.
Embodiment 6
A kind of method of the standby polyester acrylate micro nanometer fiber of scale no-solvent electrically spinning, the electrostatic that this method uses
Device for spinning is similar to the device of embodiment 1, and difference lies in the seal box of the oxygen barrier mechanism of the device of embodiment 2 is true for glass
Empty drier, the glass evacuated drier connection vacuum pump, the ultraviolet source are located in seal box, and ultraviolet source can irradiate
Described to collect the aluminium sheet being extremely grounded between spinning nozzle and collector, the liquid storage mechanism of embodiment 6 is to be connected with spinning nozzle
Aluminum tank body.
This method comprises the following steps：
(1) spinning precursor liquid is configured：0.1 gram of Liquid photoinitiators (photoinitiator is added in conical flask
1173,2- hydroxy-2-methyl -1- phenyl -1- acetone, Aldrich), add 1 gram of polyester acrylate (CN750, Sha Duo
Agate (Guangzhou) Chemical Co., Ltd.), shading stirring is carried out with magnetic stirring apparatus, using 30 degree of heating water baths, when stirring 1 is small, is made
Photoinitiator and urethane acrylate mixed dissolution are uniform；2 days are stood under room temperature available light, makes urethane acrylate
The pre-polymerization occurred to a certain extent obtains precursor solution；
(2) electrospinning micro nanometer fiber：By the liquid storage machine of the prepared precursor solution injection electrostatic spinning apparatus of step (1)
In structure, spinning nozzle is 1.2 millimeters of aluminum nozzles of ejection end internal diameter, opens vacuum pump, close encapsulation case after the completion of vacuumizing, is closed
Close vacuum pump, the spacing of spinning nozzle jet port and aluminium foil collector is 6 centimetres, 24 kilovolts of spinning voltage, with ultraviolet source work(
350 watts of rate, the fiber sprayed to spinneret are irradiated, and the spacing of ultraviolet source and collector is 50 centimetres, by 10 minutes,
Polyester acrylate micro nanometer fiber is collected on aluminium foil collector.
The above, be only the present invention explanation embodiment, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, on the premise of the method for the present invention is not departed from, that makes some changes
Protection scope of the present invention is also should be regarded as into supplement, the place of not elaborating not is known in those skilled in the art to the present invention
The prior art, all those skilled in the art, without departing from the spirit and scope of the present invention, utilize above institute
The equivalent variations for a little variation, modification and evolution that the technology contents of announcement are made, are the equivalent embodiment of the present invention；Together
When, the variation, modification and evolution for any equivalent variations that all substantial technologicals according to the present invention do above-described embodiment, still
Belong to the scope of technical scheme.
Claims (9)
- A kind of 1. method of the standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning, it is characterised in that including following Step：(1) spinning precursor liquid is configured：The liquid prepolymer of photo-curing material is uniformly mixed with photoinitiator under light protected environment, Being stood again under natural light environment makes its pre-polymerization, obtains spinning precursor liquid；(2) electrospinning micro nanometer fiber：The spinning precursor liquid that step (1) is matched somebody with somebody is placed in electrostatic spinning apparatus connection spinning nozzle In liquid storage mechanism, and the spinning nozzle of the electrostatic spinning apparatus and collector are placed under few oxygen environment and carry out electrospinning, electrospinning During the jet stream that is sprayed with ultraviolet source to spinning nozzle be irradiated, you can collected on the collector of electrostatic spinning apparatus To photo-curing material micro nanometer fiber；Electrostatic spinning apparatus in the step (2) includes high voltage power supply, liquid storage mechanism, spinning Nozzle, oxygen barrier mechanism, ultraviolet source and collector, the high-voltage power cathode connect spinning nozzle, spinning nozzle connection storage The liquid storage mechanism of spinning precursor liquid, the collector connect high voltage power supply anode or are directly grounded, and the oxygen barrier mechanism includes interior The seal box of portion's anaerobic or few oxygen, the spinning nozzle and collector be located in seal box, ultraviolet source be located at seal box it is interior or Its ultraviolet light launched can be injected in seal box, and ultraviolet source can irradiate spinning nozzle and collect interelectrode space.
