CN101161872A - Method for preparing high-strength polymer nano-fibre - Google Patents
Method for preparing high-strength polymer nano-fibre Download PDFInfo
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Abstract
The present invention relates to a high-intensity nano-fiber preparation method. A high-intensity polymer nano-fiber is prepared in a limited space of dimensional nano-fiber through rigid molecules or semirigid molecules in assembling orientation with electrospinning technology; electrospinning rigid polymer polystyrene benzodiazepines oxazoline (PBO) and polybenzimidazole (PBI) are put to a mixed solvent of methanesulfonic acid and trifluoroacetic acid to form a solution in a high-voltage electric field with the electrical field strength between 30 kV/m and 300 kV/m; the proportion of the methanesulfonic acid to the trifluoroacetic acid is between 1/5 and 1; the concentration range of the polymer is between 1 percent mass concentration and 5 percent mass concentration; ultrafine fiber with the diameter between 50 nm and 500 nm is produced. The invention has molecule assembly on a series of rigid polymer molecules or semirigid polymer molecules with the electrospinning technology to prepare the high-intensity polymer nano-fiber with the rigid molecules or semirigid molecules along the fiber axial orientation.
Description
Affiliated field
The invention belongs to a kind of technology of preparing of high intensity nano fibre.The present invention carries out direct or indirect molecule assembling with electrospinning to polymer, prepares high-intensity rigidity or semi-rigid polymer nanofiber.
Background technology
The diameter of electric spinning polymer nanofiber has been contained 1 nanometer and has been arrived several microns wide spectrum size range, its length has then covered several centimetres to several meters scope (depending on the shape and the collection mode of fiber collecting device), the monodimension nanometer material characteristic of this high length can directly be used it as the macrostructure material, form nano fiber non-woven fabric.This nano fiber non-woven fabric (non-wovenfabric) is the height holeization, and the aperture can be as small as several nanometers, has good filtering property.Because strength problem, can only have that the backing material of suitable intensity is compound to be used for or to develop the air inlet that is used for various engines (from automobile, tank engine to the turbine factory building) with other, filtering dust collecting dust, smog, bacterium even virus are gone up in fire-fighting, medical treatment and military protection.On the other hand, because the good hygroscopicity that excellent handle that the flexibility of small diameter fibers causes and high-specific surface area cause makes the electric spinning polymer nanofiber have the great potential that enters the comfortableness apparel industry; Aspect aerospace, the scientists of the U.S. then causes low-density electric spinning polymer nano-fiber cloth to be manufactured on the light sail that advances spacecraft in the space in research with this height holeization.
For the nonwoven fabric that polymer nanofiber is formed can break through must with the limitation of the compound use of other backing material, make pure broken polymer nanofiber articles for use (as light, comfortable, nanofiber protective clothing efficiently; The light sail of high-strength low-density etc.), must increase substantially the intensity of polymer nanofiber.The tradition crude fibre can make polymer molecule to heavens along the fiber axial orientation by the spinning first break draft, thereby improves the mechanical performance of fiber significantly.The electric spinning polymer nanofiber is because 1) diameter is too little, 2) jet (nanofiber is produced by the jet of this polymer solution) excessive velocities, 3 in the electrospinning process) track of jet is fluid, and can't improve the mechanical performance of fiber with traditional drafting method.
Summary of the invention
The object of the present invention is to provide a kind of mechanical stretching that need not pass through in the traditional handicraft, just can form the method for molecule along the high-strength polymer nano-fibre of fiber axial orientation.
Concrete grammar of the present invention is as follows: a kind of preparation method of high intensity nano fibre comprises directly and indirect two kinds of methods.1) direct method: electricity consumption spining technology, in the confined space of 1-dimention nano fiber, be orientated assembling preparation high-strength polymer nano-fibre by rigidity or semi-rigid molecule, in electric-field intensity is the solution that electrospinning rigid polymer polyhenylene Ben Bing Er oxazole (PBO) and polybenzimidazoles (PBI) form in methanesulfonic acid and trifluoroacetic acid mixed solvent in 30 to 300kV/m the high voltage electric field, the ratio of methanesulfonic acid/trifluoroacetic acid is listed as between 1/5-1, the concentration range of polymer is between 1% to 5% mass concentration, produce the superfine fibre of diameter at 50nm to 500nm, be subjected to the drawing-off effect of high-pressure electrostatic driving force in the tiny jet that the rigid polymer molecule produces and be orientated assembling in electrostatic spinning, form the high intensity nano fibre of molecule along the fiber axial orientation, its strength range is between 0.5GPa to 2.5GPa.
