CN111926438A - Ultraviolet-resistant high-strength high-modulus PBO fiber and preparation method thereof - Google Patents

Ultraviolet-resistant high-strength high-modulus PBO fiber and preparation method thereof Download PDF

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CN111926438A
CN111926438A CN202010831346.1A CN202010831346A CN111926438A CN 111926438 A CN111926438 A CN 111926438A CN 202010831346 A CN202010831346 A CN 202010831346A CN 111926438 A CN111926438 A CN 111926438A
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pbo
fiber
heat treatment
ultraviolet
modulus
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张永刚
郝梦圆
钱鑫
王雪飞
支建海
李德宏
宋书林
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/224—Selection or control of the temperature during stretching

Abstract

The invention relates to the field of fiber modification processing, and discloses a preparation method of an ultraviolet-resistant high-strength high-modulus PBO fiber, which comprises the steps of under the protection of inert gas, passing the PBO-AS fiber applied with axial tension through a heat treatment channel to obtain the ultraviolet-resistant high-strength high-modulus PBO fiber; the temperature of the heat treatment channel is 600-700 ℃, the time of the PBO-AS fiber passing through the heat treatment channel is not more than 10min, the tensile strength of the PBO fiber can be kept to the maximum extent by strictly controlling the heat treatment temperature and the heat treatment time, the tensile modulus of the PBO fiber is improved, the improvement on the ultraviolet resistance of the PBO fiber is greatly facilitated, the application value of the PBO fiber can be greatly improved, the preparation cost is low, the industrialization is easy, and the like.

Description

Ultraviolet-resistant high-strength high-modulus PBO fiber and preparation method thereof
Technical Field
The invention relates to the field of fiber modification processing, in particular to an ultraviolet-resistant high-strength high-modulus PBO fiber and a preparation method thereof.
Background
The poly-p-Phenylene Benzobisoxazole (PBO) fiber is a high-performance organic fiber with high thermal stability, high molecular orientation degree and chain rigidity, and is a member of a heterocyclic aromatic high polymer family with a rigid rod-like structure. The PBO fiber has excellent mechanical property, the strength and the modulus of the PBO fiber are two times higher than those of Kevlar fiber, the PBO fiber depends on a conjugated polymer main chain between the benzobisoxazole and a benzene ring, and the PBO fiber can generate the delocalization and resonance effect of pi electrons, so that the PBO structure tends to be stable. The PBO fiber spinning adopts a dry jet wet spinning technology, in the process, molecular chains of the PBO are highly oriented along the fiber axis, and high crystallinity and orientation degree are endowed by the tension action applied to the fiber axis. The conjugated aromatic heterocyclic structure on the PBO molecular chain and the solid-phase carbide after heat treatment enable the fiber to have excellent heat resistance and flame retardance. The thermal decomposition temperature of the PBO fiber reaches 650 ℃ in a nitrogen atmosphere, the PBO fiber can be used for a long time at 300 ℃, and the Limiting Oxygen Index (LOI) of the PBO fiber is 68, so that the PBO fiber can be widely applied to the fields of aerospace, fire prevention, bulletproof prevention and the like.
Even PBO fibers with such excellent properties still have a fatal defect in their use. Under the irradiation of ultraviolet light, the aging process of the PBO fiber is rapid, the mechanical property is rapidly reduced, the PBO fiber loses the practical value, and the application of the PBO fiber is greatly limited. Therefore, studies on the ultraviolet light aging resistance of PBO fibers have been receiving attention. At present, related researches mainly focus on methods of inorganic nanoparticle surface modification, blending of ultraviolet absorbers, stabilizers and PBO polymerization solution and the like. The former is simple and rapid to operate, for example, CN 102277726A discloses a method for resisting ultraviolet light aging of poly-p-phenylene benzobisoxazole fiber, which comprises the steps of preparing a solution A containing a coupling agent and an acid medium, and a solution B containing an accelerator precipitate, mixing the solution A and the solution B, allowing PBO fiber to enter under the assistance of ultrasonic oscillation, and forming a 0.02-0.05 mm uniform ultraviolet light aging resistant gel coating on the surface of the PBO fiber, wherein the internal structure of the PBO is not changed, but irreversible damage to the fiber body is difficultly avoided in the modification treatment process, so that the fiber strength is reduced, the cost is high, and the industrialization difficulty is high;
the ultraviolet light resistance of the latter is not stable enough, and substances such as ultraviolet absorbers in PBO gradually lose with the prolonging of the service time, and the ultraviolet light resistance of the PBO is also reduced. In recent years, in-situ copolymerization methods for improving the ultraviolet light resistance of PBO fibers are gradually accepted by researchers, and the method effectively overcomes the defects of the two methods, for example, CN 101906677A discloses a preparation method of ultraviolet light aging resistant poly-p-phenylene benzobisoxazole fibers.
