CN102560894A - Production method of polybenzoxazole nanofiber nonwoven fabric and its application - Google Patents
Production method of polybenzoxazole nanofiber nonwoven fabric and its application Download PDFInfo
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Abstract
The invention discloses a production method of a polybenzoxazole nanofiber nonwoven fabric and its application to the fabric in fields of high-temperature filtering, battery diaphragms, garment fabrics and the like. The polybenzoxazole nanofiber nonwoven fabric is made by converting corresponding hydroxyl polyimide nanofiber nonwoven fabric at high temperature, the polyimide which is the previous existence of polybenzoxazole is subjected to decarboxylation at 450-500 DEG C to be converted into corresponding polybenzoxazole. The polybenzoxazole nanofiber nonwoven fabric has the advantages of high temperature resistance, high chemical stability, high porosity, high mechanical strength and high breathability, moisture penetrability and permeability, and is applicable to high-temperature filtering, garment fabrics and battery diaphragms.
Description
Technical field
The present invention relates to a kind ofly spin method and the application thereof that the polyimide nano-fiber pyrolytic conversion forms Ju Ben Bing Er oxazole nano-fiber for production of non-woven by static, specifically is a kind of high temperature resistant, the high porosity of battery diaphragm, high temperature filtration, garment material, Ju Ben Bing Er oxazole nano-fiber for production of non-woven of good mechanical properties of can be used for.
Background technology
Polyhenylene Ben Bing Er oxazole (PBO) is a fragrant heterocycle macromolecular compound of gathering of one type of rigid rod, and its heat decomposition temperature is up to 670 ° of C, and limited oxygen index (LOI) is up to 68.The modulus of Theoretical Calculation pbo fiber is at 460-730 GPa, and theoretical TENSILE STRENGTH estimation is at 16-26 GPa.This polymer fiber is not only a kind of heat-resistance and flame-retardant fiber, the high-performance fiber of still a kind of high-strength, Gao Mo, and mechanical mechanics property even better than Kevlar is described as " the emerging fiber of 21 century ".This pbo fiber generally is to be solvent with the polyphosphoric acids, extrudes the spinneret orifice spinning through high pressure, and fibre diameter is generally more than 10 mm.Because neither fusion of PBO, also insoluble or be insoluble in OOS, therefore, be difficult to prepare PBO nanofiber and non-weaving cloth thereof through melting electrostatic spinning or solution electrostatic spinning.The present invention utilizes a kind of polyimides pyrolysis at high temperature changing into Ju Ben Bing Er oxazole of hydroxyl to prepare PBO nanofiber and non-weaving cloth thereof; Promptly utilize the precursor polyamic acid of the soluble HMW hydroxyl of OOS polyimides to carry out nanofiber and the non-manufacturing cloth thereof that electrostatic spinning prepares the hydroxyl polyamic acid; And imidization forms hydroxyl polyimide nano-fiber and non-weaving cloth thereof under higher temperature; Latter's effect between carbonyl under higher temperature because on hydroxyl and the imide ring; Inner molecular reaction taking place, cause molecular structure to take place to reset and decarboxylation, forms Ju Ben Bing Er oxazole chemical constitution.Consequently hydroxyl polyamic acid nanofiber and non-weaving cloth thereof at high temperature through imidization with oxazole formation high-strength high temperature-resistant Ju Ben Bing Er oxazole nanofiber and non-weaving cloth thereof, solved the difficult problem of high-strength high temperature-resistant Ju Ben Bing Er oxazole nanofiber and non-weaving cloth mass preparation thereof.
Summary of the invention
The object of the present invention is to provide the application of preparation method and this contrivance of a kind of high-strength high temperature-resistant Ju Ben Bing Er oxazole nanofiber and non-weaving cloth thereof in high temperature filtration, garment material and battery diaphragm field.This Ju Ben Bing Er oxazole nanofiber and non-weaving cloth thereof be through soluble hydroxyl polyamic acid in the OOS through high-voltage electrostatic spinning, high-temperature sub amination with the oxazole processing is obtained; The polyimide structures of the precursor hydroxyl polyamic acid of this Ju Ben Bing Er oxazole imidization under 200-300 ° of C formation hydroxyl; The latter is transformed into Ju Ben Bing Er oxazole structure after resetting Tuo Suo oxazoleization under the high temperature of 450-500 ° of C, transition process is shown below:
Hydroxyl polyamic acid precursor chemical structural formula
Hydroxyl polyimides chemical structural formula
Ju Ben Bing Er oxazole chemical structural formula
Wherein, R
1Be the residue structure that contains the dianhydride of aromatic ring, R is the residue structure that the dianhydride structure division stays in pyrolytic process in the polyimide molecule.N is the polymer repeat unit number, between 100 to 300.The n value is big more, and polymer molecular weight is big more, to form the nanofiber fibre strength high more.
