CN100526524C - No-solvent electrically spinning process for preparing micron and nanometer fiber - Google Patents
No-solvent electrically spinning process for preparing micron and nanometer fiber Download PDFInfo
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- CN100526524C CN100526524C CNB2007100553014A CN200710055301A CN100526524C CN 100526524 C CN100526524 C CN 100526524C CN B2007100553014 A CNB2007100553014 A CN B2007100553014A CN 200710055301 A CN200710055301 A CN 200710055301A CN 100526524 C CN100526524 C CN 100526524C
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Abstract
The present invention belongs to the field of micron/nanometer fiber preparing technology, and is especially no-solvent electrically spinning and ultraviolet curing process for preparing micron/nanometer fiber. The reacted components include acrylate oligomer, active diluent and photoinitiator. The process includes pre-polymerizing to form oligomer, electrically spinning while irradiating with ultraviolet ray to decompose the photoinitiator for generating free radical initiating the polymerization of the pre-polymer and splitting fiber to generate micron/nanometer fiber. The process has material utilizing rate as high as 100 %, no environmental pollution caused by volatized solvent and low production cost.
Description
Technical field
The invention belongs to the technology of preparing of micro nanometer fiber, be specifically related under condition of no solvent, utilize electrospinning silk technology and UV-curing technology to combine and prepare the method for micro nanometer fiber.
Background technology
Electrospinning silk technology has become one of most important means of preparation micro nanometer fiber.Along with developing rapidly of nanosecond science and technology, the problem of environmental pollution and production cost more and more causes people's attention.Though people have prepared many micro nanometer fibers by the method for electrospinning silk, but in solvent spinning, generally need with an organic solvent, and its use amount can reach 80-95% at most, the production cost that this certainly will cause bigger pollution and increase micro nanometer fiber to environment is restricted the industrialization of electrically spinning process for preparing micron and nanometer fiber on certain degree.Also do not see at present the relevant report of no-solvent electrically spinning process for preparing micron and nanometer fiber.
Summary of the invention
The purpose of this invention is to provide and a kind ofly under condition of no solvent, utilize electrical spinning method and ultra-violet curing method to combine to prepare eco-friendly and the method for micro nanometer fiber cheaply, enlarge the micro nanometer fiber kind, promote micro nanometer fiber with the fastest speed industrialization.
Step of the present invention is as follows:
(1) light trigger with 0.05～3g joins 5～15g macromolecule repetitive less than in 10 the oligomer that has the acrylate end group, add 2～12g reactive diluent again, and shading at room temperature stirred 10～30 hours, so that initator dissolves fully;
(2) under 50～90 ℃, continue shading and stirred 2～30 hours, remove light shield then, at room temperature continue to stir 1～20 day, so that oligomer generation pre-polymerization to a certain degree in the reaction system;
(3) gained solution is put into to have internal diameter be that the spray fiber tube of the shading of 0.5mm～3.0mm spinneret carries out the electrospinning silk, spinneret is 10～60cm to the distance between the negative electrode dash receiver, be that the ultraviolet source of 30～500W shines the spray silk that gushes out from spinneret with power in the electrospinning silk process, ultraviolet source is 2～60cm apart from the distance in spray the Silk Road footpath, distance apart from spinneret is 2～20cm, the electrospinning filament voltage is 10～28KV, after 5～30 minutes, on the negative electrode dash receiver, obtain micro nanometer fiber.
Annotate: the light trigger that is fit to has: benzil derivative (as: α; α '-dimethyl benzil ketals), acetophenone derivs (as: α; α-diethoxy acetophenone), alpha-alcohol ketone derivative (as: 1-hydroxyl-cyclohexyl benzophenone), α-amido ketone derivatives (as: [2-methyl 1-(the false sulfydryl phenyl of 4-)-2-morpholine-1-acetone]), acyl group phosphorus oxygen thing (as: 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide).
The oligomer that is fit to is the acrylic resin that contains carbon-carbon double bond, for example: epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, pure acrylic resin, epoxy resin, water-based UV oligomer (as: aromatic acid acrylic acid half ester), carboxylic acrylate oligomer (as: acroleic acid esterification polyacrylic resin), amino acrylate oligomer (as: melamine acrylic resin), the dual cure of isocyanato group containing oligomer (as: hexamethylene diisocyanate).
