CN1644772A - Preparation of poly-p-phenylene benzodioxazole fibers - Google Patents
Preparation of poly-p-phenylene benzodioxazole fibers Download PDFInfo
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- CN1644772A CN1644772A CN 200410099003 CN200410099003A CN1644772A CN 1644772 A CN1644772 A CN 1644772A CN 200410099003 CN200410099003 CN 200410099003 CN 200410099003 A CN200410099003 A CN 200410099003A CN 1644772 A CN1644772 A CN 1644772A
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Abstract
A process for preparing poly-p-phenylene benzdioxazole (PBO) fibres includes such steps as prepolymerizing by adding part (90-99%) of terephthalic acid to obtain low-viscosity prepolymer, mixing the rest of terephthalic acid with polyphosphoric acid (PPA) to obtain slurry, mixing it with prepolymer and polycondensating in a dual-screw extruder, and liquid-crystal spinning.
Description
Technical field
The present invention relates to a kind of polyparaphenylene Ben Bing Er oxazole (PBO) fiber preparation method.
Background technology
Polyparaphenylene's benzene and two oxazoles (PBO) fiber are spun company and are successfully realized suitability for industrialized production the nineties in last century by the invention of USAF material laboratory, the participation development of Dow chemical company, Japanese Japan, and its commodity are called " Zylon ".The TENSILE STRENGTH of Zylon is 5.8GPa, and stretch modulus is 300GPa, is respectively the twice of aramid fiber; In addition, Zylon also has excellent heat endurance (heat decomposition temperature is up to 650 ℃) and anti-flammability (LOI=68).Therefore, pbo fiber has important use to be worth in fields such as Aero-Space, defence and military, communications and transportation, sports equipment, building, high temperature protections, the irreplaceable effect of other material is arranged.Particularly the mankind entered since the information age, and the competition of various countries aspect overall national strength is growing more intense, and the developmental research of future war weaponry and space resources is deepened continuously, and these need be support with lighter, stronger, more energy-conservation advanced material all.Be the development of high-strength, the Gao Mo of representative, high temperature resistant, flame-retarding high performance fibrous material and advanced composite material thereof with PBO and be applied in the development level that has reflected a national hard-core technology to a certain extent, and become the material resources that a class has strategic importance.
At present, Chang Gui method is: pbo fiber is by terephthalic acid (TPA) (TPA) and 4, and 6-diamino resorcin hydrochlorate (DAR) polymerization in polyphosphoric acids (PPA) medium obtains the polymer solution that obtains again with the fiber spinning from crystalline state technology.The PBO synthetic route is as follows:
The key of the pbo fiber that processability is good is the preparation and the spinning moulding technology thereof of high molecular weight PBO polymer.In the polymerization later stage, the viscosity of polymerization system rises very fast, the viscosity of PBO/PPA solution is looked the unusual more than 2000Pas (180 ℃) of PBO molecular weight, this can cause following problem: the one, and polymerization system can stick into one and be attached on the agitator, make agitator lose mixed function, use special agitator (patent: ZL 02294359.5) though can partly address this problem, only the molecular weight of PBO still is difficult to improve like this; The 2nd, polymerization system viscosity height, mobile poor, and can not contact (otherwise PPA moisture absorption) with air, so just be difficult to polymer material is transferred to screw extruder with spinning moulding.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of polyparaphenylene Ben Bing Er oxazole fiber preparation method, addressing the above problem, thereby realize stable, the serialization production of fiber.