Therefore, a simple and effective preparation method of the ultraviolet-resistant PBO fiber is a problem to be solved urgently in the field of research of the PBO fiber at present.
Disclosure of Invention
The invention aims to provide a simple and convenient PBO fiber treatment method with low cost and high efficiency, and the PBO fiber with excellent ultraviolet light resistance and high modulus can be prepared on the premise of keeping the tensile strength of the PBO fiber to the maximum extent.
In order to achieve the purpose, the invention adopts the technical scheme that:
under the protection of inert gas, PBO (poly (p-phenylene benzobisoxazole)) primary-spun common filament (PBO-AS) fibers with axial tension applied are made to pass through a heat treatment channel at a constant speed to obtain the ultraviolet-resistant high-strength high-modulus PBO fibers; the temperature of the heat treatment channel is 600-700 ℃, and the time for the PBO-AS fiber to pass through the heat treatment channel is not more than 10 min.
The conjugated structure of PBO determines the ultraviolet sensitivity, particularly the O-C ═ N structure on the oxazole ring is susceptible to ultraviolet aging and is converted into free radicals, further leading the PBO main chain to open and break bonds, and finally affecting the mechanical properties of the PBO fiber. The invention adopts short-time high-temperature heat treatment on the PBO, so that the chemical structure of the PBO fiber can be changed, and the conjugated structure which is easy to be activated by ultraviolet radiation is damaged and converted into the non-conjugated six-membered ring structure which is more resistant to ultraviolet radiation. The inventor finds out through experiments that after the fiber is treated at the temperature of 600-700 ℃ for a short time, the PBO fiber structure generates the chromogenic group C ═ O conjugated with the benzene ring and the color assisting group N-H, so that the red shift degree of the ultraviolet spectrum is more serious, and the original B band absorbs from about 400nm to near 500nm, so that the original color of the PBO fiber is purple or even blue. Meanwhile, along with the red shift of the maximum absorption band of the PBO, the photosensitivity and the absorption of ultraviolet rays in the environment are reduced, and in addition, the visible light absorption of a 500-1000 nm wave band is obviously improved, so that the ultraviolet absorption of 300-400 nm is shared, and the ultraviolet resistance of the PBO fiber can be expected to be improved.
The heat-treated PBO surface in this study exhibited a distinctive purple (or deep blue) color, closely related to the destruction of benzoxazole conjugated structure and the formation of new six-membered rings due to thermal reactions during the PBO high temperature treatment. Meanwhile, the change of the chemical structure also causes the change of a plurality of physical and chemical properties, wherein the most important is the change of the light absorption property, the change not only affects the color of the PBO fiber, but also has great influence on the ultraviolet light sensitivity of the PBO fiber, thereby being beneficial to the improvement of the ultraviolet light resistance of the PBO fiber, and the PBO-HT fiber obtained by the preparation method after 800h ultraviolet irradiation test still has the strength retention rate of more than 90%, and the result further verifies the conclusion. In addition, the mechanical property of the PBO is obviously changed, and particularly, the Young modulus of the PBO is improved to 132.9 percent of the original Young modulus, so that the PBO has two advantages. The method has the advantages of low damage to the mechanical property of the original fiber, excellent ultraviolet resistance, stable effect, low cost, easy industrialization and the like, is a PBO fiber modification mode with great potential, and has great practical value.