Particularly, R
1Be a kind of in the following structure:
R is a kind of in the following structure:
High-strength high temperature-resistant Ju Ben Bing Er oxazole nanofiber of the present invention and non-weaving cloth thereof are with 3; 3 '-dihydroxybiphenyl diamines (diamines of hydroxyl) is a raw material with aromatic dianhydride (HAB); Condensation forms the polyamic acid of hydroxyl; Through high-voltage electrostatic spinning technology preparation hydroxyl polyamic acid nanofiber and non-weaving cloth thereof; Imidization obtains hydroxyl polyimide nano-fiber and non-weaving cloth thereof under 200-300 ° of C higher temperatures; Oxazole formation high-strength high temperature-resistant Ju Ben Bing Er oxazole nanofiber and non-weaving cloth thereof Xia 450-500 ° of C high temperature are with the filter material of this battery diaphragm as lithium ion battery, high-temperature smoke gas filtration, protective (fire prevention, rainproof, bacteriological protection) garment material etc.
This high-strength high temperature-resistant Ju Ben Bing Er oxazole nanofiber and non-weaving cloth thereof form through imidization of 200-300 ° of C higher temperature and the processing of 450-500 ° of C Gao Wen oxazole.Its key is hydroxyl in the hydroxyl polyimide structures and imide ring carbonyl generation inner molecular reaction under the high temperature; And carry out molecular structure and reset and decarboxylic reaction; Form the higher and better benzoxazole structure of structural symmetry of heat resistance, thereby give this nanofiber and non-weaving cloth has characteristics such as higher heat resistance and excellent mechanical intensity.
High-strength high temperature-resistant Ju Ben Bing Er oxazole nanofiber of the present invention and non-weaving cloth thereof have following characteristic: fibre diameter is 50 ~ 800 nm; Decomposition temperature is 630-700 ° of C; Monofilament tensile strength is greater than 2 GPa; The non-weaving cloth TENSILE STRENGTH is greater than 80 MPa, and porosity is 75-90%, characteristic such as in organic solvent, does not dissolve fully.Have this specific character gather benzene and two oxazole nanofibers and non-weaving cloth is high temperature resistant, heat resistanceheat resistant contraction, resistance to chemical attack; The battery diaphragm that high hole is filtered, high strength is suitable for doing lithium ion battery, the filter material of high-temperature smoke gas filtration, protective (fire prevention, rainproof, bacteriological protection) garment material etc. will be widely used in electrokinetic cell industry, high-temperature smoke gas filtration industry and the protective clothing industry.
The specific embodiment
Following examples will help those of ordinary skill in the art further to understand the present invention, but not limit the present invention in any form.
Embodiment 1:3, the preparation of 3 '-dihydroxybiphenyl diamines // biphenyl dianhydride (HAB//BPDA) Ju Ben Bing Er oxazole nano-fiber for production of non-woven
(1) the synthetic and electricity of polymer spins: get 3 after a certain amount of purification by the 1.0:1.0 mol ratio; 3 '-dihydroxybiphenyl diamines (HAB) and biphenyl dianhydride (BPDA) and proper amount of solvent N; N-dimethylacetylamide (DMAC), in the polymerization reaction kettle of 10 ° of C, stirring reaction 4 hours; Obtaining mass concentration is 10%, and absolute viscosity is hydroxyl polyimide precursor (polyamic acid) solution of 5.6 Pa * S.This hydroxyl polyamic acid solution is implemented electrostatic spinning in electric-field intensity is the electric field of 300 kV/m, be that 1 meter stainless steel guipure is that gatherer is collected polyamide acid nano-fiber for production of non-woven with width, and tape running speed is 3.0 m/min.