Method of the present invention comprises the steps:
The polymerization of PBO is divided into pre-polymerization and two stages of aftercondensated, terephthalic acid (TPA) during pre-polymerization (TPA) inventory is 90～99% of total inventory, the slurry of the low viscosity performed polymer that obtains after the pre-polymerization, 1 remaining～10%TPA and polyphosphoric acids (PPA), mix by double screw extruder, finish aftercondensated, and then be transported to filament spinning component and carry out fiber spinning from crystalline state.Specifically comprise the steps:
(1) with 4, the terephthalic acid (TPA) (TPA) and the P of 6-diamino resorcin hydrochlorate (DAR), polyphosphoric acids (PPA), total inventory 90～99%
2O
5Under 120～185 ℃ temperature, react, reaction time is 20～24 hours, other reaction conditions can be with reference to the method for Chinese patent (CN 1513899A) description, obtain performed polymer, zero of resulting PBO/PPA solution is cut viscosity and is about 320Pas (under 185 ℃), and the inherent viscosity of PBO is [η]=2～15dL/g at this moment;
4, the feeding quantity of 6-diamino resorcin hydrochlorate is 1.283 times of terephthalic acid (TPA) gross weight; Mol ratios such as DAR and TPA must guarantee;
The feeding quantity of polyphosphoric acids (PPA) is 7～9 times of terephthalic acid (TPA) (TPA) weight; The preferred P that uses
2O
5Weight concentration is the polyphosphoric acids of 70～85wt%;
P
2O
5Feeding quantity be 0.5～0.6 times of polyphosphoric acids weight;
According to the present invention, can preferably adopt patent: ZL 02294359.5 disclosed special agitator;
(2) with polyphosphoric acids (PPA), P
2O
5Slurry and the performed polymer formed with the terephthalic acid (TPA) (TPA) of surplus are transported to double screw extruder simultaneously, and extrusion reaction obtains the aftercondensated product, and the inherent viscosity of the PBO that aftercondensated obtains is=10～30dL/g;
The feeding quantity of polyphosphoric acids (PPA) is 10～30 times of terephthalic acid (TPA) (TPA) weight; The preferred P that uses
2O
5Weight concentration is the polyphosphoric acids of 70～85wt%;
P
2O
5Feeding quantity be 0.5～0.6 times of polyphosphoric acids weight;
The weight of TPA/PPA slurry is 5～10% of performed polymer weight;
TPA/PPA slurry and the performed polymer time of staying in double screw extruder is 10～20min;
Screw rod divides three warm areas, and temperature is set at 180～185 ℃, 180～185 ℃ and 185～190 ℃ respectively;
The aftercondensated product is delivered to filament spinning component carries out fiber spinning from crystalline state, temperature is 185～190 ℃, the solution thread is after 60～70 ℃, length are the air gap of 25～35cm, to enter coagulating bath through excess temperature, and coagulating agent is that weight concentration is the phosphate aqueous solution of 10～25wt%, the gained fiber enters water-bath again, remove residual phosphoric acid with further washing, reel winding speed 90～110m/min, in 95～105 ℃ of vacuumize 0.5～2h, obtain flavous pbo fiber at last.
Adopt GB/T14335-1993 to detect, the fiber number of product fiber is 1.6～3.5dtex, adopts GB/T14344-1993 to detect, is the TENSILE STRENGTH of fiber? 1～4.5GPa, extension at break is 1～3%, heat decomposition temperature is 450～650 ℃ in the air.
Said fiber spinning from crystalline state refers to " being in the spinning of the polymeric liquid (melting body or solution) under the liquid crystal state ", and (make progress with performance study for Li Jinhuan, topaz east by synthetic, spinning, the microfacies structure of Xu Hui .PBO fiber at document for this fiber spinning from crystalline state technology.Polymer material science and engineering.2003,19 (6): detailed description has been arranged 46-50).
Adopt the inherent viscosity of the prepared polyparaphenylene Ben Bing Er oxazole (PBO) of method of the present invention can reach 10～30dL/g, this method is particularly conducive to the conveying of polymer material, avoid it to contact the back moisture absorption with air, can form the continuous process flow process of PBO polymerization, spinning in view of the above.