Preferably, the temperature of the heat treatment channel is 630-670 ℃, and the time for the PBO-AS fiber to pass through the heat treatment channel is 10s-5 min. The temperature of the heat treatment channel and the heat treatment time of the fiber have a key influence on the ultraviolet light resistance, tensile strength and modulus of the fiber, when the temperature is too high, the modulus of the fiber is improved, but the tensile strength is obviously reduced, but the temperature is too low, the material cannot achieve the ultraviolet light resistance effect, and the modulus is lower.
Further preferably, the temperature of the heat treatment channel is 630-650 ℃, and when the time that the PBO-AS fiber passes through the heat treatment channel at the temperature is 30s-3min, the obtained PBO fiber has good comprehensive performance of ultraviolet light resistance, tensile strength and modulus.
The inert gas is nitrogen or inert rare gas with the purity of more than 99.999 percent, and the fiber is protected from oxidative degradation in the heat treatment process.
The axial tension is 5-15N. Under the action of high-temperature heat treatment and drawing force, the preferential orientation of crystals in the PBO microfiber is improved, the crystals are more closely arranged, the crystallinity is also improved, and the improvement of the tensile modulus of the PBO fiber is greatly facilitated.
Preferably, the axial tension is 8-12N. Excessive drawing tension can lead to the generation of broken filaments, which can have adverse effects on the mechanical properties of the PBO fibers; while too little draw tension will be insufficient to promote preferential orientation during PBO heat treatment, the resulting fiber will have better tensile modulus properties under this axial tension.
The PBO-AS fiber has an axial draft ratio of 1.05 to 1.5. The certain draft ratio is beneficial to the disappearance of dislocation and the improvement of the density of a heat treatment fiber body, so that the PBO microcrystals are arranged more tightly along the axial direction; meanwhile, the creep deformation brought by the drafting can eliminate and transfer the cross-linking among the micro fibers, and the preferred orientation of the fibers along the axial direction is improved, so that the tensile modulus of the fibers is improved.
Preferably, the axial draft ratio of the PBO-AS fiber is 1.05-1.1. Too small a draft ratio is not sufficient to eliminate dislocations, and the change in bulk density is not significant enough; the excessive draft ratio can cause slight damage to the PBO precursor, so that the tensile strength of the PBO fiber is lost, and tests show that when the axial draft ratio is 1.05-1.1, the comprehensive performances of the tensile strength, the tensile modulus, the ultraviolet resistance and the like of the fiber are better.
The invention also discloses the ultraviolet light resistant high-strength high-modulus PBO fiber prepared by the preparation method, and the tensile strength of the ultraviolet light resistant high-strength high-modulus PBO fiber is kept above 90% after the ultraviolet light resistant high-strength high-modulus PBO fiber is aged for 800 hours.
The invention also provides a device for realizing the preparation method of the ultraviolet-resistant high-strength high-modulus PBO fiber, which comprises a fiber releasing disc, a guide wheel, a front drafting driving wheel, a heat treatment device, a rear drafting driving wheel and a fiber collecting device which are sequentially arranged according to the fiber trend, wherein the surface of the guide wheel is provided with a groove for guiding the position of a fiber bundle. The front and rear traction driving wheels control the traction speed of the filament bundle through a servo motor, and the filament collecting device is provided with an induction device which can feed back the thickness of the filament bundle on the filament tube and adjust the linear speed of the filament collecting roller.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method can keep the tensile strength of the PBO fiber to the maximum extent by strictly controlling the heat treatment temperature and time, improves the tensile modulus, is greatly beneficial to improving the ultraviolet resistance of the PBO fiber, and can greatly improve the application value of the PBO fiber.
(2) The PBO fiber prepared by the method has stable ultraviolet light resistance, the tensile strength can still be kept above 90% after 800h of ultraviolet light aging, the ultraviolet light resistance is stable, the tensile strength of the untreated PBO fiber is reduced to 49.81% of the original strength after the PBO fiber is aged by the ultraviolet light, and the effect is obviously improved.