(2) imidization and two oxazoleizations: top gained polyamic acid nano-fiber for production of non-woven is placed high temperature furnace, in blanket of nitrogen, add hot imidization two oxazoleizations.Heating schedule is: with 20
°The programming rate of C/min is heated to 250 from room temperature
°C stops 10min, with 15 under this temperature
°The programming rate of C/min is heated to 350
°C, and under this temperature, stop 10min, with 15
°The speed of C/min is warming up to 450
°C stopped 10 minutes under this temperature, with 5
°The speed of C/min is warming up to 500
°C stopped 10 minutes under this temperature, cut off the electricity supply then, naturally cooled to room temperature, collected HAB//BPDA type Ju Ben Bing Er oxazole nano-fiber for production of non-woven.
(3) performance characterization: fibre diameter is that 100 ~ 300 nm, PBO nano monofilament are by force 4.5 GPa, and the formula modulus of raising is 195 GPa, and elongation at break is 3.8%; The non-weaving cloth TENSILE STRENGTH is that 75 MPa, elongation at break are 10%, heat decomposition temperature is 650 ° of C, non-weaving cloth porosity is 86%, the specific area of non-weaving cloth is 37.2 m
2/ g.
Embodiment 2:3, the preparation of 3 '-dihydroxybiphenyl diamines // biphenyl dianhydride/pyromellitic acid anhydride (HAB//BPDA/PMDA) Ju Ben Bing Er oxazole nano-fiber for production of non-woven
(1) the synthetic and electricity of polymer spins: get 3 after a certain amount of purification by the 1.0:0.7:0.3 mol ratio; 3 '-dihydroxybiphenyl diamines (HAB), biphenyl dianhydride (BPDA) and pyromellitic acid anhydride and proper amount of solvent N; N-dimethylacetylamide (DMAC), in the polymerization reaction kettle of 5 ° of C, stirring reaction 6 hours; Obtaining mass concentration is 8%, and absolute viscosity is hydroxyl polyimide precursor (polyamic acid) solution of 5.2 Pa * S.This hydroxyl polyamic acid solution is implemented electrostatic spinning in electric-field intensity is the electric field of 350 kV/m, be that 1 meter stainless steel guipure is that gatherer is collected polyamide acid nano-fiber for production of non-woven with width, and tape running speed is 3.0 m/min.
(2) imidization and two oxazoleizations: top gained polyamic acid nano-fiber for production of non-woven is placed high temperature furnace, in blanket of nitrogen, add hot imidization and two oxazoleizations.Heating schedule is: with 20
°The programming rate of C/min is heated to 250 from room temperature
°C stops 10min, with 15 under this temperature
°The programming rate of C/min is heated to 350
°C, and under this temperature, stop 10min, with 15
°The speed of C/min is warming up to 450
°C stopped 10 minutes under this temperature, with 5
°The speed of C/min is warming up to 500
°C stopped 10 minutes under this temperature, cut off the electricity supply then, naturally cooled to room temperature, collected HAB//BPDA/PMDA type Ju Ben Bing Er oxazole nano-fiber for production of non-woven.
(3) performance characterization: fibre diameter is that 80 ~ 250 nm, PBO nano monofilament are by force 5.4 GPa, and the formula modulus of raising is 260 GPa, and elongation at break is 3.0%; The non-weaving cloth TENSILE STRENGTH is that 86 MPa, elongation at break are 8%, heat decomposition temperature is 650 ° of C, non-weaving cloth porosity is 83%, the specific area of non-weaving cloth is 39.8 m
2/ g.
Embodiment 3:3, the preparation of 3 '-dihydroxybiphenyl diamines // benzophenone dianhydride/diphenyl sulfone dianhydride (DHB//BTDA/DSDA) Ju Ben Bing Er oxazole nano-fiber for production of non-woven
(1) the synthetic and electricity of polymer spins: get 3 after a certain amount of purification by the 1.0:0.5:0.5 mol ratio; 3 '-dihydroxybiphenyl diamines (HAB), benzophenone dianhydride (BTDA), diphenyl sulfone dianhydride (DSDA) and proper amount of solvent N; N-dimethylacetylamide (DMAC), in the polymerization reaction kettle of 5 ° of C, stirring reaction 4 hours; Obtaining mass concentration is 10%, and absolute viscosity is hydroxyl polyimide precursor (polyamic acid) solution of 5.0 Pa * S.This hydroxyl polyamic acid solution is implemented electrostatic spinning in electric-field intensity is the electric field of 300 kV/m, be that 1 meter stainless steel guipure is that gatherer is collected polyamide acid nano-fiber for production of non-woven with width, and tape running speed is 3.0 m/min.
