CN101613892B - Preparation method of poly(p-phenylene benzobisoxazole) composite fiber containing nano-TiO2 - Google Patents
Preparation method of poly(p-phenylene benzobisoxazole) composite fiber containing nano-TiO2 Download PDFInfo
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- CN101613892B CN101613892B CN2009100547436A CN200910054743A CN101613892B CN 101613892 B CN101613892 B CN 101613892B CN 2009100547436 A CN2009100547436 A CN 2009100547436A CN 200910054743 A CN200910054743 A CN 200910054743A CN 101613892 B CN101613892 B CN 101613892B
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Abstract
The invention relates to a poly(p-phenylene benzobisoxazole) (PBO) composite fiber containing nano-TiO2 preparation method, comprising the following steps: dissolving 4,6-diaminoresorcinol hydrochloride and terephthalic acid and a certain number of phosphorus pentoxide in equal molar ratio in polyphosphoric acid, removing hydrogen chloride gas, heating and polymerizing to obtain poly(p-phenylene benzobisoxazole), then adding poly(p-phenylene benzobisoxazole) and phosphoric acid solution containing nano-TiO2 in a double-screw extruder and obtaining PBO composite fiber containing nano-TiO2 by dry-jet wet spinning; the invention uses nano-TiO2 particles with ultraviolet shielding property and utilizes the strong shearing and high effective blending of the double-screw extruder to prepare the composite fiber; compared with pure PBO fiber, the ultraviolet aging resistance property is effectively improved while the mechanical properties are not reduced.
Description
[technical field]
The present invention relates to the synthetic and preparing technical field of compound, be specifically related to a kind of preparation method who contains the polyparaphenylene benzene and the two oxazole composite fibres of nano titanium oxide.
[background technology]
Polyphenylene Ben Bing Er oxazole (Poly-p-phenylene benzobisthiazole), be called for short PBO, it is a kind of lyotropic liquid crystal macromolecule, have high strength, high-modulus, high temperature resistant and excellent specific property that environmental stability is good, its performance surpasses famous Kevlar fiber, and a new generation that is regarded as advanced configuration composite in the fields such as Aeronautics and Astronautics, national defence, celestial body detecting strengthens the body fiber.
But according to " DOW Chemical " and " Japan is spun ", the mechanical strength of pbo fiber fiber under the ultraviolet-visible light irradiation can descend by a relatively large margin.Peter. the outstanding person. watt assorted people such as (Peter J.Walsh) finds that pbo fiber is through 750W/m
2Ultraviolet-visible light irradiation after 150 hours and 270 hours, the forfeiture of the fiber surface degree of order.So they consider still, can not effectively stop the light degradation of fiber like this at pbo fiber surface applied one deck flake graphite, powdery carbon black and glassy state titanium dioxide.Therefore, how to overcome the illumination ageing of pbo fiber, just become the technical problem that this area needs to be resolved hurrily.
[summary of the invention]
The object of the present invention is to provide a kind of preparation method of pbo fiber of anti-illumination ageing, to overcome the defective of existing pbo fiber.
For achieving the above object, the technical scheme taked of the present invention is:
A kind of preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide may further comprise the steps:
(1) adopting hydrophilic rutile type nano titanic oxide is raw material, and its particle diameter is between 30～60nm;
(2) 1 parts by mass nano titanium oxide being scattered in 200 parts by mass, concentration is 85% phosphoric acid (H
3PO
4) in, add the phosphorus pentoxide (P of 170～310 parts by mass after ultrasonic
2O
5), making the mass fraction of phosphorus pentoxide in solution is 80～85%, makes through stirring to contain nano titanium oxide dispersion again;
(3) with polyphosphoric acids (PPA), etc. mol ratio 4,6-diamino resorcin hydrochlorate (DAR2HCl) adds in the reactor with terephthalic acid (TPA) (TA), begin to stir, under 110～120 ℃ of conditions, vacuumized 30 hours, remove hydrogen chloride (HCl), the polymerisation that progressively heats up under 130～160 ℃ of conditions then 20 hours makes polyparaphenylene Ben Bing Er oxazole (PBO) pre-polymer solution;
(4) nano titanium oxide dispersion and polyparaphenylene Ben Bing Er oxazole (PBO) pre-polymer solution are placed engagement type double screw extruder in the same way, the screw speed of double screw extruder is 10～200rpm, screw slenderness ratio is greater than 30, material stopped in the engagement type double screw extruder 10～60 minutes, the degree of polymerization and the polymerisation degree of polyparaphenylene Ben Bing Er oxazole are further improved, under 180～210 ℃ of conditions, react then and extrude, obtain containing the polyparaphenylene Ben Bing Er oxazole polymer of nano titanium oxide;
(5) the polyparaphenylene benzene that will contain nano titanium oxide is also done spray-wet spinning spinning behind the two oxazole polymer filtrations, obtain containing the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide, the content of nano titanium oxide is 1～10wt.% in the composite fibre.