The specific embodiment
Embodiment 1
In the 5L prepolymerization kettle that is equipped with agitator described in the patent (ZL 02294359.5), add 4 of 225.8g successively, the P of 6-diamino resorcin hydrochlorate (DAR), 1045.6g
2O
5Concentration is the polyphosphoric acids (PPA), 157.59g terephthalic acid (TPA) (TPA, total inventory 90%) of 80wt% and the P of 539g
2O
5, sealed reactor.
Reactor internal reaction material is warming up to 50 ℃, kept 1 hour, material is tentatively mixed, slowly be warming up to 65 ℃ again, kept 1 hour, material is further dissolved.
In reactor, fill the dry high purity nitrogen of purchase, make reacting kettle inner pressure reach 1.0MPa, be warming up to 120 ℃ simultaneously, kept 7 hours, open relief valve, remove reacting kettle inner pressure.Reaction mass is warming up to 145 ℃ again, reacted 6 hours, residue HCl is discharged fully, be muted color, remove vacuum in the reactor then, then reaction mass is warming up to 185 ℃, reacted 12 hours until detecting at gas escape orifice place with the pH test paper.Zero of resulting PBO/PPA solution is cut viscosity and is about 320Pas (under 185 ℃), and the inherent viscosity of PBO is [η]=1.83dL/g at this moment.
In the later stage of above-mentioned reaction, in having the 2L slurry still of agitator described in the patent (ZL 02294359.5), another one adds the P of 400g
2O
5Concentration is the PPA of 80wt%, the P of 210g
2O
5With the TPA of 100g, be warming up to 185 ℃ then, stir, obtain the TPA/PPA slurry of thickness.
With measuring pump performed polymer and TPA/PPA slurry are transported to the double screw extruder of φ 25 * 2, L/D=30 simultaneously respectively, the rotating speed of control measuring pump, the conveying capacity that makes performed polymer is 100g/min; The conveying capacity that makes the TPA/PPA slurry is 6.58g/min; The rotating speed of control double screw extruder makes the time of staying of mixed material in screw rod maintain 10min.Screw rod divides three warm areas, and temperature is set at 185 ℃, 185 ℃ and 190 ℃ respectively.The inherent viscosity of the PBO that obtains after aftercondensated is finished is=7.21dL/g.
Material goes out to be delivered to filament spinning component by measuring pump behind two spiral shell extruders and to carry out fiber spinning from crystalline state.It is 0.09mm that orifice diameter is adopted in spinning, and the spinneret orifice number is 32 spinnerets, carries out spinning in 190 ℃.The solution thread is after 65 ℃, length are the air gap of 30cm, to enter coagulating bath through excess temperature, and coagulating agent is phosphate aqueous solution (a 20wt% phosphoric acid).The gained fiber enters in the tank again, is wound on the bobbin winding speed 100m/min, dry 1h in 100 ℃ of vacuum drying ovens after further residual phosphoric acid is removed in washing.Obtain flavous fiber at last, adopt GB/T14335-1993 and GB/T14344-1993 standard to detect: fiber number is 1.67dtex, and the TENSILE STRENGTH of fiber is 0.86GPa, and extension at break is 2%, and heat decomposition temperature is 482 ℃ in the air.
Embodiment 2
In the 5L prepolymerization kettle that is equipped with agitator described in the patent (ZL 02294359.5), add 4 of 225.8g successively, the P of 6-diamino resorcin hydrochlorate (DAR), 1045.6g
2O
5Concentration is the polyphosphoric acids (PPA), 162.84g terephthalic acid (TPA) (TPA, total inventory 93%) of 80wt% and the P of 539g
2O
5, sealed reactor.
Reactor internal reaction material is warming up to 50 ℃, kept 1 hour, material is tentatively mixed, slowly be warming up to 65 ℃ again, kept 1 hour, material is further dissolved.
