CN103911766A - Trans-rubber fiber material, preparation method and applications thereof - Google Patents
Trans-rubber fiber material, preparation method and applications thereof Download PDFInfo
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- CN103911766A CN103911766A CN201310021197.2A CN201310021197A CN103911766A CN 103911766 A CN103911766 A CN 103911766A CN 201310021197 A CN201310021197 A CN 201310021197A CN 103911766 A CN103911766 A CN 103911766A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 50
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- 239000000835 fiber Substances 0.000 claims abstract description 73
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- 238000009987 spinning Methods 0.000 claims description 94
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- 238000010041 electrostatic spinning Methods 0.000 claims description 14
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
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- 238000001291 vacuum drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001523 electrospinning Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
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- 230000005855 radiation Effects 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
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- 229920003194 trans-1,4-polybutadiene polymer Polymers 0.000 abstract 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
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- 229910000881 Cu alloy Inorganic materials 0.000 description 1
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- 229920000459 Nitrile rubber Polymers 0.000 description 1
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Landscapes
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a trans-rubber fiber material. The trans-rubber is selected from one or more of trans-1, 4-polyisoprene, trans-1, 4-polybutadiene, trans-1, 4-butadiene-isoprene copolymerization rubber, trans-1, 4-butadiene-piperylene copolymerization rubber, trans-1, 4-polydiolefin rubber alloy and trans-1, 4-alkadiene homopolymer and/or homopolymer epoxidation or chlorination modified derivatives and derivatives. The diameter of the trans-rubber is in a range of 100nm to 10 microns. The invention further provides a preparation method and applications of the trans-rubber fiber material. The trans-rubber fiber material has the advantages of being fine in diameter, low in weight, large in specific surface area, large in porosity, small in mass-to-volume ratio, capable of maintaining good fiber morphology after being put for a period and free of fiber dissolving and deformation of other fibers in the prior art.
Description
Technical field
The invention belongs to fibrous material field, be specifically related to a kind of trans IR fiber material, Preparation Method And The Use.
Background technology
Trans rubber comprises anti-form-1,4-polyisoprene, anti-form-1,4-polybutadiene, anti-form-1,4-butadiene-isoprene copolymer glue, anti-form-1,4-butadiene-pentadiene copolymer rubber, anti-form-1,4-polydiene rubber alloy etc.Trans rubber and cis-rubber have identical chemical composition, but molecular chain configuration is completely contradicted.The group of cis-rubber is at the homonymy of two key key axles, and strand is random coil shape, and therefore cis-rubber shows as soft elastomer at normal temperatures, is widely used in tire industry; The group of trans rubber is at the heteropleural of two key key axles, and strand is orderly folded chain, the easy crystallization of homopolymers.Current trans rubber can be used as the medical function materials such as artificial limb cover, sports safety rehabilitation protector and brace, also can be used as thermostimulation shape-memory material, as shape tube joint, temperature detect switch (TDS), Multi-core cable joint etc.In addition, trans rubber not only ABRASION RESISTANCE is outstanding, its resistance to tearing, cryogenic property, and the performance such as adherence and green strength is also very outstanding, is therefore applicable to do tyre stock, resistance to rolling and the compression heat generation that can effectively reduce tire, significantly improve fatigue performance.Specific position according to trans rubber in material spectrum, also has many useful performances and purposes to have to be developed, and its development prospect is very wide beyond doubt.
Electrostatic spinning is to prepare at present nanofiber simple effective method the most, and its fibre diameter making can be between the μ m of 10nm～1000.The principle of electrostatic spinning is first to apply high-pressure electrostatic to polymer fluid, charged polymer liquid drops in and under the effect of electric field force, overcomes surface tension and form and spray thread, spray thread and form the unstable volatilization of flowing and being accompanied by solvent of various ways aloft, finally drop on the receiving system of ground connection and form polymer fiber.The fiber making with respect to conventional method, electrospinning fibre has great specific area and surface-to-volume ratio, is particularly suitable as tissue engineering material and uses, and has wide practical use at aspects such as filter membrane, hypersensitization sensor, intelligent clothings simultaneously.