(2) imidization and two oxazoleizations: top gained polyamic acid nano-fiber for production of non-woven is placed high temperature furnace, in blanket of nitrogen, add hot imidization and two oxazoleizations.Heating schedule is: with 20
°The programming rate of C/min is heated to 250 from room temperature
°C stops 10min, with 15 under this temperature
°The programming rate of C/min is heated to 350
°C, and under this temperature, stop 10min, with 15
°The speed of C/min is warming up to 450
°C stopped 10 minutes under this temperature, with 5
°The speed of C/min is warming up to 480
°C stopped 10 minutes under this temperature, cut off the electricity supply then, naturally cooled to room temperature, collected HAB//BTDA/DSDA type Ju Ben Bing Er oxazole nano-fiber for production of non-woven.
(3) performance characterization: fibre diameter is that 80 ~ 250 nm, PBO nano monofilament are by force 4.2 GPa, and the formula modulus of raising is 200 GPa, and elongation at break is 4.0%; The non-weaving cloth TENSILE STRENGTH is that 65 MPa, elongation at break are 10%, heat decomposition temperature is 630 ° of C, non-weaving cloth porosity is 82%, the specific area of non-weaving cloth is 40.5 m
2/ g.
Embodiment 4:3, the preparation of 3 '-dihydroxybiphenyl diamines // terphenyl dianhydride/biphenyl dianhydride (HAB//TPDA/BPDA) Ju Ben Bing Er oxazole nano-fiber for production of non-woven
(1) the synthetic and electricity of polymer spins: get 3 after a certain amount of purification by the 1.0:0.6:0.4 mol ratio; 3 '-dihydroxybiphenyl diamines (HAB), terphenyl dianhydride (TPDA), biphenyl dianhydride (BPDA) and proper amount of solvent N; N-dimethylacetylamide (DMAC), in the polymerization reaction kettle of 10 ° of C, stirring reaction 4 hours; Obtaining mass concentration is 8%, and absolute viscosity is hydroxyl polyimide precursor (polyamic acid) solution of 6.0 Pa * S.This hydroxyl polyamic acid solution is implemented electrostatic spinning in electric-field intensity is the electric field of 400 kV/m, be that 1 meter stainless steel guipure is that gatherer is collected polyamide acid nano-fiber for production of non-woven with width, and tape running speed is 3.0 m/min.
(2) imidization and two oxazoleizations: top gained polyamic acid nano-fiber for production of non-woven is placed high temperature furnace, in blanket of nitrogen, add hot imidization and two oxazoleizations.Heating schedule is: with 20
°The programming rate of C/min is heated to 250 from room temperature
°C stops 10min, with 15 under this temperature
°The programming rate of C/min is heated to 350
°C, and under this temperature, stop 10min, with 15
°The speed of C/min is warming up to 450
°C stopped 10 minutes under this temperature, with 5
°The speed of C/min is warming up to 500
°C stopped 10 minutes under this temperature, cut off the electricity supply then, naturally cooled to room temperature, collected HAB//TPDA/BPDA type Ju Ben Bing Er oxazole nano-fiber for production of non-woven.
(3) performance characterization: fibre diameter is that 80 ~ 250 nm, PBO nano monofilament are by force 6.2 GPa, and the formula modulus of raising is 280 GPa, and elongation at break is 3.0%; The non-weaving cloth TENSILE STRENGTH is that 90 MPa, elongation at break are 10%, heat decomposition temperature is 680 ° of C, non-weaving cloth porosity is 83%, the specific area of non-weaving cloth is 40.1 m
2/ g.
