CN106894107B - Polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber and preparation method thereof - Google Patents
Polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber and preparation method thereof Download PDFInfo
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- CN106894107B CN106894107B CN201710127991.3A CN201710127991A CN106894107B CN 106894107 B CN106894107 B CN 106894107B CN 201710127991 A CN201710127991 A CN 201710127991A CN 106894107 B CN106894107 B CN 106894107B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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Abstract
The invention provides a polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber and a preparation method thereof. The polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is characterized by comprising 98.5-99.5 wt% of polyphenylene sulfide PPS resin and 0.5-1.5 wt% of modified halloysite nanotubes. The polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber prepared by the method has excellent breaking strength and thermal oxidation resistance; after the material is treated at the high temperature of 230 ℃ for 72 hours, the material still has high mechanical property retention rate which reaches 73.4-92.3%.
Description
Technical Field
The invention belongs to the field of hybrid composite fibers and preparation thereof, and particularly relates to a polyphenylene sulfide/halloysite nanotube hybrid composite fiber and a preparation method thereof.
Background
Polyphenylene sulfide fibers are high-performance fibers widely used in recent years, and have excellent heat resistance, corrosion resistance, flame retardancy, good mechanical properties, and the like. Once the polyphenylene sulfide fiber is produced, it is immediately noticed by various countries. Nowadays, the needle-punched filter felt is widely applied to the fields of military industry, high-temperature filtration and chemical protection, and particularly as an environment-friendly filter material, the needle-punched filter felt made of polyphenylene sulfide fiber is widely applied to dust removal and filtration of high-temperature flue gas of coal-fired boilers such as power generation, steel, cement, garbage incinerators and the like. The material has high cost performance and good dust removal effect, and is a more ideal heat-resistant and corrosion-resistant material.
However, the polyphenylene sulfide fiber also has a defect that the polyphenylene sulfide fiber is not negligible, compared with other high temperature resistant fibers, the polyphenylene sulfide fiber has poor thermal oxidation resistance, and is easy to generate oxidation reaction at high temperature, so that the polyphenylene sulfide fiber is yellow in color, low in strength and the like, and the service life of the product is greatly reduced. The reason why the polyphenylene sulfide fiber is easily oxidized is ultimately determined by its molecular structure. In the molecular structure of polyphenylene sulfide, a C-S bond is the weakest link in polyphenylene sulfide macromolecules. Sulfur in the molecular structure is easily lost electrons due to instability of electrons at the outermost layer and is combined with oxygen, so that oxidation occurs to cause degradation.
At present, few researches on improving the thermal oxidation resistance of polyphenylene sulfide fibers at home and abroad are carried out, and the improvement method mainly comprises two methods, one method is to add one antioxidant or a plurality of antioxidants into polyphenylene sulfide and improve the thermal oxidation resistance of the polyphenylene sulfide by utilizing the synergistic effect of the antioxidants, for example, a patent with the publication number of CN102560734B, which adds one or two chain termination antioxidants into raw polyphenylene sulfide powder to improve the thermal oxidation resistance of the polyphenylene sulfide, but the traditional antioxidants have the defects of low relative molecular weight, poor thermal stability, easy migration, poor extraction resistance and the like, and the defects can cause the great reduction of the mechanical property of the material and the obvious shortening of the service life. Another approach is to combine inorganic nano-materials with organic antioxidants to form a composite antioxidant modifier added to the polyphenylene sulfide material to improve the thermal oxidation stability of polyphenylene sulfide, which is a main trend in recent years, for example, patent publication No. CN102560718B, in which antioxidant and inorganic filler particles are made into a PPS fiber surface treatment solution, and the PPS fiber surface treatment solution is coated on the surface of the polyphenylene sulfide fiber by dipping or spraying, and dried to constant weight to obtain the antioxidant polyphenylene sulfide fiber. Therefore, there is a need to develop new modified fillers to impart higher thermal oxidation resistance to polyphenylene sulfide fibers.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber with higher thermal oxidation resistance and a preparation method thereof.
In order to solve the technical problem, the invention provides a polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber which is characterized by comprising 98.5-99.5 wt% of polyphenylene sulfide (PPS) resin and 0.5-1.5 wt% of modified halloysite nanotubes.
Preferably, the purity of the modified halloysite nanotube is higher than 99.5%, the length is 500-1000nm, and the length-diameter ratio is 8.8-9.7.
Preferably, the modified halloysite nanotube has a large inner cavity structure, the inner diameter of the tube is 23.6-38.5nm, and the mass ratio of Si/A1 is 1.33-6.27.