In more than ten years in the past, electrostatic spinning becomes with advantages such as its simple general-purpose the representative technology of preparing nano-fiber material.Up to the present, existingly exceed 200 kinds of macromolecular materials and make fiber product by electrostatic spinning.U.S. Pat 20030215624 and US20040013873 provide the electrospinning fibre of multiple polymers, comprising: polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polysulfones, Merlon, polyurethane, polymethyl methacrylate, polyvinyl chloride, polyamide, polyvinylpyrrolidone etc.Chinese patent CN200710043808.8 provides a kind of method and application thereof that utilizes electrostatic spinning to prepare ethylene propylene diene rubber nanofiber.Chinese patent CN200910079247.6 provides a kind of preparation method of rubber nano fibre, they adopt coaxial electrostatic spinning method, having prepared rubber is sandwich layer, the nanofiber that water-soluble polymer is shell, and selected rubber is butadiene rubber, butyl rubber, silicon rubber and acrylonitrile-butadiene rubber.Document [Macromol.Mater.Eng.2010,295:305-309] has been reported the electrospinning fibre of cis-Isosorbide-5-Nitrae-polyisoprene, has prepared the fiber of two kinds of patterns, and wherein a kind of surface is Bamboo-shaped, and diameter 20～60 μ m, may be used for microelectronic; Another kind of smooth surface, diameter 5～8 μ m.
Although multiple polymers has been made fibrous material by electrospinning at present, the electrostatic spinning of trans rubber there is not yet relevant report.The performance characteristics of trans rubber uniqueness combine with electrostatic spinning technique preparation nanofiber tool diameter thin; the advantages such as quality is light, and specific area is large, and porosity is large, mass volume ratio is little; in the future at medical tissue engineering scaffold material; wound clad material, medicament transport releasable material, isolated by filtration material; catalysis support materials; insulation blocking material, radiation proof material, the fields such as clothes material have a wide range of applications.
Summary of the invention
One of object of the present invention is to provide a kind of trans IR fiber material, described trans rubber is selected from anti-form-1,4-polyisoprene, anti-form-1,4-polybutadiene, anti-form-1,4-butadiene-isoprene copolymer glue, anti-form-1,4-butadiene-pentadiene copolymer rubber, anti-form-1,4-polydiene rubber alloy, anti-form-1, one or more in the epoxidation of 4-diene homopolymers and/or copolymer or chlorination modified derivative and derivative thereof, wherein said alkadienes is preferably the anti-form-1 of C4-C5,4-alkadienes.
The weight average molecular weight of described trans rubber is 10,000～2,000,000, is preferably 10,000-500,000, more preferably 20,000-200,000, most preferably 50,000-100,000, and trans Isosorbide-5-Nitrae structure molar fraction content is greater than 80%.
Preferably, the diameter of described trans IR fiber is at 100nm～10 μ m, preferably 100nm～2000nm, more preferably 300nm～2000nm, most preferably 500nm～1000nm.
Preferably, in described trans IR fiber material, the arrangement of fiber can be lack of alignment, unidirectional array, cross arrangement, curling unordered, curling unidirectional array, curling cross arrangement or the collection of filaments.
Preferably, the fiber in described trans IR fiber material can be the fiber that smooth fiber, beading fiber, satin ribbon-like fibre, branched fiber, nucleocapsid shape fiber, hollow form fiber or surface contains hole.
Two of object of the present invention is to provide a kind of preparation method of described trans IR fiber material, said method comprising the steps of:
(1) preparation of spinning solution: trans rubber powder is dissolved in solvent at 20～60 ℃, and being mixed with concentration is the polymer solution of the homogeneous transparent of 0.1～20.0w/v% (g/mL), is cooled to room temperature stand-by;
(2) electrostatic spinning: the spinning solution preparing is packed in the device for storing liquid of electrospinning device, the piston of device for storing liquid is connected with charging gear, the spinning head of device for storing liquid connects the positive pole of high voltage source, carries out under the following conditions spinning and obtains trans IR fiber or tunica fibrosa: voltage is 10～60kV; The feeding rate of solution is 10～200 μ L/min; Distance between the spinning head of device for storing liquid and the receiving system of ground connection is 5～50cm; The temperature of spinning environment is 10～60 ℃; The humidity of spinning environment is 10%～80%;
(3) the trans IR fiber or the tunica fibrosa that step (2) are obtained are put into vacuum drying oven vacuumize, 20～40 ℃ of baking temperatures, and drying time, 24～48h, obtained trans IR fiber material.