2) indirect method: comprise two steps, elder generation's electrospinning: take from synthesizing polyamides acid (PAA) solution, inherent viscosity is 2-7dl/g, add softex kw (DEMAB) and DMAc, form polymer quality concentration be about concentration between 1% and 20%, the DEMAB mass concentration is that 0.05-0.5%, absolute viscosity are the spinning solution of 6-15Pa.S, in being 100 to 300kV/m electric field, electric-field intensity implements electrostatic spinning, the rotary flywheel that with the linear velocity is 24-48m/s is the nanofiber gatherer, collects the oriented nanofibers film; Imidization again: nano fibrous membrane or single nanofiber are in the imidization stove of blanket of nitrogen, programming rate with 20-30 ℃/min is heated to 250 ℃ from room temperature, and at 250 ℃ of about 30min of following stop, programming rate with 1-2 ℃/min is heated to 330-400 ℃ then, and under this temperature, stop about 30min, naturally cool to room temperature and take out.
To be molecular chain length will be forced to form the nanofiber that molecule is orientated along the assembling of fiber axial orientation in fiber in the confined space of 1-dimention nano fiber greater than the rigidity of nanofiber diameter or semi-rigid molecule basic concept of the present invention.As, molecular diameter be about 0.5nm, the rigid polymer molecule of chain length 500nm assembles in diameter is the fiber of 100nm, most probable assembling form is: rigid rod-like molecules along fiber axis to orientation to heavens.
The present invention utilizes the static spinning technique, the rigid polymer molecule is assembled preparation high performance polymer nanofiber.Included two kinds of methods: 1. direct method: rigid polymer is dissolved in the appropriate solvent, rigid molecule solution arrives the place, tip of high voltage electric field one utmost point through capillary channel, and the drop that links to each other with the tip of formation, under the effect of high voltage electric field, drop produces awl point (being Tailor cone) along the direction of an electric field distortion, and then the surface tension that overcomes drop produces jet, another utmost point of directive high voltage electric field, the i.e. gatherer of nanofiber.In the high-speed motion of jet by another utmost point of utmost point directive, along the direction of motion of jet orientation, when solvent volatilizees in motion process at a high speed, jet concentrates rigid molecule gradually, is to put to be solidified into the nanofiber of molecule along the fiber axial orientation in jet.The power that molecule is orientated in jet from: 1) bar-shaped object is along the direction of motion orientation of taking advantage of a situation, to reduce the resistance of motion; 2) between the rigid molecule with parallel each other, as much as possible near and produce the interaction force of intermolecular maximum and be orientated gathering; 3) jet is from the high-speed motion of another utmost point of utmost point directive, constantly concentrate weight reducing, change to nano level diameter from micron-sized jet diameter, the rigidity solute molecule of solvation with the liquid jet diameter diminish and preferred orientation, trend towards parallelly with the variation of complying with jet diameter, make jet reach the nanoscale minor diameter with the direction of motion; 4) charged jet is under the driving of high voltage electric field, in air from the high-speed motion of another utmost point of utmost point directive, jet is outer to produce hysteresis with windage, the movement velocity inequality that causes jet, form the jet-core region to the velocity gradient between extexine, the movement velocity of this inequality causes the direction of motion orientation of the rigid polymer molecule of solvation along jet in the jet, thereby forms the nanofiber of rigid polymer molecule along the fiber axial orientation.As the polyhenylene Ben Bing Er oxazole (PBO) of rigidity, polyhenylene benzo diimidazole (PBI) etc., be dissolved in the mixed solvent of trifluoroacetic acid (TFA) and methanesulfonic acid (MSA), in high voltage electric field, carry out electrostatic spinning and form high-intensity electric spinning polymer nanofiber.2. indirect method: the rigid polymer precursor solution of electrospinning flexibility in high voltage electric field, form the nanofiber of the flexible precursor of rigid polymer, the nanofiber of this flexible precursor at high temperature changes into the rigid polymer nanofiber.In the conversion process of rigid molecule, the confined space of 1-dimention nano fiber forces polymer molecule to be orientated in nanofiber at flexible molecule, forms high-intensity polymer nanofiber.