(3) The preparation method disclosed by the invention is simple to operate, energy-saving and environment-friendly, is easy for industrial production, has a cost far lower than that of common modes such as surface modification and copolymerization, is stable in effect, and cannot lose effectiveness due to loss of the ultraviolet absorbent.
Drawings
FIG. 1 is a schematic view of a PBO fiber heat treatment device of the present invention, wherein 1 is a filament releasing disc, 2 is a guiding wheel, 3 is a front drawing driving wheel, 4 is a heat treatment device, 5 is a rear drawing driving wheel, and 6 is a filament collecting device.
FIG. 2 shows the UV-visible near-IR absorption spectra of PBO-AS and PBO-HT.
FIG. 3 is a graph of the tensile strength of the fibers of examples 2-5 and comparative example 1 before and after UV light aging.
FIG. 4 shows the surface topography of the PBO-AS fiber of comparative example 1 before and after UV aging, wherein a), b), c) represent UV aging for 0h, 240h, 800h, respectively.
FIG. 5 shows the surface topography of PBO-630-30s fiber of example 2 before and after UV aging, a), b), c) respectively representing UV aging for 0h, 240h, 800 h.
FIG. 6 shows the surface topography of PBO-630-1 fiber of example 3 before and after UV aging, a), b), c) respectively representing UV aging for 0h, 240h, 800 h.
FIG. 7 shows the surface topography of PBO-640-30s fiber of example 4 before and after UV aging, a), b), c) respectively representing UV aging for 0h, 240h, 800 h.
FIG. 8 is the surface topography of the PBO-650-30s fiber of example 5 before and after UV aging, a), b), c) representing UV aging for 0h, 240h, 800h, respectively.
FIG. 9 is a graph of heat treatment temperature versus mechanical properties of PBO-HT fibers.
FIG. 10 is a graph of the relationship between heat treatment time and mechanical properties of PBO-HT fibers.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The PBO fiber heat treatment device comprises a filament releasing disc 1, a guide wheel 2, a front drafting driving wheel 3, a heat treatment device 4, a rear drafting driving wheel 5 and a filament collecting device 6 in sequence according to the fiber direction as shown in figure 1, wherein the surface of the guide wheel 2 is provided with a groove for guiding the position of a filament bundle. The front and rear traction driving wheels control the traction speed of the filament bundle through a servo motor, and the filament collecting device 6 is provided with an induction device which can feed back the thickness of the filament bundle on the filament tube and adjust the linear speed of the filament collecting roller. In the following examples, the heat treatment apparatus is a tube furnace, and PBO-AS is newly spun ordinary yarn.
Example 1
Fixing the newly spun PBO-AS fiber bundle yarns on each device shown in figure 1 in sequence, introducing 99.9999% of nitrogen into the tubular furnace for 10min to exhaust air in the tubular furnace, wherein the gas flow rate is 2cm3/min, setting the temperature rise degree of the tubular furnace, raising the temperature to 630 ℃ at the temperature rise rate of 10 ℃/min, starting a drafting device after the temperature of the tubular furnace is kept at 630 ℃, enabling the fibers to pass through a 20cm tubular furnace heating area at the drafting rate of 60cm/min, namely, the heat treatment time of the fibers is 20s, and collecting the PBO-HT fibers (marked AS PBO-630-20s) after heat treatment.
The axial tension of the filament feeding disc 1 is set to be 8N, after the drafting device is started, the linear speed of the front drafting driving wheel 3 is set to be 60cm/min, and the linear speed of the rear drafting driving wheel 5 is set to be 63cm/min (corresponding to the drafting ratio of 1: 1.05).
