CN101498057A - Preparation of rubber nano fibre - Google Patents
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- CN101498057A CN101498057A CNA2009100792476A CN200910079247A CN101498057A CN 101498057 A CN101498057 A CN 101498057A CN A2009100792476 A CNA2009100792476 A CN A2009100792476A CN 200910079247 A CN200910079247 A CN 200910079247A CN 101498057 A CN101498057 A CN 101498057A
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Abstract
The invention relates to a method of preparing rubber nanometer fibers. The method adopts a coaxial electrostatic spinning method which uses a rubber as a sandwich layer solution and a water-soluble polymer solution as a casing solution, exerts high-pressure static electricity and then carries out coaxial electrostatic spinning. The preparation method is simple, has good spinning continuity and stability and stable figures of the prepared rubber fibers and is widely applicable to the fields of biomedicine, antibacterium, sterilization, toughened plastics, and the like.
Description
Technical field:
The present invention relates to a kind of preparing rubber nanometer fibers.Prepared rubber nano fibre can be used for fields such as biomedicine, antibiotic and sterilizing, toughened plastics.
Background technology:
Electrostatic spinning technique is realized in 1934 by Formhals etc. the earliest.(make an appointment with the nineteen ninety-five front and back) particularly recently for over ten years the eighties from eighties of last century, be subjected to the promotion of Nano-technology Development upsurge, static spins again and receives publicity, utilize this technology, be easy to many Polymer Processing are become the superfine fibre of different fibre structures, different scale (sub-micron is to nanometer).
The polymer nanofiber that utilizes electrostatic spinning technique successfully to prepare comprises polyamide (PA6, PA66), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), PLA (PLA), cellulose acetate (CA), polyurethane (PU), polycaprolactone many polymeric matrixs such as (PCL).Chinese patent " a kind of preparation method of affinity vinyl cyanide base co-polymer superfine fibre film and application " (publication number CN101185851) is dissolved in acrylonitrile copolymer in the solvent, carry out electrostatic spinning, prepare a kind of affinity vinyl cyanide co-polymer superfine fibre film, fibre diameter is 80-800nm.United States Patent (USP) " Electrospunelectroactive polymers " (publication number 20060057377) will have the polymer of polar group, be dissolved in the solvent as polyamide, polyurethane, polyacrylic acid etc., carry out electrostatic spinning, prepared the polymer nanofiber with conduction activity, fibre diameter is 10-10000nm.On utilize method of electrostatic spinning to prepare at present polymer nanofiber-based is the polymeric matrix that normal temperature is in glassy state or crystalline state, because the big molecule of these polymer is under electrostatic induction by super drawing and after ejecting fiber, can change glassy state or crystalline state again into rapidly in the quick volatilization process of solvent or in the fast cooling cooling procedure and be fixed up, fiber is indeformable, controls the continuity and the stability of spinning process easily.Yet, be in the polymer of elastomeric state for normal temperature, prepare preparing rubber nanometer fibers as electrostatic spinning, document or patent report are seldom arranged.Main cause is that rubber macromolecule conformation number is many, and glass transition temperature is below 0 ℃, non-crystallizable under the normal temperature, have high elasticity, the mobility of macromolecular chain is strong, and strand is short slack time, 3 problems are difficult to solve when causing the electrospinning silk: (1) is in spray silk process, when solvent volatilized fast, fiber was replied fast because of the high elastic deformation of rubber molecule, and disturbance takes place near spinning nozzle, be difficult to the continuity and the stability of control spinning, fiber surface also has beading often; (2) IR fiber of high elongation is replied fast because of high elastic deformation, causes single fiber discontinuous, even ruptures; (3) the difficult control that distributes of fibre diameter thick (more than the 1 μ m), diameter; (4) the most formidable is that the uncrosslinked IR fiber that is in elastomeric state shape under the gravity effect changes very soon, easily melts also in fiber lap-joint especially, causes fiber to be piled up together and may form film, is difficult to keep the pattern of fiber.Document [Polymeric Nanofibers, American Chemical Society, Washington, DC, 2005] reported the electrostatic spinning of carbon black filled butyl rubber solution, found that the spinnability of butyl rubber solution increases along with carbon black loading increases, fibre diameter reduces, and DIMENSIONAL STABILITY increases.But, the diameter major part of butyl rubber fiber about several microns, and because not crosslinked rapidly, permelting and film forming.