Specific embodiment
Example 1
The preparation of high strength biphenyl acid anhydride/p-phenylenediamine (PPD) polyimides [Poly (p-phenylenebiphenyltetracarboximide)] (BPDA/PDA PI) nanofiber is synthetic: get biphenyl dianhydride (BPDA) 5.8842g (20mmol) and p-phenylenediamine (PPD) (PDA) 2.1628g (20mmol) and be dissolved in 72.42g N ' N-dimethylacetylamide (DMAC) or the N ' dinethylformamide (DMF), under intense mechanical stirs, after-5 ℃ of low temperature react 8 hours down, rising 3 ℃ reacted 8 hours down, form concentration expressed in percentage by weight and be about biphenyl acid anhydride/p-phenylenediamine (PPD) polyamic acid (BPDA/PDA PAA) [Poly (p-phenylenebiphenyldicarboxyldicarboxamide)] solution of 10%, this polyamic acid is the precursor of polyimides (BPDA/PDA PI).The reaction equation and the monomer structure formula synthetic and that transform to polyimides of polyamic acid are as follows:
Electrospinning: get above-mentioned synthesizing polyamides acid (BPDA/PDA PAA) solution (inherent viscosity is 5.2dl/g) 10g, add softex kw (DEMAB) 25mg and DMAc15g, form that polymer quality concentration is about 4%, the DEMAB weight concentration is 0.1%, absolute viscosity is the spinning solution of 6.601Pa.S, in being the electric field of 150KV/m, electric-field intensity implements electrostatic spinning, the flywheel that with the linear velocity is the high speed rotating of 24m/s is the nanofiber gatherer, collects the oriented nanofibers film.
Imidization: nano fibrous membrane or single nanofiber are in the imidization stove of blanket of nitrogen, programming rate with 20-30 ℃/min is heated to 250 ℃ from room temperature, and at 250 ℃ of following 30min that stop, programming rate with 1-2 ℃/min is heated to 370 ℃ then, and under 370 ℃, stop 30min, naturally cool to room temperature.
Mechanics Performance Testing: the TENSILE STRENGTH of single nanofiber: 1.6GPa, elastic modelling quantity: 64GPa, elongation at break: 2.5-3%; The TENSILE STRENGTH of oriented nanofibers film: 0.65GPa, elastic modelling quantity: 15GPa, elongation at break: 6%.
Example 2
The preparation of high strength biphenyl dianhydride/benzidine polyimides [Poly (biphenylenebiphenyltetracarboximide)] (BPDA/BPA PI) nanofiber
Synthetic: as to get biphenyl dianhydride (BPDA) 5.8842g (20mmol) and benzidine (BPA) 3.6848g (20mmol) is dissolved among 86.12g DMAc or the DMF, under intense mechanical stirs, after-5 ℃ of low temperature react 8 hours down, rising 3 ℃ reacted 8 hours down, form concentration expressed in percentage by weight and be about biphenyl dianhydride/benzidine polyamic acid (BPDA/BPA PAA) [Poly (biphenylenebiphenyldicarboxyldicarboxamide)] solution of 10%, this polyamic acid is the precursor of polyimides (BPDA/BPA PI).
Electrospinning: get above-mentioned synthesizing polyamides acid (BPDA/BPA PAA) solution (inherent viscosity is 4.3dl/g) 10g, add DEMAB19.6mg and DMAc9.6g, form that polymer quality concentration is about 5.1%, the weight concentration of DEMAB is about 0.1%, absolute viscosity is the spinning solution of 6.551Pa.S, in being the electric field of 150KV/m, electric-field intensity implements electrostatic spinning, the flywheel that with the linear velocity is the high speed rotating of 24m/s is the nanofiber gatherer, collects the oriented nanofibers film.
Imidization: nano fibrous membrane or single nanofiber are in the imidization stove of blanket of nitrogen, programming rate with 20-30 ℃/min is heated to 250 ℃ from room temperature, and at 250 ℃ of following 30min that stop, programming rate with 1-2 ℃/min is heated to 370 ℃ then, and under 370 ℃, stop 30min, naturally cool to room temperature.