Example 2
According to the process of example 1, the tube furnace is heated to 630 ℃ at a rate of 10 ℃/min, after the temperature of the tube furnace is kept at 630 ℃, the drafting device is started, the fiber passes through the heating zone of the tube furnace of 20cm at a drafting rate of 40cm/min, namely the heat treatment time of the fiber is 30s, and the heat-treated PBO-HT fiber (marked as PBO-630-30s) is collected. The axial tension of the filament feeding disc 1 is set to be 8N, after the drafting device is started, the linear speed of the front drafting driving wheel 3 is set to be 40cm/min, and the linear speed of the rear drafting driving wheel 5 is set to be 42cm/min (corresponding to the drafting ratio of 1: 1.05).
Example 3
According to the process of example 1, the temperature of the tube furnace is raised to 630 ℃ at the speed of 10 ℃/min, after the temperature of the tube furnace is kept at 630 ℃, the drafting device is started, the fiber passes through the heating area of the tube furnace of 20cm at the drafting speed of 20cm/min, namely the heat treatment time of the fiber is 1min, and the PBO-HT fiber (marked as PBO-630-1) after the heat treatment is collected. The axial tension of the filament feeding disc 1 is set to be 8N, after the drafting device is started, the linear speed of the front drafting driving wheel 3 is set to be 20cm/min, and the linear speed of the rear drafting driving wheel 5 is set to be 21cm/min (corresponding to the drafting ratio of 1: 1.05).
Example 4
According to the process of example 1, the tube furnace is heated to 640 ℃ at a speed of 10 ℃/min, after the temperature of the tube furnace is kept at 640 ℃, the drafting device is started, the fiber passes through a 20cm tube furnace heating zone at a drafting speed of 40cm/min, namely the heat treatment time of the fiber is 30s, and the heat-treated PBO-HT fiber (marked as PBO-640-30s) is collected. The axial tension of the filament feeding disc 1 is set to be 8N, after the drafting device is started, the linear speed of the front drafting driving wheel 3 is set to be 40cm/min, and the linear speed of the rear drafting driving wheel 5 is set to be 42cm/min (corresponding to the drafting ratio of 1: 1.05).
Example 5
According to the process of example 1, the tube furnace is heated to 650 ℃ at a rate of 10 ℃/min, after the temperature of the tube furnace is kept at 650 ℃, the drafting device is started, the fiber passes through the heating zone of the tube furnace of 20cm at a drafting rate of 40cm/min, namely the heat treatment time of the fiber is 30s, and the heat-treated PBO-HT fiber (marked as PBO-650-30s) is collected. The axial tension of the filament feeding disc 1 is set to be 8N, after the drafting device is started, the linear speed of the front drafting driving wheel 3 is set to be 40cm/min, and the linear speed of the rear drafting driving wheel 5 is set to be 42cm/min (corresponding to the drafting ratio of 1: 1.05).
Example 6
According to the process of example 1, the temperature of the tube furnace is raised to 630 ℃ at the speed of 10 ℃/min, after the temperature of the tube furnace is kept at 630 ℃, the drafting device is started, the fiber passes through the heating area of the tube furnace of 20cm at the drafting speed of 2cm/min, namely the heat treatment time of the fiber is 10min, and the PBO-HT fiber (marked as PBO-630-10) after heat treatment is collected. The axial tension of the filament feeding disc 1 is set to be 8N, after the drafting device is started, the linear speed of the front drafting driving wheel 3 is set to be 2cm/min, and the linear speed of the rear drafting driving wheel 5 is set to be 2.1cm/min (corresponding to the drafting ratio of 1: 1.05).
Performance testing
The PBO-AS fiber obtained in examples 2-5 was tested for its uv-vis nir absorption spectrum using non-heat-treated PBO-AS fibril AS comparative example 1, and AS a result, AS shown in fig. 2, it can be seen that the PBO-AS fiber of comparative example 1 has high absorbance in the uv region of 200-350nm, while the PBO-HT fiber of examples 2-5, which was heat-treated and slightly oxidized, produced chromophore C ═ O and chromophore N — H conjugated to benzene rings, so the uv spectrum was more red-shifted, and the original B band absorption was red-shifted from about 400nm to about 500nm, thus showing a purple color or even a blue color different from the original color of the PBO fiber. Meanwhile, along with the red shift of the maximum absorption band of the PBO-HT, the photosensitivity and the absorption of ultraviolet rays in the environment are reduced, and in addition, the visible light absorption of a 500-1000 nm wave band is obviously improved, and the ultraviolet absorption of 300-400 nm is shared, so that the ultraviolet light resistance of the PBO-HT fiber is obviously improved.