Preferably, the surface of the modified halloysite nanotube is coated with a rough and dense silicon dioxide layer, the diameter of the nano silicon dioxide particles on the layer surface is 5-20nm, and the surface hydroxyl content is 1.5-3OH/nm2。
The invention also provides a preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber, which is characterized by comprising the following steps:
step 1: adding the halloysite nanotube and a sulfuric acid solution into a three-neck flask, stirring at 50-80 ℃ for reaction, centrifuging, washing the obtained solid to neutrality, centrifuging and drying to obtain the acid-leached and etched halloysite nanotube;
step 2: placing deionized water, absolute ethyl alcohol and the acid-leached halloysite nanotube prepared in the step 1 into a container, performing ultrasonic dispersion, then adding a catalyst, stirring, adding a silicon source, stirring for reaction, after the reaction is finished, obtaining a product through centrifugation, washing, centrifuging and drying to obtain the modified halloysite nanotube;
and step 3: and extruding and granulating the modified halloysite nanotube and polyphenylene sulfide, and carrying out melt spinning to obtain the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber.
Preferably, the centrifugation treatment in the step 1 is centrifugation at the rotating speed of 5000r/min for 5 min.
Preferably, the drying in step 1 is drying in an oven at 80 ℃ for 24 h.
Preferably, the stirring time after the catalyst is added in the step 2 is 30-60min, and the stirring time after the silicon source is added is 6-10 h.
Preferably, the ratio of the deionized water to the absolute ethyl alcohol is 1-3: 1.
Preferably, the catalyst is ammonia water, the dosage of which is 0.2-2% of the system, and the silicon source is tetraethoxysilane, the dosage of which is 0.1-1% of the system.
Preferably, the stirring speed in step 2 is 100-500 r/min.
Preferably, the spinning temperature of the melt spinning process in the step 3 is 325 ℃, the spinning speed is 600m/min, and the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is prepared by secondary drafting with the total drafting multiple being 3.8 times.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the halloysite nanotube is modified by a chemical method, and compared with the common halloysite nanotube, the surface of the modified halloysite nanotube is coated with a rough and compact silicon dioxide layer, wherein the diameter of the nano silicon dioxide particles on the layer surface is 5-20nm, the hydroxyl content is obviously improved, and the modified halloysite nanotube has a larger inner diameter of a tube cavity (23.6-38.5 nm). And drying and mixing the modified halloysite nanotube and polyphenylene sulfide, and carrying out melt spinning to obtain the halloysite nanotube-polyphenylene sulfide composite material. The polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber prepared by the method has excellent breaking strength and thermal oxidation resistance; the breaking strength is 3.02-3.95 cN/dtex. After being treated at 230 ℃ for 72 hours, the material still has high mechanical property retention rate which reaches 73.4-92.3%.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is composed of 99.5 wt% of polyphenylene sulfide PPS resin and 0.5 wt% of modified halloysite nanotubes.
The preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber comprises the following steps:
(1) adding 5g of halloysite nanotubes (Zhengzhou gold sunshine ceramic Co., Ltd., pipe diameter of 60-80NM, length of 600 plus one 1000NM) and 400mL of 2mol/L sulfuric acid solution into a three-mouth flask, continuously carrying out mechanical stirring reaction at 50 ℃ for 48h, stopping the reaction, carrying out centrifugal treatment on a product obtained after the reaction at the rotating speed of 5000r/min for 5min, repeatedly washing the solid obtained by centrifugation with deionized water until the pH value of the aqueous solution is neutral, then centrifuging, placing the solid in an oven at 80 ℃ for drying for 24h, and storing a sample in a dryer after the drying is finished to obtain the acid-leached and etched halloysite nanotubes.