The diluent that is fit to is contract the propylene glycol double methacrylate (DPGDA) or the propylene glycol double methacrylate (TPGDA) that contracts of 1,6 hexylene glycol double methacrylate (HDDA), two.
As preferred practical range of the present invention, be to stir 2～20 hours in the step (2) 50～90 ℃ of following shadings, remove light shield then and at room temperature stirred 1～15 day under (20～30 ℃), so that the prepolymerization that oligomer acquires a certain degree in the system; After the black paper bag of spray fiber tube external application was wrapped up in, with the aluminium foil parcel, the spinneret internal diameter was 0.5mm～2.5mm again, and the insertion copper electrode is an anode, receives product with aluminium foil as negative electrode, and distance is 10～55cm between two-plate.(power 30～500W) is apart from spray the Silk Road footpath 2～55cm, and applying voltage is that 10～25KV carries out the electrospinning silk, opens ultraviolet source (lamp) simultaneously and carries out polymerization, after spinning in 5～25 minutes, will obtain transparent micro nanometer fiber on minus plate for uviol lamp.
Mechanism of the present invention can be done following understanding: in spinning process, after the pre-polymer solution that reaches certain pre-polymerization degree leaves and sprays the fiber tube mouth of pipe, the photon energy that light trigger in the jet absorbs ultraviolet source produces living radical, living radical causes prepolymer and carries out cross-linking reaction, and the splitting with fiber in the flight course of jet takes place, thereby forms polymer micro-nanometer fiber.
The no-solvent electrically spinning method of utilizing that this method is successful is in the world first prepared micro nanometer fiber, it is simple that this experimental technique has an experimentation, is convenient to operation and repeats, and do not need complicated process conditions, environmental friendliness has the excellent results of the promotion and application of being easy to.
Description of drawings
Fig. 1: be the embodiment of the invention 1 employed electrospinning silk equipment work schematic diagram;
Fig. 2: be the employed electrospinning silk of embodiment of the invention 2-7 equipment work schematic diagram;
Fig. 3: the polymer nanofiber stereoscan photograph that is obtained for embodiment 1;
Fig. 4: for the polymer microfiber that embodiment 2 is obtained is tieed up stereoscan photograph;
Fig. 5: the polymer nanofiber stereoscan photograph that is obtained for embodiment 3;
Fig. 6: for the polymer microfiber that embodiment 4 is obtained is tieed up stereoscan photograph;
Fig. 7: for the polymer microfiber that embodiment 5 is obtained is tieed up stereoscan photograph;
Fig. 8: for the polymer microfiber that embodiment 6 is obtained is tieed up stereoscan photograph;
Fig. 9: for the polymer microfiber that embodiment 7 is obtained is tieed up stereoscan photograph;
As shown in Figure 1,1 be high voltage source as positive pole, 2 for being surrounded by the glass spray fiber tube of black paper and aluminium foil, 3 spinning solutions for ejecting, 4 is copper rod, 5 are the polymer micro-nanometer fiber of splitting, 6 is that the aluminium foil dash receiver is as negative electrode.7 is the UV-LED spot light.
As shown in Figure 2,1 be high voltage source as positive pole, 2 for being surrounded by the glass spray fiber tube of black paper and aluminium foil, 3 spinning solutions for ejecting, 4 is copper rod, 5 are the polymer micro-nanometer fiber of splitting, 6 is that the aluminium foil dash receiver is as negative electrode.7 is PHILIPS 400W ultraviolet source.
The specific embodiment
Embodiment 1:
In the 20ml conical flask, in 2.19g polyester acrylate (Gencure PEO 2257), add 0.07g light trigger 1-hydroxyl-cyclohexyl benzophenone (Gencure 184), with black paper it is covered to place under the room temperature and stirred following 24 hours.With spinning solution pack into the spray fiber tube in, the internal diameter of spinneret is 1mm, with black paper with behind the spinning head parcel, with aluminium foil it is superscribed again, the insertion copper electrode is an anode, receives product with aluminium foil as negative electrode, and distance is 45cm between two-plate, at distance spinning nozzle 2cm place, a 800mw/cm is placed at the 2cm place apart from spray the Silk Road footpath
2The UV-LED spot light, when applying voltage and be 17kV and carry out the electrospinning silk, open the UV-LED spot light and shine, after 10 minutes, will obtain average length on aluminium foil is that 4.5 μ m, diameter are the staple fibre of 400nm.