In step (1), depending on the dissolubility to different rubber, solvent for use can be for being selected from one or more in alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, the halogenated hydrocarbons such as carrene, chloroform, carbon tetrachloride, acetone, normal heptane, cyclohexane, oxolane, benzene,toluene,xylene, ethyl acetate, DMF.
In step (2), spinning condition is preferably as follows: voltage is 15～40kV; The feeding rate of solution is 40～100 μ L/min; Distance between the spinning head of device for storing liquid and the receiving system of ground connection is 10～20cm; Spinning environment temperature is 25～35 ℃; Spinning ambient humidity is 20%～40%.
In step (2), if the fiber of preparation lack of alignment, receiving system can adopt metal plate; If the fiber of preparation unidirectional array, receiving system can adopt swing roller, rotating frame, rotating circular disk, parallel annulus or parallel flat; If the fiber of preparation cross arrangement, receiving system can adopt multipair parallel flat; If the preparation collection of filaments, receiving system can adopt swing roller and before swing roller, place ground connection syringe needle and collect.
In step (2), if prepare uniform fabric nonwoven cloth or film, the Appropriate of swing roller rotating speed is 50～100r/min, and the Appropriate of spinning head translational speed is 200～300mm/min, and nonwoven fabric or tunica fibrosa thickness can be adjusted voluntarily according to the spinning time.
Described trans rubber solutions electrostatic spinning process equipment used comprises: high voltage source, charging pump, spinning head, gathering-device, environment temperature control appliance etc.High voltage source generally can adopt positive negative dc high voltage output source, and the maximum voltage of output is at 40～60kV; The way of output of charging pump can adopt the rear pump feed of multiple output frequency, and general maximum output area is below 300 μ L/min; The good conductors such as spinning head material selection stainless steel, copper or iron-nickel alloy, spinnerette diameters is below 1mm, can also need to adopt according to output the mode of a single spraying spinning or many shower nozzles distribution spinning, the parallel distribution of spinning head is generally selected in the spinning of many shower nozzles, can 1～5 row's spinning head, single spinning head quantity is generally below 20, and between adjacent spinning head, distance is 1～5cm; Gathering-device can for the direct collection of aluminium foil or stainless steel, copper, iron-nickel alloy etc., good conductor be wiry is arranged in parallel or the netted collection of cross arrangement, gathering-device part can adopt the various forms of collectors such as rotating circular disk, flat board, cylinder, also can adopt as required to the poor solvent of selected system the liquid collection mode as collection system; Electrospun ambient temperature control device can adopt infrared lamp mode of heating, Resistant heating mode, recirculated hot air mode of heating, and general maximum heating temperature is not higher than 60 ℃, and system is that PID controls, and general control precision is within the scope of ± 3 ℃.
In electrostatic spinning process, thickness and the uniformity etc. of the stability of all effect of multiple parameters electrostatic spinning processes, continuity, fiber, the molecular weight of for example rubber, solution concentration, solvent volatility, voltage swing, solution feed speed, fiber receiving range, spinning environment temperature, humidity, spinning ambient air speed, the translational speed of spinning head, rotating speed or the translational speed etc. of collector.The present invention is by regulating the parameter (solution concentration, spinning voltage, solution feed speed, fiber receiving range etc.) of electrostatic spinning can effectively control the diameter of gained fiber.
Three of object of the present invention is to provide a kind of described trans IR fiber material for medical tissue engineering scaffold material, wound clad material, medicament transport releasable material; isolated by filtration material; catalysis support materials, insulation blocking material, the purposes of radiation proof material or clothes material.
Four of object of the present invention is to provide the purposes of a kind of described trans rubber for the preparation of fibrous material.Preferably, the weight average molecular weight of described trans rubber is 10,000～2,000,000, and trans Isosorbide-5-Nitrae structure molar fraction content is greater than 80%, and more preferably, the diameter of described fiber is 100nm～10 μ m.