The PBO-HT fibers obtained in examples 2 to 5 were subjected to UV aging test, and resin-impregnated specimens were prepared using E44 epoxy resin and triethylene tetramine (curing agent) in acetone as a solvent according to ASTM D4018-17, and tensile test was performed using an Instron 5569A universal material tester to test the tensile strength of the fibers at various aging times, the results of which are shown in Table 1 and FIG. 3.
TABLE 1 tensile Strength of fibers aged with different UV lights
Figure BDA0002638089600000091
Since PBO is a typical sheath-core structured fiber and the reduction in tensile strength caused by uv light aging is largely due to the destruction of its sheath, the present study also observed the surface microstructure of PBO fibers after uv light aging at different times. The surface morphology of the fibers of examples 2 to 5 and comparative example 1 before and after UV aging was observed and the results are shown in FIGS. 4 to 8, wherein a), b), and c) represent UV aging times of 0h, 240h, and 800h, respectively.
In comparison with fig. 4-8, the uv-aging of the non-heat-treated PBO-AS fiber in comparative example 1 initiated from the destruction of the skin structure, and the relatively smooth surface thereof was subject to a large amount of surface destruction such AS swelling, swelling and cracking after uv-aging, and the generation of such surface defects became more severe AS the degree of aging increased, AS can be seen from c) of fig. 4, the surface of the 800 h-aged PBO-AS fiber was severely damaged, and surface cracks and ravines became vertical and horizontal, and even microfibrillar, which further resulted in a sharp decrease in the strength of the PBO-AS, and only 49.81% of the original strength was maintained.
In contrast, in fig. 5-8, the surface defect degree of the PBO-HT fiber after heat treatment is greatly reduced, no large cracks are generated even after 800h of uv aging, only slight wrinkles and bulges occur, and microfibrillation does not occur, so that the internal structure of the fiber is well protected, and the mechanical properties of the PBO-HT fiber are maintained.
Effect of different Heat treatment temperatures on mechanical Properties
According to the preparation process of example 1, the fixed heat treatment time is 30s, and the mechanical properties of the PBO-HT fibers at different heat treatment temperatures within the range of 360-720 ℃ are tested, and the results are shown in FIG. 9. The test result shows that the rise of the heat treatment temperature has adverse effect on the tensile strength of the PBO-HT fibers, so the heat treatment temperature is preferably 630-660 ℃; the heat treatment at the temperature of 700 ℃ is beneficial to improving the tensile modulus of the fiber, but the heat treatment at the temperature of above 700 ℃ can cause chain scission and decomposition of PBO macromolecules, so that the mechanical property of the PBO macromolecules is seriously reduced.
Effect of different Heat treatment times on mechanical Properties
According to the preparation process of the embodiment 1, the fixed heat treatment temperature is 630 ℃, the mechanical properties of the fiber after different heat treatment times within 30-600 s are tested, as shown in fig. 10, the tensile strength loss of the PBO fiber caused by the heat treatment is minimum, the tensile strength of the fiber is reduced when the treatment time is prolonged, and the modulus of the fiber is only slightly increased. Furthermore, the heat treatment for more than 300s can destroy the rigid rod-like structure of macromolecules in the fiber, and further cause great reduction of the overall mechanical performance of the PBO fiber.

Claims (9)

1. The preparation method of the ultraviolet-resistant high-strength high-modulus PBO fiber is characterized in that under the protection of inert gas, the PBO-AS fiber applied with axial tension passes through a heat treatment channel to obtain the ultraviolet-resistant high-strength high-modulus PBO fiber; the temperature of the heat treatment channel is 600-700 ℃, and the time for the PBO-AS fiber to pass through the heat treatment channel is not more than 10 min.