(2) Placing 100ml of deionized water, 140ml of absolute ethyl alcohol and 0.5g of the acid-leached and etched halloysite nanotube prepared in the step (1) in a 500ml three-neck flask, ultrasonically dispersing for 30min, then adding 2g of ammonia water with the concentration of 25%, wherein the pH value of the system is 11, then mechanically stirring at the rotating speed of 300r/min for 30min at the temperature of 25 ℃, then adding 0.6g of ethyl orthosilicate, reacting for 6h under the mechanical stirring at the rotating speed of 300r/min, obtaining a product after the reaction is finished, respectively washing 3 times by using ethanol and water, then centrifuging, placing the product in a blast oven for drying at the temperature of 90 ℃ for 24h, then placing in a vacuum oven for standing at the temperature of 90 ℃ for 12h, and then placing in a dryer for storage to obtain the modified halloysite nanotube. The modified halloysite nanotube has the purity of 99.5 percent, the length of 600-1000nm and the length-diameter ratio of 9.0-9.5. The modified halloysite nanotube has a large inner cavity structure, the inner diameter of the tube is 23.6-25.4nm, and the mass ratio of Si to Al is 1.33-2.25. The surface of the modified halloysite nanotube is coated with a layer of rough and compact silicon dioxide layer, the diameter of the nano silicon dioxide particles on the layer surface is 5-10nm, and the surface hydroxyl content is 1.5-2.0OH/nm2。
(3) Then putting the dried modified halloysite nanotube and polyphenylene sulfide slices (the polyphenylene sulfide slices are spinning-grade polyphenylene sulfide slices, the relative molecular mass is 3-5 ten thousand) into a double-screw extruder for extrusion granulation, wherein the rotating speed of the screws is 100r/min, and the temperature of each heating section of the double-screw extruder is as follows: the first section (feed zone) was 285 deg.C, the second section (extrusion zone) 305 deg.C, the third section (metering zone) 305 deg.C, the fourth section (homogenization zone) 305 deg.C, and the fifth section (outlet zone) 305 deg.C. Preparing a polyphenylene sulfide/modified halloysite nanotube hybrid composite slice; the mass fraction of the modified halloysite nanotube is 0.5%, and the mass fraction of the PPS resin is 99.5%.
(4) And adding the dried polyphenylene sulfide/modified halloysite nanotube hybrid composite slice into melt spinning equipment, wherein the spinning temperature is 325 ℃, carrying out melt spinning, winding and stretching at the spinning speed of 600m/min to obtain a primary yarn, wherein the winding speed is 600m/min, and carrying out secondary drafting, wherein the total drafting multiple is 3.8 times, so as to obtain the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber.
Through the characterization, the breaking strength of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is 3.95cN/dtex, and the breaking strength retention rate of the fiber is 73.4% after the fiber is treated at the high temperature of 230 ℃ for 72 hours.
Example 2
A polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is composed of 99.0 wt% of polyphenylene sulfide PPS resin and 1.0 wt% of modified halloysite nanotubes.
The preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber comprises the following steps:
(1) adding 10g of halloysite nanotubes (Zhengzhou Jinyangtao ceramics Co., Ltd., pipe diameter of 60-80nm, length of 600-1000nm) and 450mL of 2mol/L sulfuric acid solution into a three-mouth flask, continuously carrying out mechanical stirring reaction at 70 ℃ for 72h, stopping the reaction, carrying out centrifugal treatment on a product obtained after the reaction at the rotating speed of 5000r/min for 5min, repeatedly washing the solid matter obtained by centrifugation with deionized water until the pH value of the aqueous solution is neutral, then centrifuging, placing the solid matter in an oven at 80 ℃ for drying for 24h, and storing a sample in a dryer after the drying is finished to obtain the acid-leached and etched halloysite nanotubes.
(2) Remove 130mlPutting the seed water, 180ml of absolute ethyl alcohol and 0.7g of acid-etched halloysite nanotube prepared in the step (1) into a 500ml three-neck flask, ultrasonically dispersing for 30min, then adding 2.5g of ammonia water with the concentration of 28%, wherein the pH value of the system is 12, then mechanically stirring at the rotation speed of 300r/min for 40min at the temperature of 25 ℃, then adding 0.75g of ethyl orthosilicate, reacting for 8h under the mechanical stirring at the rotation speed of 300r/min, after the reaction is finished, obtaining a product by centrifuging, respectively washing 3 times by using ethanol and water, centrifuging, putting the product into a blast oven, drying for 24h at the temperature of 90 ℃, then placing into a vacuum oven for 12h at the temperature of 90 ℃, and then placing into a dryer for storage to obtain the modified halloysite nanotube. The modified halloysite nanotube has the purity of 99.6 percent, the length of 600-1000nm and the length-diameter ratio of 8.8-9.2. The modified halloysite nanotube has a large inner cavity structure, the inner diameter of the tube is 25.6-28.9nm, and the mass ratio of Si to Al is 2.34-4.25. The surface of the modified halloysite nanotube is coated with a rough and compact silicon dioxide layer, the diameter of the nano silicon dioxide particles on the layer surface is 8-15nm, and the surface hydroxyl content is 1.8-2.3OH/nm2。
(3) Then putting the dried modified halloysite nanotube and polyphenylene sulfide slices (the polyphenylene sulfide slices are spinning-grade polyphenylene sulfide slices, the relative molecular mass is 3-5 ten thousand) into a double-screw extruder for extrusion granulation, wherein the rotating speed of the screws is 100r/min, and the temperature of each heating section of the double-screw extruder is as follows: the first section (feed zone) was 285 deg.C, the second section (extrusion zone) 305 deg.C, the third section (metering zone) 305 deg.C, the fourth section (homogenization zone) 305 deg.C, and the fifth section (outlet zone) 305 deg.C. Preparing a polyphenylene sulfide/modified halloysite nanotube hybrid composite slice; the mass fraction of the modified halloysite nanotube is 1.0%, and the mass fraction of the PPS resin is 99.0%.