Summary of the invention
The object of the present invention is to provide a kind of preparing rubber nanometer fibers.Adopting the coaxial electrostatic spinning method, is sandwich layer solution with the rubber solutions that contains unsaturated carbon-carbon double bond, and water-soluble polymer solution is a shell solution, applies to carry out coaxial electrostatic spinning behind the high-pressure electrostatic and make.Rubber solutions adds inorganic salts electrolyte and nano silicon, improves the static spinnability of rubber solutions; The spatial constraints of outer layer copolymer fiber delays fibre deformation to reduce the elastic recovery distortion of rubber molecule during simultaneously by coaxial electrostatic spinning; Before the electrostatic spinning, in rubber solutions, add proper amount of cross-linking agent, when static spins that the fiber original position is crosslinked fast, make rubber molecule form the three-dimensional crosslinked network structure fast, the pattern of stable fibers, solve static and spin high elastic rubber and be difficult to that serialization and stabilisation, fibre diameter are thick, the difficult problem of shape stability difference, prepare crosslinked rubber nano fibre.
A kind of preparing rubber nanometer fibers provided by the invention, adopting the coaxial electrostatic spinning method, is sandwich layer solution with the rubber solutions, and water-soluble polymer solution is a shell solution, apply and carry out coaxial electrostatic spinning behind the high-pressure electrostatic and make, concrete preparation condition and step are as follows:
(1) will contain the rubber, inorganic salts electrolyte dissolution of unsaturated carbon-carbon double bond in room temperature effumability organic solvent, adding modification reinforcer stirs and is mixed with rubber solutions, the mass percentage concentration of rubber solutions is 5%-20%, and the mass ratio of rubber, inorganic salts electrolyte and modification reinforcer is 100:0.5-25:5-30; Before static spins, in rubber solutions, add the crosslinking agent of 0.5-10 parts by mass;
(2) the water-soluble polymer dissolution that room temperature is glassy state or crystalline state is stirred to dissolving fully in organic solvent, and making mass percentage concentration is the shell solution of 5%-20%;
(3) setting spinning head and dash receiver distance is 8-25cm, and the flow velocity of adjusting sandwich layer solution is 0.5-2.0ml/h, and spinnerette diameters is 0.5～1.0mm, and the flow velocity of shell solution is 0.5-3.0ml/h, and spinnerette diameters is 1.0～1.5mm; After treating stable the outflow, applying electrostatic potential is 10-30kV, coaxial electrostatic spinning (shown in Fig. 1 device), collection obtains rubber/water-soluble polymer composite nano fiber, treat that rubber phase in the composite fibre is after original position under 20～50 ℃ the lower temperature is fast crosslinked, the use deionized water dissolving is removed the water-soluble polymer skin in the composite fibre, obtains rubber nano fibre after the drying at room temperature.
The described rubber that contains unsaturated carbon-carbon double bond can be selected butadiene rubber, butyl rubber, silicon rubber or acrylonitrile-butadiene rubber for use, preferred butyl rubber or acrylonitrile-butadiene rubber.
Described room temperature is the water-soluble polymer of glassy state or crystalline state can select polyvinylpyrrolidone, polyethylene glycol oxide or polyvinyl alcohol for use.In the coaxial electrostatic spinning process, after the shell polymer molecule becomes fibre, can change glassy state or crystalline state again into rapidly in the quick volatilization process of solvent or in the fast cooling cooling procedure and be fixed up, make fiber indeformable.Simultaneously,, can reduce the answer distortion of sandwich layer IR fiber, improve the static spinnability of rubber by the spatial constraints of shell nanofiber.And the shell fiber is a water-soluble polymer, can remove easily and quickly by after using deionized water dissolving, does not influence the pattern and the DIMENSIONAL STABILITY of sandwich layer IR fiber.
Described inorganic salts electrolyte can be selected NaCl, AgNO for use
3Or CaCl
2Deng strong electrolyte, most of genus heveas are nonpolar, and the solution conductivity rate is low, and the static tensile force that is subjected to is little, is unfavorable for electrostatic spinning, add electrolyte to improve the conductance of rubber solutions, improve the spinnability of rubber solutions.