In reactor, fill the dry high purity nitrogen of purchase, make reacting kettle inner pressure reach 1.0MPa, be warming up to 120 ℃ simultaneously, kept 7 hours, open relief valve, remove reacting kettle inner pressure.Reaction mass is warming up to 145 ℃ again, reacted 6 hours, residue HCl is discharged fully, be muted color, remove vacuum in the reactor then, then reaction mass is warming up to 185 ℃, reacted 12 hours until detecting at gas escape orifice place with the pH test paper.Zero of resulting PBO/PPA solution is cut viscosity and is about 550Pas (under 185 ℃), and the inherent viscosity of PBO is [η]=4.72dL/g at this moment.
In the later stage of above-mentioned reaction, in having the 2L slurry still of agitator described in the patent (ZL 02294359.5), another one adds the P of 400g
2O
5Concentration is the PPA of 80wt%, the P of 210g
2O
5With the TPA of 70g, be warming up to 185 ℃ then, stir, obtain the TPA/PPA slurry of thickness.
With measuring pump performed polymer and TPA/PPA slurry are transported to the double screw extruder of φ 25 * 2, L/D=30 simultaneously respectively, the rotating speed of control measuring pump, the conveying capacity that makes performed polymer is 100g/min; The conveying capacity that makes the TPA/PPA slurry is 6.28g/min; The rotating speed of control double screw extruder makes the time of staying of mixed material in screw rod maintain 20min.Screw rod divides three warm areas, and temperature is set at 185 ℃, 185 ℃ and 190 ℃ respectively.The inherent viscosity of the PBO that obtains after aftercondensated is finished is=11.94dL/g.
Material goes out to be delivered to filament spinning component by measuring pump P3 behind the twin-screw and to carry out fiber spinning from crystalline state.It is 0.09mm that orifice diameter is adopted in spinning, and the spinneret orifice number is 32 spinnerets, carries out spinning in 190 ℃.The solution thread is after 65 ℃, length are the air gap of 30cm, to enter coagulating bath through excess temperature, and coagulating agent is phosphate aqueous solution (a 20wt% phosphoric acid).The gained fiber enters in the tank again, is wound on the bobbin winding speed 85m/min, dry 1h in 100 ℃ of vacuum drying ovens after further residual phosphoric acid is removed in washing.Obtain flavously at last, fiber number is the pbo fiber of 1.82dtex, and the TENSILE STRENGTH of fiber is 1.64GPa, and extension at break is 3%, and heat decomposition temperature is 596 ℃ in the air.
Embodiment 3
In the 5L prepolymerization kettle that is equipped with agitator described in the patent (ZL 02294359.5), add 4 of 225.8g successively, the P of 6-diamino resorcin hydrochlorate (DAR), 1045.6g
2O
5Concentration is the polyphosphoric acids (PPA), 168.1g terephthalic acid (TPA) (TPA, total inventory 96%) of 80wt% and the P of 539g
2O
5, sealed reactor.
Reactor internal reaction material is warming up to 50 ℃, kept 1 hour, material is tentatively mixed, slowly be warming up to 65 ℃ again, kept 1 hour, material is further dissolved.
In reactor, fill the dry high purity nitrogen of purchase, make reacting kettle inner pressure reach 1.0MPa, be warming up to 120 ℃ simultaneously, kept 7 hours, open relief valve, remove reacting kettle inner pressure.Reaction mass is warming up to 145 ℃ again, reacted 6 hours, residue HCl is discharged fully, be muted color, remove vacuum in the reactor then, then reaction mass is warming up to 185 ℃, reacted 12 hours until detecting at gas escape orifice place with the pH test paper.Zero of resulting PBO/PPA solution is cut viscosity and is about 940Pas (under 185 ℃), and the inherent viscosity of PBO is [η]=8.86dL/g at this moment.
In the later stage of above-mentioned reaction, in having the 2L slurry still of agitator described in the patent (ZL 02294359.5), another one adds the P of 500g
2O
5Concentration is the PPA of 80wt%, the P of 250g
2O
5With the TPA of 50g, be warming up to 185 ℃ then, stir, obtain the TPA/PPA slurry of thickness.