Mechanics Performance Testing: the TENSILE STRENGTH of single nanofiber: 1.2GPa, elastic modelling quantity: 50GPa,
Elongation at break: 3%; The TENSILE STRENGTH of oriented nanofibers film: 0.55GPa, elastic modelling quantity: 7.3GPa, elongation at break: 8%.
Example 3
(the preparation of 4,4 '-oxydianilinebiphenyltetracarboximide) (BPDA/ODA) polyimide nano-fiber of high strength biphenyl dianhydride/ether diamine polyimides Poly
Synthetic: as to get biphenyl dianhydride (BPDA) 5.8842g (20mmol) and ether diamine (ODA) 4.0048g (20mmol) is dissolved among 89gDMAc or the DMF, under intense mechanical stirs, after-5 ℃ of low temperature react 8 hours down, rising 3 ℃ reacted 8 hours down, forming concentration expressed in percentage by weight is about biphenyl dianhydride/ether diamine polyamic acid (BPDA/ODA PAA) of 10% [Poly (4,4 '-oxydianilinebiphenyldicarboxyldicarboxamide)] solution, this polyamic acid are the precursors of polyimides (BPDA/ODA PI).
Electrospinning: get above-mentioned synthesizing polyamides acid (BPDA/ODA PAA) solution (inherent viscosity is 4.5dl/g) 10g, add DEMAB20.8mg and DMAc10.8g, form polymer quality concentration and be 4.8%, the weight concentration of DEMAB is about 0.1%, absolute viscosity is the spinning solution of 6.71Pa.S, in being the electric field of 150KV/m, electric-field intensity implements electrostatic spinning, the flywheel that with the linear velocity is the high speed rotating of 24m/s is the nanofiber gatherer, collects the oriented nanofibers film.
Imidization: nano fibrous membrane or single nanofiber are in the imidization stove of blanket of nitrogen, programming rate with 20-30 ℃/min is heated to 250 ℃ from room temperature, and at 250 ℃ of following 30min that stop, programming rate with 10 ℃/min is heated to 370 ℃ then, and under 370 ℃, stop 30min, naturally cool to room temperature.
Mechanics Performance Testing: the TENSILE STRENGTH of single fiber nanometer dimension: 0.81GPa, elastic modelling quantity: 5.68GPa, elongation at break: 17%; The TENSILE STRENGTH of oriented nanofibers film: 0.49GPa, elastic modelling quantity: 1.85GPa, elongation at break: 36%.
Example 4
(the preparation of 4,4 '-oxydianilinepyromelliticimide) (PMDA/ODA) polyimide nano-fiber of high strength pyromellitic acid dianhydride/ether diamine polyimides Poly
Synthetic: as to get pyromellitic acid dianhydride (PMDA) 4.3624g (20mmol) and ether diamine (ODA) 4.0048g (20mmol) is dissolved among 75.3gDMAc or the DMF, under intense mechanical stirs, after-5 ℃ of low temperature react 8 hours down, rising 3 ℃ reacted 8 hours down, forming concentration expressed in percentage by weight is about pyromellitic acid dianhydride/ether diamine polyamic acid (PMDA/ODA PAA) of 10% [Poly (4,4 '-oxydianiline pyromelliticamide)] solution, this polyamic acid are the precursors of polyimides (PMDA/ODA PI).
Electrospinning: get above-mentioned synthetic polyamic acid (PMDA/ODA PAA) solution (inherent viscosity is 5.5dl/g) 10g, add DEMAB26.3mg and DMAc16.3g, form polymer quality concentration and be 3.8%, the DEMAB weight concentration is about 0.1%, absolute viscosity is the spinning solution of 7.79Pa.S, in being the electric field of 150KV/m, electric-field intensity implements electrostatic spinning, the flywheel that with the linear velocity is the high speed rotating of 24m/s is the nanofiber gatherer, collects the oriented nanofibers film.
Imidization: nano fibrous membrane or single nanofiber are in the imidization stove of blanket of nitrogen, programming rate with 20-30 ℃/min is heated to 250 ℃ from room temperature, and at 250 ℃ of following 30min that stop, programming rate with 10 ℃/min is heated to 370 ℃ then, and under 370 ℃, stop 30min, naturally cool to room temperature.