2. The method for preparing the ultraviolet light resistant high-strength high-modulus PBO fiber AS claimed in claim 1, wherein the temperature of the heat treatment channel is 630-670 ℃, and the time for the PBO-AS fiber to pass through the heat treatment channel is 10s-5 min.
3. The method for preparing the ultraviolet-resistant high-strength high-modulus PBO fiber AS claimed in claim 1, wherein the temperature of the heat treatment channel is 630-650 ℃, and the time for the PBO-AS fiber to pass through the heat treatment channel is 30s-3 min.
4. The method for preparing the ultraviolet-resistant high-strength high-modulus PBO fiber as claimed in claim 1, wherein the inert gas is nitrogen or inert rare gas with a purity of 99.999% or more.
5. The preparation method of the ultraviolet-resistant high-strength high-modulus PBO fiber as claimed in claim 1, wherein the axial tension is 5-15N.
6. The preparation method of the ultraviolet-resistant high-strength high-modulus PBO fiber according to claim 5, wherein the axial tension is 8-12N.
7. The method for preparing the ultraviolet-resistant high-strength high-modulus PBO fiber according to claim 1, wherein the PBO-AS fiber has an axial draft ratio of 1.05-1.5.
8. The preparation method of the ultraviolet-resistant high-strength high-modulus PBO fiber according to claim 7, wherein the axial draft ratio of the PBO-AS fiber is 1.05-1.1.
9. The ultraviolet-resistant high-strength high-modulus PBO fiber prepared by the preparation method of any one of claims 1 to 8, wherein the tensile strength of the ultraviolet-resistant high-strength high-modulus PBO fiber is kept above 90% after the ultraviolet light aging for 800 hours.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906677A (en) * 2010-08-31 2010-12-08 华东理工大学 Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber
KR20150049403A (en) * 2013-10-30 2015-05-08 금오공과대학교 산학협력단 Process Of Surface Coating Of PBO Yarn For Enhancing UV Resistance
US9211508B2 (en) * 2013-09-27 2015-12-15 Uop Llc Polybenzoxazole membranes from self-cross-linkable aromatic polyimide membranes
CN106012492A (en) * 2016-05-30 2016-10-12 哈尔滨工业大学 Method for improving ultraviolet resistance of POB fibers by using bifunctional hyperbranched siloxane
CN107620204A (en) * 2017-11-09 2018-01-23 成都新晨新材科技有限公司 A kind of pbo fiber of ultraviolet resistance and preparation method thereof
CN108486861A (en) * 2018-04-25 2018-09-04 浙江梵彼斯特轻纺发展有限公司 A kind of preparation process of anti-ultraviolet ageing pbo fiber

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906677A (en) * 2010-08-31 2010-12-08 华东理工大学 Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber
US9211508B2 (en) * 2013-09-27 2015-12-15 Uop Llc Polybenzoxazole membranes from self-cross-linkable aromatic polyimide membranes
KR20150049403A (en) * 2013-10-30 2015-05-08 금오공과대학교 산학협력단 Process Of Surface Coating Of PBO Yarn For Enhancing UV Resistance
CN106012492A (en) * 2016-05-30 2016-10-12 哈尔滨工业大学 Method for improving ultraviolet resistance of POB fibers by using bifunctional hyperbranched siloxane
CN107620204A (en) * 2017-11-09 2018-01-23 成都新晨新材科技有限公司 A kind of pbo fiber of ultraviolet resistance and preparation method thereof
CN108486861A (en) * 2018-04-25 2018-09-04 浙江梵彼斯特轻纺发展有限公司 A kind of preparation process of anti-ultraviolet ageing pbo fiber

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
卢姍姍等: "聚对苯撑苯并双噁唑纤维改性技术的研究进展", 《合成纤维工业》 *
霍倩等: "紫外光照射对PBO纤维结构与性能的影响", 《合成纤维工业》 *

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