With measuring pump performed polymer and TPA/PPA slurry are transported to the double screw extruder of φ 25 * 2, L/D=30 simultaneously respectively, the rotating speed of control measuring pump, making the conveying capacity of performed polymer is 100g/min, the conveying capacity that makes the TPA/PPA slurry is 5.89g/min; The rotating speed of control twin-screw R3 makes the time of staying of mixed material in screw rod maintain 15min.Screw rod divides three warm areas, and temperature is set at 185 ℃, 185 ℃ and 190 ℃ respectively.The inherent viscosity of the PBO that obtains after aftercondensated is finished is=24.34dL/g.
Material goes out to be delivered to filament spinning component by measuring pump behind the double screw extruder and to carry out fiber spinning from crystalline state.It is 0.09mm that orifice diameter is adopted in spinning, and the spinneret orifice number is 32 spinnerets, carries out spinning in 190 ℃.The solution thread is after 65 ℃, length are the air gap of 30cm, to enter coagulating bath through excess temperature, and coagulating agent is phosphate aqueous solution (a 20wt% phosphoric acid).The gained fiber enters in the tank again, is wound on the bobbin winding speed 60m/min, dry 1h in 100 ℃ of vacuum drying ovens after further residual phosphoric acid is removed in washing.Obtain flavously at last, fiber number is the pbo fiber of 2.37dtex, and the TENSILE STRENGTH of fiber is 4.41GPa, and extension at break is 2%, and heat decomposition temperature is 630 ℃ in the air.
Embodiment 4
In the 5L prepolymerization kettle that is equipped with agitator described in the patent (ZL 02294359.5), add 4 of 225.8g successively, the P of 6-diamino resorcin hydrochlorate (DAR), 1045.6g
2O
5Concentration is the polyphosphoric acids (PPA), 173.35g terephthalic acid (TPA) (TPA, total inventory 99%) of 80wt% and the P of 539g
2O
5, sealed reactor.
Reactor internal reaction material is warming up to 50 ℃, kept 1 hour, material is tentatively mixed, slowly be warming up to 65 ℃ again, kept 1 hour, material is further dissolved.
In reactor, fill the dry high purity nitrogen of purchase, make reacting kettle inner pressure reach 1.0MPa, be warming up to 120 ℃ simultaneously, kept 7 hours, open relief valve, remove reacting kettle inner pressure.Reaction mass is warming up to 145 ℃ again, reacted 6 hours, residue HCl is discharged fully, be muted color, remove vacuum in the reactor then, then reaction mass is warming up to 185 ℃, reacted 12 hours until detecting at gas escape orifice place with the pH test paper.Zero of resulting PBO/PPA solution is cut viscosity and is about 1340Pas (under 200 ℃), and the inherent viscosity of PBO is [η]=14.36dL/g at this moment.
In the later stage of above-mentioned reaction, in having the 2L slurry still of agitator described in the patent (ZL 02294359.5), another one adds the P of 300g
2O
5Concentration is the PPA of 80wt%, the P of 165g
2O
5With the TPA of 10g, be warming up to 185 ℃ then, stir, obtain the TPA/PPA slurry of thickness.
With measuring pump performed polymer and TPA/PPA slurry are transported to the double screw extruder of φ 25 * 2, L/D=30 simultaneously respectively, the rotating speed of control measuring pump, making the conveying capacity of performed polymer is 100g/min, the conveying capacity that makes the TPA/PPA slurry is 4.36g/min; The rotating speed of control twin-screw R3 makes the time of staying of mixed material in screw rod maintain 10min.Screw rod divides three warm areas, and temperature is set at 190 ℃, 195 ℃ and 200 ℃ respectively.The inherent viscosity of the PBO that obtains after aftercondensated is finished is=21.73dL/g.