The terephthalic acid (TPA) (TA) that above-mentioned steps (3) adopts passes through the air-flow pulverization process in advance, and the terephthalic acid (TPA) average grain diameter after the processing is below 4 μ m, and 90% less than 6 μ m; Terephthalic acid (TPA) after the processing (TA) should be kept in the vacuum desiccator, must be in 95 ℃ of baking ovens before using drying 24 hours.
In step (3), the employed agitator of reactor is a double ribbon agitator, and the hand of spiral of its hurricane band is identical with mixing direction; Reactor is in negative pressure state always.
In step (3), under 100 ℃ of conditions, outgas naturally earlier, progressively strengthen vacuum then and vacuumize and remove hydrogen chloride.
The polymerisation that progressively heats up under 130～160 ℃ of conditions in the described step (3) is: 130 ℃ kept 4 hours down, and 140 ℃ kept 2 hours down, and 150 ℃ kept 5 hours down, and 160 ℃ kept 4 hours down.
In the described step (3), emit on the material under the too high prerequisite not influencing, progressively improve the speed of agitator of reactor, maximum can be to 80rpm; Adjusting agitator counter-rotating in per 20 minutes 1 minute, the phenomenon of uniting appears in material in reactor.
Described be transferred to polyparaphenylene Ben Bing Er oxazole (PBO) pre-polymer solution in the engagement type double screw extruder before, should earlier polyparaphenylene Ben Bing Er oxazole (PBO) pre-polymer solution be inserted in the storage tank that has attemperator and be incubated, at this moment, the temperature of storage tank tank skin is 150～170 ℃, the temperature of base plate is 160～180 ℃, and then is pressed in the engagement type double screw extruder by hydraulic pump.
The engagement type double screw extruder that adopts in the described step (4) mainly is made up of two screw rods that mesh in the same way, contains the reverse thread groove on the forward screw thread, so that make material reach abundant mixing within a short period of time, thereby improves the uniformity of polymer solution.
Good effect of the present invention is:
With double screw extruder as reactor, the characteristics of utilizing its efficient blend and reaction to extrude, the advantages of situ aggregation method and physical blending method is got up, both be fit to the industrialization manufacturing of composite fibre, can make full use of the performance of nano titanium oxide again, obtain PBO composite fibre with excellent anti ultraviolet ageing performance.
[specific embodiment]
A comparative example and four embodiment of the preparation method of the polyparaphenylene Ben Bing Er oxazole composite fibre that the present invention contains nano titanium oxide below are provided.
Comparative example
In the 50L reactor that has double spiral agitator, adding 8660g phosphorus pentoxide concentration successively is the polyphosphoric acids (PPA) of 80.6wt.%, terephthalic acid (TPA) (TA), the 5386gP that the 1560g average grain diameter is 4 μ m
2O
5, 2000g 4,6-diamino resorcin hydrochlorate (DAR2HCl) and 10g stannous chloride (SnCl
2), sealed reactor starts stirring, and in 100 ℃ of following degassings naturally.
Vacuumize after 2 hours, under the prerequisite of not overflow, progressively strengthen vacuum to the vacuum meter maximum range.Progressively improve rotating speed to 60～80rpm then, adjusting agitator counter-rotating in per 20 minutes 1 minute; Be warming up to 110 ℃ after 24 hours, keep being warming up to 120 ℃ after 8 hours, assert after 2 hours that (inspection removing hydrogen chloride degree adopts liquor argenti nitratis ophthalmicus fully in the degassing, can think that the degassing is fully when in vacuum pumps gas port three minutes, detecting less than white precipitate), close air outlet valve, stop to vacuumize, begin progressively to heat up polymerization: 130 ℃ kept 4 hours down, 140 ℃ kept 2 hours down, and 150 ℃ kept 5 hours down, and 160 ℃ kept 4 hours down; At this moment, obtain the PBO pre-polymer solution that the PBO intrinsic viscosity is 10dL/g.
Above-mentioned PBO pre-polymer solution is transferred in the storage tank that has attemperator is incubated, wherein, the temperature of storing tank skin is 150～170 ℃, and the temperature of base plate is 160～180 ℃; Then by hydraulic pump with material be 32 to get to draw ratio, internal diameter is in the double screw extruder of 21.7mm, the pressure of control hydraulic pump, the conveying capacity that makes prepolymer is 60g/min; Shearing force in extruder is 500S
-1, temperature between 180～210 ℃, the time of staying is about and obtains the whole polymers solution of PBO that the PBO intrinsic viscosity is 27dL/g under 30 minutes the condition.