Embodiment 5:3, the preparation of 3 '-dihydroxybiphenyl diamines // terphenyl dianhydride/pyromellitic acid dianhydride (HAB//TPDA/PMDA) Ju Ben Bing Er oxazole nano-fiber for production of non-woven
(1) the synthetic and electricity of polymer spins: get 3 after a certain amount of purification by the 1.0:0.6:0.4 mol ratio; 3 '-dihydroxybiphenyl diamines (HAB), terphenyl dianhydride (TPDA), pyromellitic acid dianhydride (PMDA) and proper amount of solvent N; N-dimethylacetylamide (DMAC), in the polymerization reaction kettle of 5 ° of C, stirring reaction 3 hours; Obtaining mass concentration is 8%, and absolute viscosity is hydroxyl polyimide precursor (polyamic acid) solution of 5.5 Pa * S.This hydroxyl polyamic acid solution is implemented electrostatic spinning in electric-field intensity is the electric field of 300 kV/m, be that 1 meter stainless steel guipure is that gatherer is collected polyamide acid nano-fiber for production of non-woven with width, and tape running speed is 3.0 m/min.
(2) imidization and two oxazoleizations: top gained polyamic acid nano-fiber for production of non-woven is placed high temperature furnace, in blanket of nitrogen, add hot imidization and two oxazoleizations.Heating schedule is: with 20
°The programming rate of C/min is heated to 250 from room temperature
°C stops 10min, with 15 under this temperature
°The programming rate of C/min is heated to 350
°C, and under this temperature, stop 10min, with 15
°The speed of C/min is warming up to 450
°C stopped 10 minutes under this temperature, with 5
°The speed of C/min is warming up to 480
°C stopped 10 minutes under this temperature, cut off the electricity supply then, naturally cooled to room temperature, collected HAB//TPDA/PMDA type Ju Ben Bing Er oxazole nano-fiber for production of non-woven.
(3) performance characterization: fibre diameter is that 100 ~ 300 nm, PBO nano monofilament are by force 6.0 GPa, and the formula modulus of raising is 260 GPa, and elongation at break is 3.5%; The non-weaving cloth TENSILE STRENGTH is that 85 MPa, elongation at break are 8%, heat decomposition temperature is 660 ° of C, non-weaving cloth porosity is 84%, the specific area of non-weaving cloth is 39.8 m
2/ g.
Embodiment 6:3, the preparation of 3 '-dihydroxybiphenyl diamines // biphenyl dianhydride/benzophenone dianhydride (HAB//BPDA/BTDA) Ju Ben Bing Er oxazole nano-fiber for production of non-woven
(1) the synthetic and electricity of polymer spins: get 3 after a certain amount of purification by the 1.0:0.5:0.5 mol ratio; 3 '-dihydroxybiphenyl diamines (HAB), biphenyl dianhydride (BPDA), benzophenone dianhydride (BTDA) and proper amount of solvent N; N-dimethylacetylamide (DMAC), in the polymerization reaction kettle of 10 ° of C, stirring reaction 4 hours; Obtaining mass concentration is 10%, and absolute viscosity is hydroxyl polyimide precursor (polyamic acid) solution of 5.8 Pa * S.This hydroxyl polyamic acid solution is implemented electrostatic spinning in electric-field intensity is the electric field of 300 kV/m, be that 1 meter stainless steel guipure is that gatherer is collected polyamide acid nano-fiber for production of non-woven with width, and tape running speed is 3.0 m/min.
(2) imidization and two oxazoleizations: top gained polyamic acid nano-fiber for production of non-woven is placed high temperature furnace, in blanket of nitrogen, add hot imidization and two oxazoleizations.Heating schedule is: with 20
°The programming rate of C/min is heated to 250 from room temperature
°C stops 10min, with 15 under this temperature
°The programming rate of C/min is heated to 350
°C, and under this temperature, stop 10min, with 15
°The speed of C/min is warming up to 450
°C stopped 10 minutes under this temperature, with 5
°The speed of C/min is warming up to 480
°C stopped 10 minutes under this temperature, cut off the electricity supply then, naturally cooled to room temperature, collected HAB//BPDA/BTDA type Ju Ben Bing Er oxazole nano-fiber for production of non-woven.
(3) performance characterization: fibre diameter is that 100 ~ 300 nm, PBO nano monofilament are by force 5.8 GPa, and the formula modulus of raising is 190 GPa, and elongation at break is 4.5%; The non-weaving cloth TENSILE STRENGTH is that 95 MPa, elongation at break are 12%, heat decomposition temperature is 670 ° of C, non-weaving cloth porosity is 83%, the specific area of non-weaving cloth is 40.2 m
2/ g.