Material goes out to be delivered to filament spinning component by measuring pump behind the double screw extruder and to carry out fiber spinning from crystalline state.It is 0.09mm that orifice diameter is adopted in spinning, and the spinneret orifice number is 32 spinnerets, carries out spinning in 200 ℃.The solution thread is after 65 ℃, length are the air gap of 30cm, to enter coagulating bath through excess temperature, and coagulating agent is phosphate aqueous solution (a 20wt% phosphoric acid).The gained fiber enters in the tank again, is wound on the bobbin winding speed 40m/min, dry 1h in 100 ℃ of vacuum drying ovens after further residual phosphoric acid is removed in washing.Obtain flavously at last, fiber number is the pbo fiber of 2.43dtex, and the TENSILE STRENGTH of fiber is 3.36GPa, and extension at break is 2%, and heat decomposition temperature is 600 ℃ in the air.
Claims (5)
1. polyparaphenylene's benzene and two oxazole fiber preparation method is characterized in that, comprise the steps:
(1) with 4, the terephthalic acid (TPA) and the P of 6-diamino resorcin hydrochlorate, polyphosphoric acids, total inventory 90～99%
2O
5React under 120～185 ℃ temperature, the reaction time is 20～24 hours, obtains performed polymer;
4, the feeding quantity of 6-diamino resorcin hydrochlorate is 1.283 times (mol ratios 1: 1) of terephthalic acid (TPA) gross weight;
The feeding quantity of polyphosphoric acids is 7～9 times of terephthalic acid (TPA) weight;
P
2O
5Feeding quantity be 0.5～0.6 times of polyphosphoric acids weight;
(2) with polyphosphoric acids, P
2O
5Slurry and the performed polymer formed with the terephthalic acid (TPA) of surplus are transported to double screw extruder simultaneously, finish reactivity and extrude in screw rod, obtain the aftercondensated product;
The feeding quantity of polyphosphoric acids is 10～30 times of terephthalic acid (TPA) weight;
P
2O
5Feeding quantity be 0.5～0.6 times of polyphosphoric acids weight;
The weight of TPA/PPA slurry is 5～10% of performed polymer weight;
(3) the aftercondensated product is delivered to filament spinning component and carries out fiber spinning from crystalline state.
2. method according to claim 1 is characterized in that, uses P
2O
5Weight concentration is the polyphosphoric acids of 70～85wt%.
3. method according to claim 1 is characterized in that, slurry and the performed polymer time of staying in double screw extruder is 10～20min.
4. method according to claim 1 is characterized in that, screw extruder divides three warm areas, and temperature is set at 180～185 ℃, 180～185 ℃ and 185～190 ℃ respectively.
5. according to each described method of claim 1～4, it is characterized in that, fiber spinning from crystalline state comprises the steps: that temperature is 185～190 ℃, and the solution thread is after 60～70 ℃, length are the air gap of 25～35cm, to enter coagulating bath through excess temperature, coagulating agent is that weight concentration is the phosphate aqueous solution of 10～25wt%, the gained fiber enters water-bath again, reels winding speed 90～110m/min, in 95～105 ℃ of vacuumize 0.5～2h, obtain fiber.