The present invention provides the fibrous material of trans rubber first, has filled up the domestic and international blank without this product, and has increased new varieties for fiber-like product.The present invention provides the preparation method of trans IR fiber material simultaneously, prepares device therefor with low cost, easy and simple to handle, controllability, reproducible, and moulding process is short, multiple programs such as can save spinning, warping, weave.
It is thin that trans IR fiber material of the present invention has diameter, the advantages such as quality is light, and specific area is large, and porosity is large, mass volume ratio is little etc., and after parking a period of time, still can keep good fiber pattern, the phenomenon of and distortion molten without fiber that in prior art, other fibers occur.
Above advantage shows that the present invention is a new technology that can produce great economic benefit and have wide DEVELOPMENT PROSPECT.
Accompanying drawing explanation
Fig. 1 is the device for spinning schematic diagram of the embodiment of the present invention 1.
1. single spinning head 4. high voltage source 5. polymeric spray of charging gear 2. device for storing liquid 3. flow 6. board joint receiving apparatus 7. earth leads
Fig. 2 is the trans IR fiber material SEM figure of the embodiment of the present invention 1.
Fig. 3 is the device for spinning schematic diagram of the embodiment of the present invention 2.
1. charging gear 2. device for storing liquid spinning head more than 3. 4. high voltage source 5. polymeric spray flow 6. framework receiving system 7. earth leads
Fig. 4 is the trans IR fiber material SEM figure of the embodiment of the present invention 2.
Fig. 5 is the device for spinning schematic diagram of the embodiment of the present invention 3.
1. charging gear 2. device for storing liquid spinning head more than 3. 4. high voltage source 5. polymeric spray flow 6. cylinder receiving system 7. earth leads
Fig. 6 is the trans IR fiber material SEM figure of the embodiment of the present invention 3.
Fig. 7 is the trans IR fiber material SEM figure of the embodiment of the present invention 4.
Fig. 8 is the trans IR fiber material SEM figure of the embodiment of the present invention 5.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
In the present invention, trans IR fiber material adopts Beijing DFS-01 of Kai Weixin Science and Technology Ltd. type Electrospun experimental facilities preparation; Fiber pattern is by Japanese JSM-7500F field emission microscopy observation; The structure of trans rubber is by German Bruker-Vertex70 type total digitalization FT-IR spectrometer and Switzerland BrukerFTPAC280 type nuclear magnetic resonance analyser characterized.
Except specified otherwise, the method and apparatus that the present invention adopts is the method and apparatus of this area routine.
Embodiment 1
(1) compound concentration is the anti-form-1 of 3.0w/v% (g/mL), 4-polyisoprene (relative molecular mass 80000g/mol, trans Isosorbide-5-Nitrae structure molar fraction is greater than 98%) solution 25mL.What wherein bathe that agent selects is chloroform.The solution preparing is stirred 24 hours in 45 ℃ of waters bath with thermostatic control, be uniformly dissolved, transparent solution, be cooled to room temperature stand-by.
(2) Fig. 1 is shown in by spinning equipment schematic diagram.Get the about 5mL of above-mentioned rubber solutions, pack in device for storing liquid, deaeration, connects spinning head (internal diameter 0.5mm), spinning head is connected to the positive pole of high voltage source.Adopt the ground connection aluminium sheet of 5cm × 15cm as receiving system, on aluminium sheet, cover the convenient fiber that receives of aluminium foil.Regulating the distance between spinning head and gathering-device is 15cm, and the environment temperature of spinning is 25 ℃, and the air velocity in environment is controlled at 0.5～0.8m
3/ hr.
(3) open high voltage source, regulation voltage is to 15kV, open charging gear, the delivery rate of controlling solution is 40 μ L/min, the drop at spinning head place overcomes surface tension and forms charged injection stream under electric field force effect, injection stream forms the unstable volatilization of flowing and being accompanied by solvent of various ways aloft, finally drops on and on receiving system, forms fiber.After continuous spinning 1h, stop charging gear and disconnect high voltage source, spinning finishes.
(4) polymer fiber on gathering-device is placed in to 30 ℃ of dry 48h of vacuum drying chamber.Gained fibrous material is lack of alignment, and fiber surface is smooth, and average fibre diameter is 500nm (seeing Fig. 2).