Mechanics Performance Testing: the TENSILE STRENGTH of single nanofiber: 0.87GPa, elastic modelling quantity: 5.92GPa, elongation at break: 16%; The TENSILE STRENGTH of oriented nanofibers film: 0.45GPa, elastic modelling quantity: 1.35GPa, elongation at break: 40%.
Example 5
High strength biphenyl dianhydride/p-phenylenediamine (PPD)/ether diamine co-Poly (p-phenylenebiphenylene4,4 '-oxydianiline biphenyltetracarboximide)
The preparation of (BPDA/PDA/ODA co-PI) random copolymerization polyimide nano-fiber
Synthetic: as to get biphenyl dianhydride (BPDA) 5.8842g (20mmol), p-phenylenediamine (PPD) (PDA) 1.947g (18mmol) and ether diamine (ODA) 0.4005g (2mmol) are dissolved among 73.5gDMAc or the DMF, under intense mechanical stirs, after-5 ℃ of low temperature react 8 hours down, rising 3 ℃ reacted 8 hours down, form concentration expressed in percentage by weight and be about biphenyl dianhydride/p-phenylenediamine (PPD)/ether diamine random copolymerization polyamic acid (BPDA/PDA/ODA PAA) [co-Poly (p-phenylenebiphenylene4 of 10%, 4 '-oxydianiline biphenyltetracarboximideamide)] solution, this polyamic acid are the precursors of random copolymerization polyimides (BPDA/PDA/ODA co-PI).
Electrospinning: get above-mentioned synthetic polyamic acid (BPDA/PDA/ODA PAA) solution (inherent viscosity is 4.6dl/g) 10g, add DEMAB20.8mg and DMAc10.8g, form polymer quality concentration and be 4.8%, the weight concentration of DEMAB is about 0.1%, absolute viscosity is the spinning solution of 6.72Pa.S, in being the electric field of 150KV/m, electric-field intensity implements electrostatic spinning, the flywheel that with the linear velocity is the high speed rotating of 24m/s is the nanofiber gatherer, collects the oriented nanofibers film.
Imidization: nano fibrous membrane or single nanofiber are in the imidization stove of blanket of nitrogen, programming rate with 20-30 ℃/min is heated to 250 ℃ from room temperature, and at 250 ℃ of following 30min that stop, programming rate with 10 ℃/min is heated to 370 ℃ then, and under 370 ℃, stop 30min, naturally cool to room temperature.
Mechanics Performance Testing: the TENSILE STRENGTH of single nanofiber: 1.61GPa, elastic modelling quantity: 40.75GPa,
Elongation at break: 4%; The TENSILE STRENGTH of oriented nanofibers film: 0.85GPa, elastic modelling quantity: 9.55GPa, elongation at break: 9%.
Example 6
High strength biphenyl dianhydride/benzidine/ether diamine co-Poly (biphenylenebiphenylene4,4 '-oxydianiline biphenyltetracarboximide)
The preparation of (BPDA/BPA/ODA co-PI) random copolymerization polyimide nano-fiber
Synthetic: as to get biphenyl dianhydride (BPDA) 5.8842g (20mmol), benzidine (BPA) 0.3685g (2mmol) and ether diamine (ODA) 3.6043g (18mmol) are dissolved among 88.7gDMAC or the DMF, under intense mechanical stirs, after-5 ℃ of low temperature react 8 hours down, rising 3 ℃ reacted 16 hours down, form concentration expressed in percentage by weight and be about biphenyl dianhydride/benzidine/ether diamine random copolymerization polyamic acid (BPDA/BPA/ODA PAA) [co-Poly (biphenylene4 of 10%, 4 '-oxydianiline biphenyltetracarboximideamide)] solution, this random copolymerization polyamic acid are the precursors of random copolymerization polyimides (BPDA/BPA/ODA co-PI).
Electrospinning: get above-mentioned synthesizing polyamides acid (BPDA/BPA/ODA PAA) solution (inherent viscosity is 4.1dl/g) 10g, add DEMAB17.2mg and DMAc7.2g, form polymer quality concentration and be 5.8%, the DEMAB weight concentration is about 0.1%, absolute viscosity is the spinning solution of 6.72Pa.S, in being the electric field of 150KV/m, electric-field intensity implements electrostatic spinning, the flywheel that with the linear velocity is the high speed rotating of 24m/s is the nanofiber gatherer, collects the oriented nanofibers film.