Described modification reinforcer is a rubber materials double bond containing silane coupler modified nano silicon commonly used, and nano silicon can be the precipitation method or fume colloidal silica.Method of modifying is traditional dry method modification, the modifier that the present invention adopts is the vinyl Ethoxysilane, behind ethanol dilution, mix in homogenizer with white carbon, the mass ratio of therein ethylene base oxethyl silane and ethanol, white carbon is 3:10:100, then 120 ℃ of dryings 2 hours.
The described room temperature effumability organic solvent that is used to prepare rubber solutions can be selected oxolane, carrene, chloroform, acetone or N, dinethylformamide for use.
The described organic solvent that is used to prepare water-soluble polymer can be selected oxolane, ethanol or N, dinethylformamide for use.
Described crosslinking agent is a kind of binary mixture, wherein a component is that each molecule organopolysiloxane of containing two silicon bonded hydrogen atoms at least is (as the strand two ends by the hydrogenated methyl polysiloxanes of trimethylsiloxy end-blocking, the strand two ends are by the dimethyl siloxane of trimethylsiloxy end-blocking-hydrogenated methyl silicone copolymers), another component is that platinum is catalyst based, the present invention adopts the alcoholic solution of chloroplatinic acid, platinum content is 1ppm～10000ppm in the catalyst, and the catalyst based mass ratio of organopolysiloxane and platinum is 1:3～4:1.Owing in crosslinking agent, added an amount of platinum metal catalyst, can make IR fiber original position under lower temperature crosslinked fast, make rubber molecule form the three-dimensional crosslinked network structure fast, the pattern of stable fibers.
The electrostatic spinning process parameter that the present invention selects: the flow velocity of sandwich layer solution is 0.5-2.0ml/h, the flow velocity of shell solution is 0.5-3.0ml/h, flow velocity is excessive, the droplet size that the nozzle place is not in time stretched is bigger, owing to solvent evaporates is solidified, can stop up spinning nozzle, flow velocity is too small, fiber collecting speed is slow, and productive rate is low.Preferred 0.5～the 1.5mm of spinnerette diameters, spinnerette diameters is too little, and polymer solution stops up easily, and spinnerette diameters is too big, flows out easily to produce drippage.Accept the preferred 8-25cm of distance, receiving range is excessive, and solvent fully volatilizees before fiber arrives collecting board, fiber destroys pattern owing to excessively stretching, and it is too small to accept distance, and fiber arrives after the collecting board, because solvent is fully volatilization not, residual solvent is more, also can destroy the pattern of fiber.The preferred 10-30KV of voltage, voltage is excessive, the IR fiber of high elongation is because elastic deformation is replied fast, and single fiber ruptures, and causes spinning discontinuous, voltage is too small, rubber solutions is because conductance is low, and the tensile force that is subjected to is little, and fiber is not fully stretched, diameter is thicker, is unfavorable for electrostatic spinning.
Preparation method of the present invention is simple, and the continuity of spinning and good stability, and the IR fiber stable appearance of preparation can solve static and spin high elastic rubber and be difficult to that serialization and stabilisation, fibre diameter are thick, the difficult problem of shape stability difference.This rubber nano fibre is expected to be widely used in fields such as biomedicine, antibiotic and sterilizing, toughened plastics.
Description of drawings:
Fig. 1 is a coaxial electrostatic spinning silk device schematic diagram.Among the figure, 1-sandwich layer solution, 2-high voltage source, 3-shell solution, 4-coaxial nozzle, 5-mixing jet, 6-gathering-device, 7-cork.
The specific embodiment:
The present invention will be described in more detail with embodiment, but embodiment is not construed as limiting the invention.