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| CN 200410099003 CN1644772A (en) | 2004-12-24 | 2004-12-24 | Preparation of poly-p-phenylene benzodioxazole fibers |
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|---|---|---|---|
| CN 200410099003 CN1644772A (en) | 2004-12-24 | 2004-12-24 | Preparation of poly-p-phenylene benzodioxazole fibers |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094255A (en) * | 2010-12-23 | 2011-06-15 | 哈尔滨工业大学 | Method for industrial continuous polymerization of poly (p-phenylenebenzobisoxazole) (PBO) |
| CN101381902B (en) * | 2008-07-25 | 2011-11-09 | 东华大学 | Method for preparing poly (p-phenylene-2,6-benzoxazole) filament by semi continuous method |
| CN102604090A (en) * | 2012-01-09 | 2012-07-25 | 东华大学 | Preparation method of liquid crystalline polyimide solution |
| CN102634023A (en) * | 2012-04-24 | 2012-08-15 | 哈尔滨工业大学 | Preparation method of poly-p-phenylenebenzobisthiazole (PBO) polymer |
| CN103305967A (en) * | 2013-07-03 | 2013-09-18 | 陕西元丰纺织技术研究有限公司 | Method for spinning poly-p-phenylenebenzobisthiazole (PBO) fibres |
| CN107761185A (en) * | 2017-11-20 | 2018-03-06 | 成都新晨新材科技有限公司 | A kind of process control method for pbo fiber production |
| CN107815745A (en) * | 2017-11-09 | 2018-03-20 | 成都新晨新材科技有限公司 | A kind of method for producing pbo fiber |
| CN109778338A (en) * | 2017-11-14 | 2019-05-21 | 中蓝晨光化工有限公司 | A kind of production technology of polyparaphenylene's benzo dioxazole fiber continuous polymerization spinning |
| CN109778342A (en) * | 2017-11-14 | 2019-05-21 | 中蓝晨光化工有限公司 | A kind of native staining method of polyparaphenylene's benzo dioxazole fiber |
| CN109943906A (en) * | 2017-12-21 | 2019-06-28 | 中蓝晨光化工有限公司 | A kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof |
-
2004
- 2004-12-24 CN CN 200410099003 patent/CN1644772A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381902B (en) * | 2008-07-25 | 2011-11-09 | 东华大学 | Method for preparing poly (p-phenylene-2,6-benzoxazole) filament by semi continuous method |
| CN102094255A (en) * | 2010-12-23 | 2011-06-15 | 哈尔滨工业大学 | Method for industrial continuous polymerization of poly (p-phenylenebenzobisoxazole) (PBO) |
| CN102604090B (en) * | 2012-01-09 | 2013-10-23 | 东华大学 | Preparation method of liquid crystalline polyimide solution |
| CN102604090A (en) * | 2012-01-09 | 2012-07-25 | 东华大学 | Preparation method of liquid crystalline polyimide solution |
| CN102634023A (en) * | 2012-04-24 | 2012-08-15 | 哈尔滨工业大学 | Preparation method of poly-p-phenylenebenzobisthiazole (PBO) polymer |
| CN103305967B (en) * | 2013-07-03 | 2015-07-08 | 陕西元丰纺织技术研究有限公司 | Method for spinning poly-p-phenylenebenzobisthiazole (PBO) fibres |
| CN103305967A (en) * | 2013-07-03 | 2013-09-18 | 陕西元丰纺织技术研究有限公司 | Method for spinning poly-p-phenylenebenzobisthiazole (PBO) fibres |
| CN107815745A (en) * | 2017-11-09 | 2018-03-20 | 成都新晨新材科技有限公司 | A kind of method for producing pbo fiber |
| CN109778338A (en) * | 2017-11-14 | 2019-05-21 | 中蓝晨光化工有限公司 | A kind of production technology of polyparaphenylene's benzo dioxazole fiber continuous polymerization spinning |
| CN109778342A (en) * | 2017-11-14 | 2019-05-21 | 中蓝晨光化工有限公司 | A kind of native staining method of polyparaphenylene's benzo dioxazole fiber |
| CN109778338B (en) * | 2017-11-14 | 2021-06-15 | 中蓝晨光化工有限公司 | Production process for continuous polymerization spinning of poly (p-phenylene benzobisoxazole) fibers |
| CN107761185A (en) * | 2017-11-20 | 2018-03-06 | 成都新晨新材科技有限公司 | A kind of process control method for pbo fiber production |
| CN107761185B (en) * | 2017-11-20 | 2018-09-18 | 成都新晨新材科技有限公司 | A kind of process control method for pbo fiber production |
| CN109943906A (en) * | 2017-12-21 | 2019-06-28 | 中蓝晨光化工有限公司 | A kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof |
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