Imidization: nano fibrous membrane or single nanofiber are in the imidization stove of blanket of nitrogen, programming rate with 20-30 ℃/min is heated to 250 ℃ from room temperature, and at 250 ℃ of following 30min that stop, programming rate with 10 ℃/min is heated to 370 ℃ then, and under 370 ℃, stop 30min, naturally cool to room temperature.
Mechanics Performance Testing: the TENSILE STRENGTH of single nanofiber: 1.41GPa, elastic modelling quantity: 15.75GPa,
Elongation at break: 9%; The TENSILE STRENGTH of oriented nanofibers film: 1.13GPa, elastic modelling quantity: 5.13GPa, elongation at break: 22%.
Example 7
High strength biphenyl dianhydride/p-phenylenediamine (PPD)/ether diamine co-Poly (p-phenylenebiphenylene4,4 '-oxydianiline biphenyltetracarboximide)
The preparation of (BPDA/PDA/ODA co-PI) block copolymerized polyimide nanofiber
Synthetic: as at first to add biphenyl dianhydride (BPDA) 5.8842g (20mmol) and p-phenylenediamine (PPD) (PDA) 1.0814g (10mmol) at a flask, BODA is excessive, in another flask, add biphenyl dianhydride (BPDA) 2.9421g (10mmol) and ether diamine (ODA) 4.0048g (20mmol), ODA is excessive, guarantee that excessive amine equates with the amount of substance of excessive acid anhydride, add 62.7g and 62.5gDMAc or DMF respectively, under intense mechanical stirs, after-5 ℃ of low temperature react 8 hours down, two reactions are lumped together, under 3 ℃ condition, continue reaction 16 hours, form concentration expressed in percentage by weight be about 10% biphenyl dianhydride/p-phenylenediamine (PPD)/ether diamine block copolymerization polyamic acid (BPDA/PDA/ODA PAA) [co-Poly (p-phenylene4,4 '-oxydianilinebiphenyltetracarboximideamide)] solution, this polyamic acid are the precursors of block copolymerized polyimide (BPDA/PDA/ODA co-PI).The synthetic reaction equation as
Electrospinning: get above-mentioned synthesizing polyamides acid (BPDA/PDA/ODA PAA) solution (inherent viscosity is 4.5dl/g) 10g, add DEMAB20.8mg and DMAc10.8g, form polymer quality concentration and be 4.8%, the DEMAB weight concentration is about 0.1%, absolute viscosity is the spinning solution of 7.02Pa.S, in being the electric field of 150KV/m, electric-field intensity implements electrostatic spinning, the flywheel that with the linear velocity is the high speed rotating of 24m/s is the nanofiber gatherer, collects the oriented nanofibers film.
Mechanics Performance Testing: filamentary TENSILE STRENGTH: 1.75GPa, elastic modelling quantity: 36.5GPa,
Elongation at break: 5%; The TENSILE STRENGTH of oriented nanofibers film: 1.21GPa, elastic modelling quantity: 11.86GPa, elongation at break: 11%.
Example 8
High strength biphenyl dianhydride/benzidine/ether diamine co-Poly (biphenylenebiphenylene4,4 '-oxydianiline biphenyltetracarboximide)
The preparation of (BPDA/BPA/ODA co-PI) block copolymerized polyimide nanofiber
Synthetic: at first add biphenyl dianhydride (BPDA) 5.8842g (20mmol) and benzidine (BPA) 1.8424g (10mmol) at a flask, BPDA is excessive; Add biphenyl dianhydride (BPDA) 2.9421g (10mmol) and ether diamine (ODA) 4.0048g (20mmol) in another flask, ODA is excessive; Guarantee that excessive amine equates with the amount of substance of excessive acid anhydride, add 69.5g and 62.5gDMAc or DMF respectively, under intense mechanical stirs, after-5 ℃ of low temperature react 8 hours down, two reactions are lumped together, under 3 ℃ condition, continue reaction 16 hours, form concentration expressed in percentage by weight be about 10% biphenyl dianhydride/benzidine/ether diamine block copolymerization polyamic acid (BPDA/BPA/ODA PAA) [co-Poly (biphenylene4,4 '-oxydianilinebiphenyltetracarboximideamide)] solution, this polyamic acid are the precursors of block copolymerized polyimide (BPDA/BPA/ODA co-PI).