Embodiment 1: 1g (100 parts) silicon rubber, 0.25gNaCl (25 parts) and the silane coupler modified fume colloidal silica of 0.3g (30 parts) are mixed in the 10g carrene, stir and be mixed with rubber solutions, obtain sandwich layer solution, before the electrostatic spinning, (organopolysiloxane A is that the strand two ends are by the hydrogenated methyl polysiloxanes of trimethylsiloxy end-blocking in the crosslinking agent to add 0.005g (0.5 part) crosslinking agent in sandwich layer solution, platinum content is 10000ppm among the alcoholic solution B of chloroplatinic acid, and A, B two constituent masses are than being 1:1); The 1.5g polyvinylpyrrolidone is dissolved in the 10g ethanol, and stirring makes shell solution; Coaxial electrostatic spinning, setting spinning head and dash receiver distance is 15cm, the flow velocity of sandwich layer solution is 1.0ml/h, spinnerette diameters is 0.5mm, the flow velocity of shell solution is 2.0ml/h, spinnerette diameters is 1.0mm, and electrostatic potential is 15KV, collects to obtain silicon rubber/polyvinylpyrrolidone composite nano fiber; Treat composite nano fiber after 40 ℃ of following original positions are crosslinked fast, composite nano fiber is immersed in removes the shell fiber in the deionized water, promptly get the silicon rubber nano fiber after the drying at room temperature.
Embodiment 2: with 1g (100 parts) butyl rubber, 0.05gAgNO
3The silane coupler modified fume colloidal silica of (5 parts) and 0.05g (5 parts) is mixed in the 10g oxolane, stir and be mixed with rubber solutions, obtain sandwich layer solution, before the electrostatic spinning, (organopolysiloxane A is that the strand two ends are by the hydrogenated methyl polysiloxanes of trimethylsiloxy end-blocking in the crosslinking agent to add 0.1g (10 parts) crosslinking agent in sandwich layer solution, platinum content is 100ppm among the alcoholic solution B of chloroplatinic acid, and A, B two constituent masses are than being 1:2); The 1.2g polyethylene glycol oxide is dissolved in the 10g ethanol, and stirring makes shell solution; Coaxial electrostatic spinning, setting spinning head and receiver sheet distance is 20cm, the flow velocity of sandwich layer solution is 0.8ml/h, spinnerette diameters is 0.6mm, the flow velocity of shell solution is 1.2ml/h, spinnerette diameters is 1.2mm, and electrostatic potential is 20KV, collects to obtain butyl rubber/polyethylene glycol oxide composite nano fiber; Treat rubber phase in the composite nano fiber after 25 ℃ of following original positions are fast crosslinked, composite nano fiber is immersed in removes the shell fiber in the deionized water, promptly get the butyl rubber nanofiber after the drying at room temperature.
Embodiment 3: with 1g (100 parts) butadiene rubber, 0.2gAgNO
3The silane coupler modified precipitated silica of (20 parts) and 0.1g (10 parts) is mixed in the 8g oxolane, stir and be mixed with rubber solutions, obtain sandwich layer solution, before the electrostatic spinning, (organopolysiloxane A is that the strand two ends are by the dimethyl siloxane of trimethylsiloxy end-blocking-hydrogenated methyl silicone copolymers in the crosslinking agent to add 0.03g (3 parts) crosslinking agent in sandwich layer solution, platinum content is 3000ppm among the alcoholic solution B of chloroplatinic acid, and A, B two constituent masses are than being 1:3); The 1.0g polyvinyl alcohol is dissolved in the 10g ethanol, and stirring makes shell solution; Coaxial electrostatic spinning, setting spinning head and receiver sheet distance is 15cm, the flow velocity of sandwich layer solution is 1.5ml/h, spinnerette diameters is 1.0mm, the flow velocity of shell solution is 3.0ml/h, spinnerette diameters is 1.5mm, and electrostatic potential is 18KV, collects to obtain butadiene rubber/polyvinyl alcohol composite nano fiber; Treat rubber phase in the composite nano fiber after 30 ℃ of following original positions are fast crosslinked, composite nano fiber is immersed in removes the shell fiber in the deionized water, promptly get the butadiene rubber nanofiber after the drying at room temperature.