Embodiment 2:
In the 20ml conical flask, in 2.19g polyester acrylate (Gencure PEO 2257), add 0.07g light trigger 1-hydroxyl-cyclohexyl benzophenone (Gencure 184), with black paper it is covered, at room temperature stirred following 24 hours.50 ℃ were being heated 2 hours, spinning solution is packed into spray in the fiber tube, and the internal diameter of spinneret is 1mm, after with black paper spinning head being wrapped up, with aluminium foil it were superscribed again, and the insertion copper electrode is an anode.Receive product with aluminium foil as negative electrode, distance is 45cm between two-plate, at distance spinning nozzle 10cm place, a PHILIPS 400W ultraviolet source is placed at the 45cm place apart from spray the Silk Road footpath, applying voltage is 17kV, open PHILIPS 400W ultraviolet source simultaneously, after 10 minutes, will on aluminium foil, obtain the fiber that diameter is 3 μ m.
Embodiment 3:
In the 20ml conical flask, in 2.19g polyester acrylate (Gencure PEO 2257), add 0.07g light trigger 1-hydroxyl-cyclohexyl benzophenone (Gencure 184), with black paper it is covered, at room temperature stirred following 24 hours.50 ℃ after heating 2 hours, at room temperature stir to place after 48h hour, spinning solution is packed in the spray fiber tube, the internal diameter of spinneret is 1mm, after with black paper spinning head being wrapped up, with aluminium foil it is superscribed again, the insertion copper electrode is an anode, receives product with aluminium foil as negative electrode.Distance is 45cm between two-plate, and at distance spinning nozzle 10cm place, a PHILIPS 400W ultraviolet source is placed at the 45cm place apart from spray the Silk Road footpath, applying voltage is 17kV, open PHILIPS 400W ultraviolet source simultaneously, after 10 minutes, will on aluminium foil, obtain the fibre bundle that diameter is about 200nm.
Embodiment 4:
In the 20ml conical flask, in 3.80g urethane acrylate (Gencure PUA910A), add 0.17g light trigger 1-hydroxyl-cyclohexyl benzophenone (Gencure 184) and 1.73g1,6-hexanediyl ester (HDDA) covers it with black paper, at room temperature stirs following 24 hours.50 ℃ heating 2 hours, at room temperature stir to place after 7h hour, and spinning solution is packed in the spray fiber tube, and the internal diameter of spinning head is 1mm, with black paper with the spinning head parcel after, with aluminium foil it is superscribed again, the insertion copper electrode is an anode.Receive product with aluminium foil as negative electrode, distance is 45cm between two-plate, at distance spinning nozzle 10cm place, a PHILIPS 400W ultraviolet source is placed at the 45cm place apart from spray the Silk Road footpath, and applying voltage is 17kV, opens PHILIPS 400W ultraviolet source simultaneously, after 10 minutes, to obtain average diameter on aluminium foil is 20 μ m, and length is the staple fibre of 1mm, and has the drop of many curing to exist.
Embodiment 5:
In the 20ml conical flask, in 3.80g urethane acrylate (Gencure PUA910A), add 0.17g light trigger 1-hydroxyl-cyclohexyl benzophenone (Gencure 184) and 1.73g 1,6-hexanediyl ester (HDDA) covers it with black paper, at room temperature stirs following 24 hours.50 ℃ heating 2 hours, at room temperature stir to place after 9h hour, and spinning solution is packed in the spray fiber tube, and the internal diameter of spinning head is 1mm, with black paper with the spinning head parcel after, with aluminium foil it is superscribed again, the insertion copper electrode is an anode.Receive product with aluminium foil as negative electrode, distance is 45cm between two-plate, and at distance spinning nozzle 10cm place, a PHILIPS 400W ultraviolet source is placed at the 45cm place apart from spray the Silk Road footpath, and applying voltage is 17kV.Cut-in voltage and PHILIPS 400W ultraviolet source after 10 minutes, will obtain diameter 10 μ m on aluminium foil simultaneously, and length is the staple fibre of 400 μ m, and have the drop of many curing to exist.