Electrospinning: get above-mentioned synthesizing polyamides acid (BPDA/BPA/ODA PAA) solution (inherent viscosity is 3.9dl/g) 10g, add DEMAB17.24mg and DMAc7.3g, form that polymer quality concentration is about 5.8%, the DEMAB weight concentration is about 0.1%, absolute viscosity is the spinning solution of 6.82Pa.S, in being the electric field of 150KV/m, electric-field intensity implements electrostatic spinning, the flywheel that with the linear velocity is the high speed rotating of 24m/s is the nanofiber gatherer, collects the oriented nanofibers film.
Mechanics Performance Testing: filamentary TENSILE STRENGTH: 1.78GPa, elastic modelling quantity: 17.9GPa,
Elongation at break: 10%; The TENSILE STRENGTH of orientation fibers film: 1.35GPa, elastic modelling quantity: 6.16GPa, elongation at break: 22%.
Example 9
High strength polyhenylene Ben Bing Er oxazole
(PBO) preparation of nanofiber of poly (phenylenebenzobisoxazole)
Synthetic: as at first to take by weighing a certain amount of polyphosphoric acids (PPA) and (contain 78%P
2O
5) deoxidation several hrs in four-hole bottle, add monomer paraphthaloyl chloride (TPC) 2.03g (10mmol) then, be lower than 60 ℃ of reaction 18h. down, after treating that TPC dissolves fully, add monomer 4,6-diamino resorcin (DAR) 2.1306g (10mmol) keeps about 18h down at 60 ℃, keep adding a certain amount of P after 6 hours under 80 ℃, 100 ℃ temperature respectively immediately
2O
5, be warmed up to 120 ℃ again and keep 20h, add a certain amount of P again
2O
5, make the P among the final PPA
2O
5Content is 84%, then 160 ℃ of reactions 6 hours, 190 ℃ of reactions 6 hours, promptly obtains the PBO of rigidity.After polymerization is finished, pour in the water polymer into precipitation and smash, with big water gaging polymer is washed till neutrality then, dry 24h under 150 ℃ vacuum condition.The synthetic reaction equation is as follows:
Electrospinning: get in the mixed solvent of formation that above-mentioned synthetic PBO (inherent viscosity is 25dl/g) 1g is dissolved in 16.4g methanesulfonic acid (MSA) and 49.28g trifluoroacetic acid (TFA), the mass concentration that forms polymer solution is about 1.5%, and the NaCl of adding 0.1% increases the electric conductivity of solution.In electric-field intensity is electrostatic spinning in the electric field of 200-250KV/m.
Mechanics Performance Testing: the TENSILE STRENGTH of single nanofiber: 2.5GPa, elastic modelling quantity 100GPa, elongation at break about 2.5%
Example 10
High strength polybenzimidazoles P-polybenzimidazole (PBI) nanometer. the preparation of fiber
Synthetic: as in mechanical agitator, thermometer, nitrogen are housed derive the dry four-hole boiling flask of pipe, to add a certain amount of polyphosphoric acids (PPA) (P
2O
5Content is 80%) 120 ℃ of deoxidations two hours, add a certain amount of P subsequently
2O
5Make P in the polyphosphoric acids
2O
5Content brings up to 84%, adds monomers dimethyl terephthalate (DMT), 80 ℃ of reaction adding monomer 3,3 ', 4,4 '-biphenyl tetramine (DAB) beginning polycondensation reactions after 2 hours down, at 200 ℃ of reaction 20h, obtains the PBI of rigidity.After polymerisation is finished, pour in the water polymer into precipitation and smash, with big water gaging polymer is washed till neutrality then, dry 24h under 150 ℃ vacuum condition.The synthetic reaction equation is as follows:
Electrospinning: get above-mentioned synthetic PBI (inherent viscosity is 7.5dl/g) 2g and be dissolved in the mixed solvent that 11g methanesulfonic acid (MSA) and 44g trifluoroacetic acid (TFA) form, the mass concentration of the polymer solution that forms is about 3.5%, and the NaCl of adding 0.1% increases the electric conductivity of solution.In electric-field intensity is electrostatic spinning in the electric field of 200-250KV/m.
Mechanics Performance Testing: filamentary TENSILE STRENGTH: 1.5GPa, elastic modelling quantity 51GPa, elongation at break about 3%.