Embodiment 7:3, the preparation of 3 '-dihydroxybiphenyl diamines // biphenyl dianhydride/diphenyl sulfone dianhydride (HAB//BPDA/DSDA) Ju Ben Bing Er oxazole nano-fiber for production of non-woven
(1) the synthetic and electricity of polymer spins: get 3 after a certain amount of purification by the 1.0:0.5:0.5 mol ratio; 3 '-dihydroxybiphenyl diamines (HAB), biphenyl dianhydride (BPDA), diphenyl sulfone dianhydride (DSDA) and proper amount of solvent N; N-dimethylacetylamide (DMAC), in the polymerization reaction kettle of 5 ° of C, stirring reaction 4 hours; Obtaining mass concentration is 10%, and absolute viscosity is hydroxyl polyimide precursor (polyamic acid) solution of 5.3 Pa * S.This hydroxyl polyamic acid solution is implemented electrostatic spinning in electric-field intensity is the electric field of 300 kV/m, be that 1 meter stainless steel guipure is that gatherer is collected polyamide acid nano-fiber for production of non-woven with width, and tape running speed is 3.0 m/min.
(2) imidization and two oxazoleizations: top gained polyamic acid nano-fiber for production of non-woven is placed high temperature furnace, in blanket of nitrogen, add hot imidization and two oxazoleizations.Heating schedule is: with 20
°The programming rate of C/min is heated to 250 from room temperature
°C stops 10min, with 15 under this temperature
°The programming rate of C/min is heated to 350
°C, and under this temperature, stop 10min, with 15
°The speed of C/min is warming up to 450
°C stopped 10 minutes under this temperature, with 5
°The speed of C/min is warming up to 500
°C stopped 10 minutes under this temperature, cut off the electricity supply then, naturally cooled to room temperature, collected HAB//BPDA/DSDA type Ju Ben Bing Er oxazole nano-fiber for production of non-woven.
(3) performance characterization: fibre diameter is that 100 ~ 300 nm, PBO nano monofilament are by force 4.5 GPa, and the formula modulus of raising is 160 GPa, and elongation at break is 4.0%; The non-weaving cloth TENSILE STRENGTH is that 65 MPa, elongation at break are 8%, heat decomposition temperature is 650 ° of C, non-weaving cloth porosity is 82.5%, the specific area of non-weaving cloth is 39.3 m
2/ g.
Embodiment 8:3, the preparation of 3 '-dihydroxybiphenyl diamines // pyromellitic acid dianhydride/benzophenone dianhydride (HAB//PMDA/BTDA) Ju Ben Bing Er oxazole nano-fiber for production of non-woven
(1) the synthetic and electricity of polymer spins: get 3 after a certain amount of purification by the 1.0:0.5:0.5 mol ratio; 3 '-dihydroxybiphenyl diamines (HAB), biphenyl dianhydride (BPDA), benzophenone dianhydride (BTDA) and proper amount of solvent N; N-dimethylacetylamide (DMAC), in the polymerization reaction kettle of 3 ° of C, stirring reaction 5 hours; Obtaining mass concentration is 10%, and absolute viscosity is hydroxyl polyimide precursor (polyamic acid) solution of 4.8 Pa * S.This hydroxyl polyamic acid solution is implemented electrostatic spinning in electric-field intensity is the electric field of 300 kV/m, be that 1 meter stainless steel guipure is that gatherer is collected polyamide acid nano-fiber for production of non-woven with width, and tape running speed is 3.0 m/min.
(2) imidization and two oxazoleizations: top gained polyamic acid nano-fiber for production of non-woven is placed high temperature furnace, in blanket of nitrogen, add hot imidization and two oxazoleizations.Heating schedule is: with 20
°The programming rate of C/min is heated to 250 from room temperature
°C stops 10min, with 15 under this temperature
°The programming rate of C/min is heated to 350
°C, and under this temperature, stop 10min, with 15
°The speed of C/min is warming up to 450
°C stopped 10 minutes under this temperature, with 5
°The speed of C/min is warming up to 480
°C stopped 10 minutes under this temperature, cut off the electricity supply then, naturally cooled to room temperature, collected HAB//PMDA/BTDA type Ju Ben Bing Er oxazole nano-fiber for production of non-woven.
(3) performance characterization: fibre diameter is that 100 ~ 300 nm, PBO nano monofilament are by force 5.0 GPa, and the formula modulus of raising is 170 GPa, and elongation at break is 3.3%; The non-weaving cloth TENSILE STRENGTH is that 65 MPa, elongation at break are that 10 %, heat decomposition temperature are that the porosity of 650 ° of C, non-weaving cloth is 84%, the specific area of non-weaving cloth is 38.2 m
2/ g.