Embodiment 4: with 1g (100 parts) acrylonitrile-butadiene rubber, 0.20g (20 parts) CaCl
2And the silane coupler modified precipitated silica of 0.15g (15 parts) is mixed in the 12g chloroform, stir and be mixed with rubber solutions, obtain sandwich layer solution, before the electrostatic spinning, (organopolysiloxane A is that the strand two ends are by the dimethyl siloxane of trimethylsiloxy end-blocking-hydrogenated methyl silicone copolymers in the crosslinking agent to add 0.08g (8 parts) crosslinking agent in sandwich layer solution, platinum content is 1000ppm among the alcoholic solution B of chloroplatinic acid, and A, B two constituent masses are than being 3:1); The 1.0g polyvinylpyrrolidone is dissolved in the 12g ethanol, and stirring makes shell solution; Coaxial electrostatic spinning, setting spinning head and receiver sheet distance is 20cm, the flow velocity of sandwich layer solution is 0.6ml/h, spinnerette diameters is 0.8mm, the flow velocity of shell solution is 1.2ml/h, spinnerette diameters is 1.2mm, and electrostatic potential is 25KV, collects to obtain acrylonitrile-butadiene rubber/polyvinylpyrrolidone composite nano fiber; Treat rubber phase in the composite nano fiber after 45 ℃ of following original positions are fast crosslinked, composite nano fiber is immersed in removes the shell fiber in the deionized water, promptly get the acrylonitrile-butadiene rubber nanofiber after the drying at room temperature.
Embodiment 5: with 1g (100 parts) silicon rubber, 0.16g CaCl
2The silane coupler modified fume colloidal silica of (16 parts) and 0.10g (10 parts) is mixed in the 8g carrene, stir and be mixed with rubber solutions, obtain sandwich layer solution, before the electrostatic spinning, (organopolysiloxane A is that the strand two ends are by the dimethyl siloxane of trimethylsiloxy end-blocking-hydrogenated methyl silicone copolymers in the crosslinking agent to add 0.08g (8 parts) crosslinking agent in sandwich layer solution, platinum content is 5000ppm among the alcoholic solution B of chloroplatinic acid, and A, B two constituent masses are than being 2:1); The 1.0g polyvinylpyrrolidone is dissolved in the 11g ethanol, and stirring makes shell solution; Coaxial electrostatic spinning, setting spinning head and dash receiver distance is 18cm, the flow velocity of sandwich layer solution is 1.2ml/h, spinnerette diameters is 0.7mm, the flow velocity of shell solution is 2.2ml/h, spinnerette diameters is 1.5mm, and electrostatic potential is 30KV, collects to obtain silicon rubber/polyvinylpyrrolidone composite nano fiber; Treat composite nano fiber after 45 ℃ of following original positions are crosslinked fast, composite nano fiber is immersed in removes the shell fiber in the deionized water, promptly get the silicon rubber nano fiber after the drying at room temperature.
Embodiment 6: 1g (100 parts) butyl rubber, 0.15gNaCl (15 parts) and the silane coupler modified fume colloidal silica of 0.20g (20 parts) are mixed in the 9g oxolane, stir and be mixed with rubber solutions, obtain sandwich layer solution, before the electrostatic spinning, (organopolysiloxane A is that the strand two ends are by the hydrogenated methyl polysiloxanes of trimethylsiloxy end-blocking in the crosslinking agent to add 0.06g (6 parts) crosslinking agent in sandwich layer solution, platinum content is 3000ppm among the alcoholic solution B of chloroplatinic acid, and A, B two constituent masses are than being 1:2); The 1.0g polyethylene glycol oxide is dissolved in the 13g ethanol, and stirring makes shell solution; Coaxial electrostatic spinning, setting spinning head and receiver sheet distance is 22cm, the flow velocity of sandwich layer solution is 0.8ml/h, spinnerette diameters is 0.6mm, the flow velocity of shell solution is 1.2ml/h, spinnerette diameters is 1.2mm, and electrostatic potential is 20KV, collects to obtain butyl rubber/polyethylene glycol oxide composite nano fiber; Treat rubber phase in the composite nano fiber after 50 ℃ of following original positions are fast crosslinked, composite nano fiber be immersed in remove the shell fiber in the deionized water, after the drying at room temperature the butyl rubber nanofiber.
The embodiment of the invention 1～embodiment 6 spinning processes are continuous, and the diameter that obtains fiber is tens nanometers to 1 micron, still can keep good fiber pattern after parking a period of time.