Claims (2)
1. the preparation method of a high intensity nano fibre is characterized in that:
The electricity consumption spining technology, in the confined space of 1-dimention nano fiber, be orientated assembling preparation high-strength polymer nano-fibre by rigidity or semi-rigid molecule, in electric-field intensity is the solution that electrospinning rigid polymer polyhenylene Ben Bing Er oxazole (PBO) and polybenzimidazoles (PBI) form in methanesulfonic acid and trifluoroacetic acid mixed solvent in 30 to 300kV/m the high voltage electric field, the ratio of methanesulfonic acid/trifluoroacetic acid is listed as between 1/5-1, the concentration range of polymer is between 1% to 5% mass concentration, produce the superfine fibre of diameter at 50nm to 500nm, be subjected to the drawing-off effect of high-pressure electrostatic driving force in the tiny jet that the rigid polymer molecule produces and be orientated assembling in electrostatic spinning, form the high intensity nano fibre of molecule along the fiber axial orientation, its strength range is between 0.5GPa to 2.5GPa.
2. the preparation method of a high intensity nano fibre, it is characterized in that: comprise two steps, elder generation's electrospinning: take from synthesizing polyamides acid (PAA) solution, inherent viscosity is 2-7dl/g, add softex kw (DEMAB) and DMAc, form polymer quality concentration and be about concentration between 1% and 20%, the DEMAB mass concentration is 0.05-0.5%, absolute viscosity is the spinning solution of 6-15Pa.S, in being 100 to 300kV/m electric field, electric-field intensity implements electrostatic spinning, the rotary flywheel that with the linear velocity is 24-48m/s is the nanofiber gatherer, collects the oriented nanofibers film; Imidization again: nano fibrous membrane or single nanofiber are in the imidization stove of blanket of nitrogen, programming rate with 20-30 ℃/min is heated to 250 ℃ from room temperature, and at 250 ℃ of about 30min of following stop, programming rate with 1-2 ℃/min is heated to 330-400 ℃ then, and under this temperature, stop about 30min, naturally cool to room temperature and take out.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100003519A1 (en) * | 2008-07-07 | 2010-01-07 | Taipei Medical University | Method of fabricating nano-fibers by electrospinning |
| CN101810971A (en) * | 2010-04-20 | 2010-08-25 | 南京际华三五二一特种装备有限公司 | Preparation method of PBO composite ultra-high temperature filter material |
| CN101974828A (en) * | 2010-09-30 | 2011-02-16 | 江西先材纳米纤维科技有限公司 | Copolymerized polyimide nanofiber nonwoven and preparation method and application thereof |
| CN102260932A (en) * | 2011-07-05 | 2011-11-30 | 深圳市中晟创新科技股份有限公司 | Preparation method of polyparaphenylene benzobisoxazole (PBO) fiber |
| CN102296376A (en) * | 2011-07-05 | 2011-12-28 | 深圳市中晟创新科技股份有限公司 | Production method of poly-p-phenylene benzodioxazole fibers |
-
2007
- 2007-09-25 CN CNA2007100095961A patent/CN101161872A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100003519A1 (en) * | 2008-07-07 | 2010-01-07 | Taipei Medical University | Method of fabricating nano-fibers by electrospinning |
| CN101810971A (en) * | 2010-04-20 | 2010-08-25 | 南京际华三五二一特种装备有限公司 | Preparation method of PBO composite ultra-high temperature filter material |
| CN101974828A (en) * | 2010-09-30 | 2011-02-16 | 江西先材纳米纤维科技有限公司 | Copolymerized polyimide nanofiber nonwoven and preparation method and application thereof |
| CN101974828B (en) * | 2010-09-30 | 2012-12-19 | 江西先材纳米纤维科技有限公司 | Copolymerized polyimide nanofiber nonwoven fabric and preparation method and application thereof |
| CN102260932A (en) * | 2011-07-05 | 2011-11-30 | 深圳市中晟创新科技股份有限公司 | Preparation method of polyparaphenylene benzobisoxazole (PBO) fiber |
| CN102296376A (en) * | 2011-07-05 | 2011-12-28 | 深圳市中晟创新科技股份有限公司 | Production method of poly-p-phenylene benzodioxazole fibers |
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