Embodiment 2
(1) compound concentration is the anti-form-1 of 5.0w/v% (g/mL), 4-polybutadiene (relative molecular mass 70000g/mol, trans Isosorbide-5-Nitrae structure molar fraction is greater than 95%) solution 250mL.What wherein solvent was selected is the mixed solvent that toluene and DMF volume ratio are 9: 1.The solution preparing is stirred 30 hours in 40 ℃ of waters bath with thermostatic control, be uniformly dissolved, transparent solution, be cooled to room temperature stand-by.
(2) Fig. 3 is shown in by spinning equipment schematic diagram.Select many spinning head apparatus, spinning head number is 3, gets respectively the about 5mL of above-mentioned rubber solutions, packs in device for storing liquid separately, and deaeration connects spinning head (internal diameter 0.5mm) simultaneously, spinning head is connected to the positive pole of high voltage source.Employing diameter is 10cm, and the ground connection rotating frame of long 20cm is as receiving system, and framework adopts parallel copper wire, and copper wire spacing is 7.5mm.Regulating the distance between spinning head and gathering-device is 20cm, and the environment temperature of spinning is 20 ℃, and the air velocity in environment is controlled at 0.5～1.0m
3/ hr.
(3) open high voltage source, regulation voltage, to 20kV, is opened charging gear, and the delivery rate of controlling solution is 50 μ L/min, and regulating the rotating speed of rotating frame is 50r/min, and the reciprocal point-to-point speed of spinning head is 200mm/min.The drop at spinning head place overcomes surface tension and forms charged injection stream under electric field force effect, and injection stream forms the unstable volatilization of flowing and being accompanied by solvent of various ways aloft, finally drops on and on receiving system, forms fiber.After continuous spinning 20h, stop charging gear and disconnect high voltage source, spinning finishes.
(4) the polymer fiber film on gathering-device is placed in to 40 ℃ of dry 48h of vacuum drying chamber.Gained fibrous material is curling unidirectional array, and fiber surface is smooth, and average fibre diameter is 1000nm (seeing Fig. 4).
Embodiment 3
(1) compound concentration is the anti-form-1 of 10.0w/v% (g/mL), 4-butadiene-isoprene copolymer glue (relative molecular mass 70000g/mol, trans Isosorbide-5-Nitrae structure molar fraction is greater than 90%) solution 300mL.The mixed solvent that what wherein solvent was selected is chloroform, toluene, DMF volume ratio are 8: 1: 1.The solution preparing is stirred to 24h in 50 ℃ of waters bath with thermostatic control, be uniformly dissolved, transparent solution, be cooled to room temperature stand-by.
(2) Fig. 5 is shown in by spinning equipment schematic diagram.Select many spinning head apparatus, spinning head number is 5, gets respectively the about 10mL of above-mentioned rubber solutions, packs in device for storing liquid separately, and deaeration connects spinning head (internal diameter 0.5mm) simultaneously, spinning head is connected to the positive pole of high voltage source.Employing diameter is 10cm, and the ground connection swing roller of long 20cm, as receiving system, covers the convenient fiber that receives of aluminium foil on cylinder.Regulating the distance between spinning head and gathering-device is 18cm, and the environment temperature of spinning is 22 ℃, and the air velocity in environment is controlled at 0.5～0.8m
3/ hr.
(3) open high voltage source, regulation voltage, to 22kV, is opened charging gear, and the delivery rate of controlling solution is 53 μ L/min, and regulating the rotating speed of swing roller is 80r/min, and the reciprocal point-to-point speed of spinning head is 150mm/min.The drop at spinning head place overcomes surface tension and forms charged injection stream under electric field force effect, and injection stream forms the unstable volatilization of flowing and being accompanied by solvent of various ways aloft, finally drops on and on receiving system, forms fiber.After continuous spinning 15h, stop charging gear and disconnect high voltage source, spinning finishes.
(4) polymer fiber on gathering-device is placed in to 45 ℃ of dry 40h of vacuum drying chamber.Gained fibrous material is cross arrangement, and fiber is ribbon shape, and average fibre diameter is 800nm (seeing Fig. 6).