The whole polymers solution of PBO through behind the measuring pump, is done spray-wet spinning spinning, obtain the fiber that average diameter is 30 μ m, its TENSILE STRENGTH is 2.5GPa, puts under the ultraviolet light to shine after 100 hours, and its strength retention is 60%.
Embodiment 1
With 1 parts by mass nano titanium oxide (TiO
2) to be scattered in 200 parts by mass, concentration be 85% phosphoric acid (H
3PO
4) in, add the phosphorus pentoxide (P of 170～310 parts by mass after ultrasonic
2O
5), making the mass fraction of phosphorus pentoxide in solution is 80～85%, makes nano titanium oxide dispersion through stirring again.
Adopt the described method of comparative example to prepare the PBO pre-polymer solution.
It is 32 that PBO pre-polymer solution and nano titanium oxide dispersion are got to draw ratio with hydraulic pump respectively, internal diameter is in the double screw extruder of 21.7mm, the rotating speed of control measuring pump, the conveying capacity that makes the PBO pre-polymer solution is 20g/min, nano titanium oxide dispersion (TiO
2/ PA) conveying capacity is 140g/min; Shearing force in extruder is 500S
-1, temperature between 180～210 ℃, the time of staying is about 30 minutes, material is done spray-wet spinning spinning through behind the measuring pump, obtaining the nanometer titanium dioxide Ti content is the PBO composite fibre of 10wt.%, its average diameter is 35 μ m, TENSILE STRENGTH is 2.0GPa, put under the ultraviolet light and shine after 100 hours, its strength retention is 55%.
Embodiment 2
Adopt and to carry out polymerization and spinning as embodiment 1 described method, the conveying capacity of different the is nanometer titanium dioxide titanium solution enters double screw extruder is 90g/min; Obtaining the nanometer titanium dioxide Ti content is the PBO composite fibre of 7wt.%, and its average diameter is 32 μ m, and TENSILE STRENGTH is 2.3GPa, puts under the ultraviolet light to shine after 100 hours, and its strength retention is 61%.
Embodiment 3
Adopt and to carry out polymerization and spinning as embodiment 1 described method, the conveying capacity of different the is nanometer titanium dioxide titanium solution enters double screw extruder is 50g/min; Obtaining the nanometer titanium dioxide Ti content is the PBO composite fibre of 4wt.%, and its average diameter is 29 μ m, and TENSILE STRENGTH is 2.6GPa, puts under the ultraviolet light to shine after 100 hours, and its strength retention is 71%.
Embodiment 4
Adopt and to carry out polymerization and spinning as embodiment 1 described method, the conveying capacity of different the is nanometer titanium dioxide titanium solution enters double screw extruder is 12g/min; Obtaining the nanometer titanium dioxide Ti content is the PBO composite fibre of 1wt.%, and average diameter is 28 μ m, and TENSILE STRENGTH is 2.4GPa, puts under the ultraviolet light to shine after 100 hours, and its strength retention is 75%.
Comparative example proves with embodiment: adopt the composite fibre (especially embodiment 4) of preparation method's preparation of the present invention to compare with the pbo fiber (seeing comparative example) that synthesizes with condition, its mechanical property still remains on original level, but its anti ageing property (irradiation was a standard in 100 hours under the ultraviolet light to put into) has improved 25%.
Claims (9)
1. a preparation method who contains the polyparaphenylene benzene and the two oxazole composite fibres of nano titanium oxide is characterized in that, may further comprise the steps:
(1) adopting hydrophilic rutile type nano titanic oxide is raw material, and its particle diameter is between 30～60nm;
(2) 1 parts by mass nano titanium oxide being scattered in 200 parts by mass, concentration is in 85% the phosphoric acid, add the phosphorus pentoxide of 170～310 parts by mass after ultrasonic, making the mass fraction of phosphorus pentoxide in solution is 80～85%, makes nano titanium oxide dispersion through stirring again;
(3) with polyphosphoric acids, etc. mol ratio 4,6-diamino resorcin hydrochlorate and terephthalic acid (TPA) add in the reactor, reactor is in negative pressure state always, its agitator that uses is double ribbon agitator, and the hand of spiral of hurricane band is identical with mixing direction, begins to stir, under 110～120 ℃ of conditions, vacuumized 30 hours, remove hydrogen chloride, the polymerisation that progressively heats up under 130～160 ℃ of conditions then 20 hours makes polyparaphenylene Ben Bing Er oxazole pre-polymer solution;
(4) nano titanium oxide dispersion and polyparaphenylene Ben Bing Er oxazole pre-polymer solution are placed engagement type double screw extruder in the same way by measuring pump by preset proportion, the screw speed of double screw extruder is 10～200rpm, screw slenderness ratio is greater than 30, material stopped in the engagement type double screw extruder 10～60 minutes, the degree of polymerization and the polymerisation degree of polyparaphenylene Ben Bing Er oxazole are further improved, under 180～210 ℃ of conditions, react then and extrude, obtain containing the polyparaphenylene Ben Bing Er oxazole polymer of nano titanium oxide;
(5) the polyparaphenylene benzene that will contain nano titanium oxide is also done spray-wet spinning spinning behind the two oxazole polymer filtrations, obtain containing the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide, the content of nano titanium oxide is 1～10wt.% in the composite fibre.