Embodiment 6:
In the 20ml conical flask, in 4.41g polyester acrylic resin (Gencure SACMAT 268), add 0.1324g light trigger 1-hydroxyl-cyclohexyl benzophenone (Gencure 184), with black paper it is covered, at room temperature stirred following 24 hours.50 ℃ heating 13 hours, at room temperature stir to place after 24h hour, and spinning solution is packed in the spray fiber tube, and the internal diameter of spinning head is 1mm, with black paper with the spinning head parcel after, with aluminium foil it is superscribed again, the insertion copper electrode is an anode.Receive product with aluminium foil as negative electrode.Distance is 45cm between two-plate, and at distance spinning nozzle 10cm place, a PHILIPS 400W ultraviolet source is placed at the 45cm place apart from spray the Silk Road footpath, and applying voltage is 17kV.Cut-in voltage and PHILIPS 400W ultraviolet source after 10 minutes, will get the double helical form micrometer fibers on aluminium foil simultaneously, and its diameter is 5 μ m.
Embodiment 7:
In the 20ml conical flask, in 4.41g polyester acrylic resin (Gencure SACMAT 268), add 0.1324g light trigger 1-hydroxyl-cyclohexyl benzophenone (Gencure 184), with black paper it is covered to place under the room temperature and stirred following 24 hours, see that the light pre-polymerization is after 2 hours, 50 ℃ of heating are after 15 hours, while hot spinning solution is packed into and spray in the fiber tube, the internal diameter of spinning head is 1mm,, with aluminium foil it is superscribed behind the spinning head parcel with black paper, the insertion copper electrode is an anode again, accept product with aluminium foil as negative electrode, distance is 45cm between two-plate, and at distance spinning nozzle 10cm place, a PHILIPS 400W ultraviolet source is placed at the 45cm place apart from spray the Silk Road footpath, when applying voltage and be 17kV and carry out the electrospinning silk, open PHILIPS 400W ultraviolet source and shine, after 10 minutes, will on aluminium foil, obtain the fiber that diameter is 5 μ m.
Claims (7)
1, the no-solvent electrically spinning preparation method of micro nanometer fiber, its step is as follows:
(1) light trigger with 0.05～3g joins 5～15g macromolecule repetitive less than in 10 the oligomer that has the acrylate end group, add 2～12g reactive diluent again, and shading at room temperature stirred 10～30 hours, so that initator dissolves fully;
(2) under 50～90 ℃, continue shading and stirred 2～30 hours, remove light shield then, at room temperature continue to stir 1～20 day, so that oligomer generation pre-polymerization to a certain degree in the reaction system;
(3) the spray fiber tube of gained solution being put into the shading that has spinneret carries out the electrospinning silk, be that the ultraviolet source of 30～500W shines the spray silk that gushes out from spinneret with power in the electrospinning silk process, after 5～30 minutes, on the negative electrode dash receiver, obtain micro nanometer fiber.
2, the no-solvent electrically spinning preparation method of micro nanometer fiber as claimed in claim 1 is characterized in that: the macromolecule repetitive is epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, pure acrylic resin, epoxy resin, aromatic acid acrylic acid half ester, acroleic acid esterification polyacrylic resin, melamine acrylic resin or hexamethylene diisocyanate less than 10 the oligomer that has the acrylate end group.
3, the no-solvent electrically spinning preparation method of micro nanometer fiber as claimed in claim 1; it is characterized in that: light trigger is α; alpha-alpha-dimethyl benzil ketals, α; α-diethoxy acetophenone, 1-hydroxyl-cyclohexyl benzophenone, [2-methyl 1-(the false sulfydryl phenyl of 4-)-2-morpholine-1-acetone] or 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide.
4, the no-solvent electrically spinning preparation method of micro nanometer fiber as claimed in claim 1 is characterized in that: diluent is contract the propylene glycol double methacrylate or the propylene glycol double methacrylate that contracts of 1,6 hexylene glycol double methacrylate, two.
5, the no-solvent electrically spinning preparation method of micro nanometer fiber as claimed in claim 1, it is characterized in that: be to stir 2～20 hours in the step (2) 50～90 ℃ of following shadings, remove light shield then and at room temperature stir 1～15 day, so that the prepolymerization that oligomer acquires a certain degree in the system.