Experiment material and result test among the above embodiment
(1) experiment material:
Used 5 kinds of dianhydrides and a kind of diamines in 8 experiment embodiments of the present invention, totally 6 kinds of monomers are synthetic through commercial channel purchase or this laboratory.
1) biphenyl dianhydride (BPDA) [CAS number: 2420-87-3] is available from Changzhou Sunlight Pharmaceutical Co., Ltd.;
2) pyromellitic acid dianhydride (PMDA) [CAS number: 89-32-7] is available from the concentric chemical industry of Wuhan Han Nan Co., Ltd;
3) diphenyl sulfone dianhydride (DSDA) [CAS number: 2540-99-0] likes that available from ladder is uncommon (Shanghai) changes into industrial development Co., Ltd;
4) benzophenone dianhydride (BTDA) [CAS number: 2421-28-5] is available from lark prestige Science and Technology Ltd.;
5) terphenyl dianhydride (TPDA) [the experiment product does not have CAS number temporarily], (this laboratory is synthetic);
6) dihydroxybiphenyl diamines (HAB) (have another name called: 3,3'-dihydroxybiphenyl amine) [CAS number: 2373-98-0] is available from Jintan City, Jiangsu Province gold promise chemical industry Co., Ltd.
(2) experimental result test and sign
The experimental result of 8 experiment embodiments is to carry out conventional property testing and sign through following instrument and equipment among the present invention.
1) polymer solution and spinning solution absolute viscosity are measured with NDJ-8S viscosimeter (Shanghai exact science instrument company);
2) diameter of electro spinning nano fiber is to measure with SEM VEGA 3 SBU (Czech Republic);
3) heat decomposition temperature of PBO nanofiber is measured with WRT-3P thermal gravimetric analyzer (TGA) (Shanghai Precision Scientific Apparatus Co., Ltd);
4) engineering properties of PBO nano fiber porous film or non-weaving cloth (intensity, extension at break etc.) is measured with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd);
5) vitrification point of PBO nano fiber porous film or non-weaving cloth is to use Diamond dynamic mechanical analysis appearance (DMA) (Perkin-Elmer, the U.S.) to measure;
6) porosity of PBO nano-fiber for production of non-woven is to calculate through following formula:
Porosity b=[1-(r/r
o)] ' 100
Wherein r is the density (gram/cm of PBO nano-fiber for production of non-woven
3), r
oDensity (gram/cm for corresponding PBO entity film (through the solution casting method preparation)
3);
7) specific area of PBO nano fiber porous film or non-weaving cloth is to measure with pore size distribution of JW-K type and specific surface area measuring instrument (precise and tiny Gao Bo, Beijing science and technology Co., Ltd).
8) PBO nano monofilament measuring mechanical property is with JQ03B filament testing machine test (Shanghai Zhongchen digital technology equipment Co., Ltd)
Claims (10)
1. one kind is gathered benzene and two oxazole nano-fiber for production of non-woven; Be the polyimide precursor of hydroxyl to be handled through pyrolytic conversion make; It is characterized in that described Ju Ben Bing Er oxazole nano-fiber for production of non-woven is to be transformed under 450-500 ℃ high temperature through its precursor polyimide nano-fiber non-weaving cloth.
2. Ju Ben Bing Er oxazole nano-fiber for production of non-woven as claimed in claim 1 is characterized in that the construction unit of said Ju Ben Bing Er oxazole is following:
Wherein, R is the residue structure that the dianhydride structure division stays in pyrolytic process in the polyimide molecule.
3. Ju Ben Bing Er oxazole nano-fiber for production of non-woven as claimed in claim 2 is characterized in that said R has following structure
In a kind of.
4. Ju Ben Bing Er oxazole nano-fiber for production of non-woven as claimed in claim 2 is characterized in that, said Ju Ben Bing Er oxazole is to be formed 450-500 ℃ of following thermal transition by the polyimides with the following chemical structure formula:
。
5. polyimide structures as claimed in claim 4 is characterized in that, said R
1Has following structure
In a kind of.