- 2. a kind of method of standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning as claimed in claim 1, its It is characterized in that, the photo-curing material of the step (1) is urethane acrylate, epoxy acrylate, polyether acrylate, poly- One or more in ester acrylate, acrylic resin.
- 3. a kind of method of standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning as claimed in claim 2, its It is characterized in that, the photo-curing material of the step (1) is urethane acrylate, the photoinitiator and urethane acrylate Mass ratio be 1:10~1:30.
- 4. a kind of method of standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning as claimed in claim 1, its It is characterized in that, the standing pre-polymerization time of the step (1) is 1~2 day.
- 5. a kind of method of standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning as claimed in claim 1, its It is characterized in that, few oxygen environment of the step (2) is less than 5% spinning environment for oxygen concentration.
- 6. a kind of method of standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning as claimed in claim 1, its It is characterized in that, the spinning voltage of the electro-spinning process of the step (2) is 10~30 kilovolts, and spinning distance is 5~50 centimetres, ultraviolet The power of light source is 300~500 watts, and ultraviolet source is 10~20 centimetres with the spacing for collecting interpolar.
- 7. a kind of method of standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning as claimed in claim 1, its It is characterized in that, the seal box of the oxygen barrier mechanism is vacuum desiccator, and the vacuum desiccator connects vacuum pump.
- 8. a kind of method of standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning as claimed in claim 1, its It is characterized in that, air inlet and gas outlet is provided with the seal box of the oxygen barrier mechanism, the air inlet connects gas source, described Gas source is source nitrogen, carbon dioxide source or inert gas source, is additionally provided with the seal box and hinders gas to be directly blown into case Interior baffle, for the baffle between air inlet and collector, being provided with the seal box prevents ultraviolet light from directly shining Penetrate the shadow shield of the jet stream at spinning nozzle ejection end, the shadow shield between ultraviolet source and spinning nozzle ejection end, Set close to spinning nozzle ejection end, the collection extremely roller collector, the collection cylinder and direct current of the roller collector The central axis of the output shaft of the output shaft docking linkage of brushless electric machine, collection cylinder and DC brushless motor coincides, direct current The electric machine controller of brushless electric machine electric connection of power supply and control motor speed.
- 9. a kind of method of standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning as claimed in claim 8, its It is characterized in that, the step (2) first opens gas source and gas, gas flow rate 3 are passed through into seal box before electro-spinning process starts ~9 milliliters/seconds, are passed through after reaching within 3~5 minutes few oxygen environment and are then turned on electrostatic spinning apparatus unlatching spinning, spinning nozzle to receipts The spacing for collecting roller is 5~50 centimetres, 3~8 centimetres of collection cylinder radius, and the DC brushless motor drive rotating rotating speed of roller is 30~90 revs/min.
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| CN107904676B (en) * | 2017-12-05 | 2020-05-29 | 青岛大学 | Double-component reaction curing type solvent-free electrospinning device |
| CN107955996B (en) * | 2017-12-05 | 2020-05-29 | 青岛大学 | Double-component reaction curing type solvent-free electro-spinning micro-nanofiber and preparation method thereof |
| CN108707976A (en) * | 2018-04-09 | 2018-10-26 | 南京捷纳思新材料有限公司 | A kind of the microfluid device for spinning and technique of solvent-free spinning |
| CN111926396B (en) * | 2020-07-31 | 2022-02-18 | 浙江理工大学 | Preparation method of nanofiber membrane cloth with interpenetrating structure |
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| CN101021017A (en) * | 2007-02-02 | 2007-08-22 | 吉林大学 | No-solvent electrically spinning process for preparing micron and nanometer fiber |
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| CN101021017A (en) * | 2007-02-02 | 2007-08-22 | 吉林大学 | No-solvent electrically spinning process for preparing micron and nanometer fiber |
| CN101611179A (en) * | 2007-02-14 | 2009-12-23 | 陶氏环球技术公司 | The solvent-free electrostatic spinning of polymer or oligomer fibers |
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