6, the no-solvent electrically spinning preparation method of micro nanometer fiber as claimed in claim 1, it is characterized in that: the internal diameter of spinneret is 0.5mm～3.0mm, spinneret is 10～60cm to the distance between the negative electrode dash receiver, ultraviolet source is 2～60cm apart from the distance in spray the Silk Road footpath, distance apart from spinneret is 2～20cm, and the electrospinning filament voltage is 10～28KV.
7, the no-solvent electrically spinning preparation method of micro nanometer fiber as claimed in claim 6 is characterized in that: the spinneret internal diameter is 0.5mm～2.5mm, and the insertion copper electrode is an anode, receives product with aluminium foil as negative electrode, and distance is 10～55cm between two-plate.Ultraviolet source is apart from spray the Silk Road footpath 2～55cm, and applying voltage is that 10～25KV carries out the electrospinning silk, after 5～25 minutes, obtains transparent micro nanometer fiber on minus plate.
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| CNB2007100553014A CN100526524C (en) | 2007-02-02 | 2007-02-02 | No-solvent electrically spinning process for preparing micron and nanometer fiber |
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| CNB2007100553014A CN100526524C (en) | 2007-02-02 | 2007-02-02 | No-solvent electrically spinning process for preparing micron and nanometer fiber |
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| CN100526524C true CN100526524C (en) | 2009-08-12 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624728B (en) * | 2008-07-07 | 2012-07-04 | 常州市久联蓄电池材料有限公司 | System for electrospinning nanofiber from polymer |
| CN101907593A (en) * | 2010-07-20 | 2010-12-08 | 浙江大学 | Polypyrrole/polyvinylidene fluoride nano fiber composite resistance type film gas-sensitive element and manufacturing method thereof |
| US9725827B2 (en) | 2012-10-02 | 2017-08-08 | Basf Se | Process for producing water-absorbing polymer fibers |
| CN103194820B (en) * | 2013-04-27 | 2014-08-27 | 青岛大学 | Method for preparing micro-nanofiber through solvent curing type electrostatic spinning |
| CN104264265B (en) * | 2014-09-16 | 2016-03-30 | 北京化工大学 | A kind of preparation method of hybrid nanofiber |
| CN104532367B (en) * | 2014-12-19 | 2016-08-24 | 青岛大学 | A kind of method that solvent-free electrostatic spinning prepares polyurethane micro nanometer fiber |
| CN105220244B (en) * | 2015-08-25 | 2018-04-17 | 青岛大学 | A kind of method of the standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning |
| CN105088367B (en) * | 2015-08-25 | 2017-12-22 | 青岛大学 | A kind of solvent-free electrostatic spinning apparatus based on UV solidifications |
| CN105506768B (en) * | 2015-11-27 | 2017-11-24 | 青岛大学 | A kind of colored micro nanometer fiber twisted wire of UV solidifications electrospinning and preparation 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 |
| CN111197184B (en) * | 2020-01-17 | 2022-04-05 | 西安交通大学 | Electrostatic spinning device |
| CN113215677A (en) * | 2021-04-21 | 2021-08-06 | 游革新 | Spandex prepared by melt spinning and method thereof |
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| EP1283283B1 (en) * | 2001-07-30 | 2005-06-01 | helsa-automotive GmbH & Co. KG | Process for the production of a fibre product |
| WO2006018026A1 (en) * | 2004-08-19 | 2006-02-23 | Coloplast A/S | Absorbent fiber material and use thereof in wound dressings |
| CN1843592A (en) * | 2006-03-22 | 2006-10-11 | 浙江大学 | Method for preparing nanometer fibrous film of glycosylated acrylon and application thereof |
| CN1880526A (en) * | 2005-06-13 | 2006-12-20 | 中国科学院化学研究所 | Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof |
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2007
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1283283B1 (en) * | 2001-07-30 | 2005-06-01 | helsa-automotive GmbH & Co. KG | Process for the production of a fibre product |
| WO2006018026A1 (en) * | 2004-08-19 | 2006-02-23 | Coloplast A/S | Absorbent fiber material and use thereof in wound dressings |
| CN1880526A (en) * | 2005-06-13 | 2006-12-20 | 中国科学院化学研究所 | Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof |
| CN1843592A (en) * | 2006-03-22 | 2006-10-11 | 浙江大学 | Method for preparing nanometer fibrous film of glycosylated acrylon and application thereof |
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