Comparative Examples 1: 1g (100 parts) silicon rubber is dissolved in the 10g carrene, and stirring is mixed with rubber solutions, and spinnerette diameters is 0.5mm, and setting spinning head and dash receiver distance is 20cm, and solution flow rate is 0.8ml/h, and electrostatic potential is 17KV.Electrostatic spinning is discontinuous, and the silicone rubber fiber that collection obtains subsides very soon and melts also.
Comparative Examples 2: 1g (100 parts) butyl rubber and the silane coupler modified fume colloidal silica of 0.05g (5 parts) are mixed in the 10g oxolane, stir and be mixed with rubber solutions, setting spinning head and receiver sheet distance is 22cm, spinnerette diameters is 0.7mm, solution flow rate is 0.6ml/h, and electrostatic potential is 20KV.Electrostatic spinning is more continuous, and it is thicker to collect the butyl rubber fibre diameter obtain, and parking subsides after a period of time very soon melts and film forming.
Claims (8)
1. preparing rubber nanometer fibers adopts the coaxial electrostatic spinning method, is sandwich layer solution with the rubber solutions, and water-soluble polymer solution is a shell solution, applies to carry out coaxial electrostatic spinning behind the high-pressure electrostatic and make, and concrete preparation condition and step are as follows:
(1) will contain the rubber, inorganic salts electrolyte dissolution of unsaturated carbon-carbon double bond in room temperature effumability organic solvent, adding modification reinforcer stirs and is mixed with rubber solutions, the mass percentage concentration of rubber is 5%-20%, and the mass ratio of rubber, inorganic salts electrolyte and modification reinforcer is 100:0.5-25:5-30; Before static spins, in rubber solutions, add the crosslinking agent of 0.5-10 parts by mass;
(2) the water-soluble polymer dissolution that room temperature is glassy state or crystalline state is stirred to dissolving fully in organic solvent, and making mass percentage concentration is the shell solution of 5%-20%;
(3) setting spinning head and dash receiver distance is 8-25cm, and the flow velocity of adjusting sandwich layer solution is 0.5-2.0ml/h, and spinnerette diameters is 0.5～1.0mm, and the flow velocity of shell solution is 0.5-3.0ml/h, and spinnerette diameters is 1.0～1.5mm; After treating stable the outflow, applying electrostatic potential is 10-30kV, coaxial electrostatic spinning, collection obtains rubber/water-soluble polymer composite nano fiber, treat that rubber phase in the composite fibre is after original position under 20～50 ℃ the lower temperature is fast crosslinked, the use deionized water dissolving is removed the water-soluble polymer skin in the composite fibre, obtains rubber nano fibre after the drying at room temperature.
2. according to the preparing rubber nanometer fibers of claim 1, it is characterized in that: the described rubber that contains unsaturated carbon-carbon double bond is butadiene rubber, butyl rubber, silicon rubber or acrylonitrile-butadiene rubber.
3. preparing rubber nanometer fibers according to claim 1 is characterized in that: described water-soluble polymer is polyvinylpyrrolidone, polyethylene glycol oxide or polyvinyl alcohol.
4. according to the preparing rubber nanometer fibers of claim 1, it is characterized in that: described inorganic salts electrolyte is NaCl, AgNO
3Or CaCl
2
5. according to the preparing rubber nanometer fibers of claim 1, it is characterized in that: described modification reinforcer is double bond containing silane coupler modified nano silicon.
6. according to the preparing rubber nanometer fibers of claim 1, it is characterized in that: the described organic solvent that is used to prepare rubber solutions is oxolane, carrene, chloroform, acetone or N, dinethylformamide.
7. according to the preparing rubber nanometer fibers of claim 1, it is characterized in that: the described organic solvent that is used to prepare water soluble polymer shell layer solution is oxolane, ethanol or N, dinethylformamide.
8. according to the preparing rubber nanometer fibers of claim 1, it is characterized in that: described crosslinking agent is a kind of binary mixture, wherein a component is the organopolysiloxane that each molecule contains two silicon bonded hydrogen atoms at least, another component is that platinum is catalyst based, platinum content is 1ppm～10000ppm in the catalyst, and the catalyst based mass ratio of organopolysiloxane and platinum is 1:3～4:1.
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