Embodiment 4
(1) compound concentration is the chlorination anti-form-1 of 0.5w/v% (g/mL), 4-polyisoprene (relative molecular mass 90000g/mol, chlorinity 20%) solution 50mL.The mixed solvent that what wherein solvent was selected is chloroform, acetone, DMF volume ratio are 7: 2: 1.The solution preparing is stirred to 40h in 45 ℃ of waters bath with thermostatic control, be uniformly dissolved, transparent solution, be cooled to room temperature stand-by.
(2) spinning equipment is with embodiment 1.Get the about 10mL of above-mentioned rubber solutions, pack in device for storing liquid, deaeration, connects spinning head (internal diameter 0.5mm), spinning head is connected to the positive pole of high voltage source.Adopt the ground connection aluminium sheet of 5cm × 15cm as receiving system, on aluminium sheet, cover the convenient fiber that receives of aluminium foil.Regulating the distance between spinning head and gathering-device is 12cm, and the environment temperature of spinning is 40 ℃, and the air velocity in environment is controlled at 0.5～0.8m
3/ hr.
(3) open high voltage source, regulation voltage is to 28kV, open charging gear, the delivery rate of controlling solution is 60 μ L/min, the drop at spinning head place overcomes surface tension and forms charged injection stream under electric field force effect, injection stream forms the unstable volatilization of flowing and being accompanied by solvent of various ways aloft, finally drops on and on receiving system, forms fiber.After continuous spinning 20min, stop charging gear and disconnect high voltage source, spinning finishes.
(4) the polymer fiber film on gathering-device is placed in to 35 ℃ of dry 40h of vacuum drying chamber.Gained fibrous material is lack of alignment, and fiber is containing bead structure, and average fibre diameter is 300nm (seeing Fig. 7).
Embodiment 5
(1) compound concentration is epoxidation trans-Isosorbide-5-Nitrae-polyisoprene (relative molecular mass 100000g/mol, epoxy content 15%) solution 100mL of 1.0w/v% (g/mL).The mixed solvent that what wherein solvent was selected is ethyl acetate, chloroform, DMF volume ratio are 6: 3: 1.The solution preparing is stirred to 40h in 40 ℃ of waters bath with thermostatic control, be uniformly dissolved, transparent solution, be cooled to room temperature stand-by.
(2) spinning equipment is with embodiment 3, but slightly improves, at the fine needle of accepting to establish before cylinder a ground connection.Select single spinning head apparatus, get respectively the about 10mL of above-mentioned rubber solutions, pack in device for storing liquid, deaeration connects spinning head (internal diameter 0.5mm) simultaneously, spinning head is connected to the positive pole of high voltage source.Employing diameter is 10cm, and the ground connection swing roller of long 20cm, as receiving system, covers the convenient fiber that receives of aluminium foil on cylinder.Regulating the distance between spinning head and gathering-device is 30cm, and the environment temperature of spinning is 35 ℃, and the air velocity in environment is controlled at 0.5～0.8m
3/ hr.
(3) open high voltage source, regulation voltage, to 27kV, is opened charging gear, and the delivery rate of controlling solution is 30 μ L/min, and regulating the rotating speed of swing roller is 100r/min, and the reciprocal point-to-point speed of spinning head is 100mm/min.The drop at spinning head place overcomes surface tension and forms charged injection stream under electric field force effect, injection stream forms the unstable volatilization of flowing and being accompanied by solvent of various ways aloft, can there is self-boundling to ground connection syringe needle place flying in jet, form fibre bundle, drawn to cylinder and collect.After continuous spinning 1.5h, stop charging gear and disconnect high voltage source, spinning finishes.
(4) polymer fiber on gathering-device is placed in to 45 ℃ of dry 40h of vacuum drying chamber.Gained fibrous material is the collection of filaments, and fiber surface is smooth, and average fibre diameter is 800nm (seeing Fig. 8).
The embodiment of the present invention 1～embodiment 5 spinning processes are continuous, and the fibre diameter obtaining is hundreds of nanometer to several microns, still can keep good fiber pattern after parking a period of time, the phenomenon of and distortion molten without fiber that in prior art, other fibers occur.