6. Ju Ben Bing Er oxazole nano-fiber for production of non-woven as claimed in claim 1 is characterized in that the diameter of nanofiber is 50 ~ 800 nm in the said non-weaving cloth.
7. Ju Ben Bing Er oxazole nano-fiber for production of non-woven as claimed in claim 1 is characterized in that the decomposition temperature of said nano-fiber for production of non-woven is greater than 630-700 ℃.
8. Ju Ben Bing Er oxazole nano-fiber for production of non-woven as claimed in claim 1 is characterized in that the porosity of said nano-fiber for production of non-woven is greater than 75-90%.
9. Ju Ben Bing Er oxazole nano-fiber for production of non-woven as claimed in claim 1 is characterized in that the mechanical strength of said non-weaving cloth is 20 ~ 100 MPa.
10. as claimed in claim 1ly gather benzene and two application of oxazole nano-fiber for production of non-woven in industries such as battery diaphragm, high temperature filtration and garment material.
Priority Applications (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795285A (en) * | 2014-10-10 | 2017-05-31 | 东丽株式会社 | Polyimide solution, heat-resistant non-woven fabric and its manufacture method |
| CN110256671A (en) * | 2013-01-16 | 2019-09-20 | 日产化学工业株式会社 | The manufacturing method and display base plate resin film formation composition of display base plate resin film |
| CN115354521A (en) * | 2022-08-16 | 2022-11-18 | 西安工程大学 | Processing method of PBO fiber wet-process non-woven material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803922A (en) * | 2005-12-29 | 2006-07-19 | 上海交通大学 | Method for preparing poly(p-phenylene benzobisoxazole)/polyimide composite material |
| CN101300378A (en) * | 2005-11-04 | 2008-11-05 | 帝人株式会社 | Polyazole fiber and method for producing same |
| CN101407588A (en) * | 2008-11-26 | 2009-04-15 | 哈尔滨工业大学 | Preparation of polyimide film |
| WO2010110975A2 (en) * | 2009-03-27 | 2010-09-30 | Uop Llc | High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes |
| 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 |
| CN102099512A (en) * | 2008-05-19 | 2011-06-15 | 汉阳大学校产学协力团 | Hollow fiber, dope solution composition for forming a hollow fiber, and method for manufacturing a hollow fiber using the same |
-
2011
- 2011-11-17 CN CN2011103637361A patent/CN102560894A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300378A (en) * | 2005-11-04 | 2008-11-05 | 帝人株式会社 | Polyazole fiber and method for producing same |
| CN1803922A (en) * | 2005-12-29 | 2006-07-19 | 上海交通大学 | Method for preparing poly(p-phenylene benzobisoxazole)/polyimide composite material |
| CN102099512A (en) * | 2008-05-19 | 2011-06-15 | 汉阳大学校产学协力团 | Hollow fiber, dope solution composition for forming a hollow fiber, and method for manufacturing a hollow fiber using the same |
| CN101407588A (en) * | 2008-11-26 | 2009-04-15 | 哈尔滨工业大学 | Preparation of polyimide film |
| WO2010110975A2 (en) * | 2009-03-27 | 2010-09-30 | Uop Llc | High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256671A (en) * | 2013-01-16 | 2019-09-20 | 日产化学工业株式会社 | The manufacturing method and display base plate resin film formation composition of display base plate resin film |
| CN106795285A (en) * | 2014-10-10 | 2017-05-31 | 东丽株式会社 | Polyimide solution, heat-resistant non-woven fabric and its manufacture method |
| JPWO2016056480A1 (en) * | 2014-10-10 | 2017-07-20 | 東レ株式会社 | Polyimide solution, heat-resistant nonwoven fabric, and method for producing the same |
| EP3216819A4 (en) * | 2014-10-10 | 2018-09-05 | Toray Industries, Inc. | Polyimide solution, heat-resistant non-woven fabric, and method for manufacturing same |
| CN106795285B (en) * | 2014-10-10 | 2020-06-05 | 东丽株式会社 | Polyimide solution, heat-resistant nonwoven fabric, and method for producing same |
| TWI732745B (en) * | 2014-10-10 | 2021-07-11 | 日商東麗股份有限公司 | Heat-resistant non-woven fabric, its manufacturing method and its application |
| CN115354521A (en) * | 2022-08-16 | 2022-11-18 | 西安工程大学 | Processing method of PBO fiber wet-process non-woven material |
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