2. the preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide according to claim 1, it is characterized in that, the terephthalic acid (TPA) that step (3) adopts passes through the air-flow pulverization process in advance, terephthalic acid (TPA) average grain diameter after the processing is below 4 μ m, and 90% less than 6 μ m.
3. the preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide according to claim 2 is characterized in that the terephthalic acid (TPA) after the processing should be kept in the vacuum desiccator, must be in 95 ℃ of baking ovens before using drying 24 hours.
4. the preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide according to claim 1, it is characterized in that, in step (3), under 100 ℃ of conditions, outgas naturally earlier, progressively strengthen vacuum then and vacuumize and remove hydrogen chloride.
5. the preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide according to claim 1, it is characterized in that, the polymerisation that progressively heats up under 130～160 ℃ of conditions in the described step (3) is: 130 ℃ kept 4 hours down, 140 ℃ kept 2 hours down, 150 ℃ kept 5 hours down, and 160 ℃ kept 4 hours down.
6. the preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide according to claim 1, it is characterized in that, in the described step (3), emit on the material under the too high prerequisite not influencing, progressively improve the speed of agitator of reactor, maximum can be to 80rpm.
7. the preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide according to claim 6 is characterized in that, adjusting agitator counter-rotating in per 20 minutes 1 minute, and the phenomenon of uniting appears in material in reactor.
8. the preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide according to claim 1, it is characterized in that, described be transferred to polyparaphenylene Ben Bing Er oxazole pre-polymer solution in the engagement type double screw extruder before, should earlier polyparaphenylene Ben Bing Er oxazole pre-polymer solution be inserted in the storage tank that has attemperator and be incubated, at this moment, the temperature of storage tank tank skin is 150～170 ℃, the temperature of base plate is 160～180 ℃, and then is pressed in the engagement type double screw extruder by hydraulic pump.
9. the preparation method who contains the polyparaphenylene Ben Bing Er oxazole composite fibre of nano titanium oxide according to claim 1, it is characterized in that, the engagement type double screw extruder that adopts in the described step (4) mainly is made up of two screw rods that mesh in the same way, contains the reverse thread groove on the forward screw thread.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101906677B (en) * | 2010-08-31 | 2011-12-21 | 华东理工大学 | Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber |
| 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 |
| CN102634970A (en) * | 2012-04-20 | 2012-08-15 | 哈尔滨工业大学 | Method for enhancing ultraviolet resistance stability of PBO (poly-p-phenylenebenzobisthiazole) fibers by depositing (PAA (polyacrylic acid)/PEI (polyethyleneimine))m/(PAA/TiO2)n films on surfaces |
| CN102634976B (en) * | 2012-04-20 | 2013-12-11 | 哈尔滨工业大学 | Method for enhancing ultraviolet resistance stability of PBO (poly-p-phenylenebenzobisthiazole) fibers by depositing (POSS (polyhedral oligomeric silsesquioxane)/TiO2)n films on surfaces |
| CN106012492B (en) * | 2016-05-30 | 2018-01-19 | 哈尔滨工业大学 | A kind of method that difunctionality hyperbranched siloxane improves pbo fiber uvioresistant performance |
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| CN101215732A (en) * | 2008-01-02 | 2008-07-09 | 东华大学 | Ultraviolet resisting PBO fibre and preparing method thereof |
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Application publication date: 20091230 Assignee: Jiangsu Tengsheng Textile Technology Group Co.,Ltd. Assignor: East China University of Science and Technology Contract record no.: 2013310000023 Denomination of invention: Poly(p-phenylene benzobisoxazole) composite fiber containing nano-TiO2 preparation method Granted publication date: 20110406 License type: Exclusive License Record date: 20130327 |
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