Claims (10)
1. a trans IR fiber material, wherein, described trans rubber is for being selected from anti-form-1,4-polyisoprene, anti-form-1,4-polybutadiene, anti-form-1,4-butadiene-isoprene copolymer glue, anti-form-1,4-butadiene-pentadiene copolymer rubber, anti-form-1,4-polydiene rubber alloy, anti-form-1, one or more in the epoxidation of 4-diene homopolymers and/or copolymer or chlorination modified derivative and derivative thereof.
2. trans IR fiber material according to claim 1, wherein, the weight average molecular weight of described trans rubber is 10,000～2,000,000, trans Isosorbide-5-Nitrae structure molar fraction content is greater than 80%.
3. trans IR fiber material according to claim 1, wherein, the diameter of described trans IR fiber is 100nm～10 μ m.
4. according to the trans IR fiber material one of claims 1 to 3 Suo Shu, wherein, in described trans IR fiber material fiber be arranged as lack of alignment, unidirectional array, cross arrangement, curling unordered, curling unidirectional array, curling cross arrangement or the collection of filaments.
5. according to the trans IR fiber material one of claims 1 to 3 Suo Shu, wherein, the fiber in described trans IR fiber material is the fiber that smooth fiber, beading fiber, satin ribbon-like fibre, branched fiber, nucleocapsid shape fiber, hollow form fiber or surface contains hole.
6. the preparation method of the trans IR fiber material described in one of claim 1 to 5, said method comprising the steps of:
(1) preparation of spinning solution: trans rubber powder is dissolved in solvent at 20～60 ℃, is mixed with the polymer solution that concentration is the homogeneous transparent of 0.1～20.0g/mL, be cooled to room temperature stand-by;
(2) electrostatic spinning: the spinning solution preparing is packed in the device for storing liquid of electrospinning device, the piston of device for storing liquid is connected with charging gear, the spinning head of device for storing liquid connects the positive pole of high voltage source, carries out under the following conditions spinning and obtains trans IR fiber or tunica fibrosa: voltage is 10～60kV; The feeding rate of solution is 10～200 μ L/min; Distance between the spinning head of device for storing liquid and the receiving system of ground connection is 5～50cm; The temperature of spinning environment is 10～60 ℃; The humidity of spinning environment is 10%～80%;
(3) the trans IR fiber or the tunica fibrosa that step (2) are obtained are put into vacuum drying oven vacuumize, 20～40 ℃ of baking temperatures, and drying time, 24～48h, obtained trans IR fiber material.
7. method according to claim 6, wherein, in step (1), solvent for use is to be selected from one or more in carrene, chloroform, carbon tetrachloride, acetone, normal heptane, cyclohexane, oxolane, benzene,toluene,xylene, ethyl acetate, DMF.
8. according to the method described in claim 6 or 7, wherein, in step (2), spinning condition is as follows: voltage is 15～40kV; The feeding rate of solution is 40～100 μ L/min; Distance between the spinning head of device for storing liquid and the receiving system of ground connection is 10～20cm; Spinning environment temperature is 25～35 ℃; Spinning ambient humidity is 20%～40%; And preferably,, in step (2), if the fiber of preparation lack of alignment, receiving system adopts metal plate; If the fiber of preparation unidirectional array, receiving system adopts swing roller, rotating frame, rotating circular disk, parallel annulus or parallel flat; If the fiber of preparation cross arrangement, receiving system adopts multipair parallel flat; If the preparation collection of filaments, receiving system adopts swing roller and before swing roller, places ground connection syringe needle and collect; If prepare uniform fabric nonwoven cloth or film, swing roller rotating speed is 50～100r/min, and spinning head translational speed is 200～300mm/min.
9. the described trans IR fiber material of one of claim 1 to 5 is used for medical tissue engineering scaffold material, wound clad material, medicament transport releasable material; isolated by filtration material; catalysis support materials, insulation blocking material, the purposes of radiation proof material or dress materials.
10. trans rubber claimed in claim 1 is for the preparation of the purposes of fibrous material, and preferably, the weight average molecular weight of described trans rubber is 10,000～2,000,000, trans 1,4 structure molar fraction content are greater than 80%, and more preferably, the diameter of described fiber is 100nm～10 μ m.
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Application publication date: 20140709 |