(4) And adding the dried polyphenylene sulfide/modified halloysite nanotube hybrid composite slice into melt spinning equipment, wherein the spinning temperature is 325 ℃, carrying out melt spinning, winding and stretching at the spinning speed of 600m/min to obtain a primary yarn, wherein the winding speed is 600m/min, and carrying out secondary drafting, wherein the total drafting multiple is 3.8 times, so as to obtain the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber.
Through the characterization, the breaking strength of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is 3.67cN/dtex, and the retention rate of the breaking strength of the fiber is 87.8% after the fiber is treated at the high temperature of 230 ℃ for 72 hours.
Example 3
A polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is composed of 98.5 wt% of polyphenylene sulfide PPS resin and 1.5 wt% of modified halloysite nanotubes.
The preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber comprises the following steps:
(1) adding 15g of halloysite nanotubes (Zhengzhou Jinyangtai ceramics Co., Ltd., pipe diameter of 60-80nm, length of 600-1000nm) and 400mL of 2mol/L sulfuric acid solution into a three-mouth flask, continuously carrying out mechanical stirring reaction at 80 ℃ for 96h, stopping the reaction, carrying out centrifugal treatment on a product obtained after the reaction at the rotating speed of 5000r/min for 5min, repeatedly washing the solid matter obtained by centrifugation with deionized water until the pH value of the aqueous solution is neutral, then centrifuging and placing in an oven at 80 ℃ for drying for 24h, and storing a sample in a dryer after the drying is finished to obtain the acid-leached and etched halloysite nanotubes.
(2) Placing 150ml of deionized water, 200ml of absolute ethyl alcohol and 0.9g of the acid-leached and etched halloysite nanotube prepared in the step (1) into a 500ml three-neck flask, ultrasonically dispersing for 30min, then adding 3g of ammonia water with the concentration of 30%, wherein the pH value of the system is 12, then mechanically stirring at the rotation speed of 300r/min for 35min at the temperature of 25 ℃, then adding 0.9g of ethyl orthosilicate, reacting for 10h under the mechanical stirring at the rotation speed of 300r/min, obtaining a product after the reaction is finished, respectively washing 3 times by using ethanol and water, then centrifuging, placing the product into a blast oven for drying for 24h at the temperature of 90 ℃, then placing into a vacuum oven for 12h at the temperature of 90 ℃, and then placing into a dryer for storage to obtain the modified halloysite nanotube. The modified halloysite nanotube has the purity of 99.8 percent, the length of 600-1000nm and the length-diameter ratio of 9.2-9.6. The modified halloysite nanotube has a large inner cavity structure, the inner diameter of the tube is 31.3-38.5nm, and the mass ratio of Si/Al is 3.34-6.27. The surface of the modified halloysite nanotube is coated with a rough and compact silicon dioxide layer, and the diameter of the nano silicon dioxide particle on the layer surface is 14-20nm, surface hydroxyl content of 2.1-3.0OH/nm2。
(3) Then putting the dried modified halloysite nanotube and polyphenylene sulfide slices (the polyphenylene sulfide slices are spinning-grade polyphenylene sulfide slices, the relative molecular mass is 3-5 ten thousand) into a double-screw extruder for extrusion granulation, wherein the rotating speed of the screws is 100r/min, and the temperature of each heating section of the double-screw extruder is as follows: the first section (feed zone) was 285 deg.C, the second section (extrusion zone) 305 deg.C, the third section (metering zone) 305 deg.C, the fourth section (homogenization zone) 305 deg.C, and the fifth section (outlet zone) 305 deg.C. Preparing a polyphenylene sulfide/modified halloysite nanotube hybrid composite slice; the mass fraction of the modified halloysite nanotube is 1.5%, and the mass fraction of the PPS resin is 98.5%.
(4) And adding the dried polyphenylene sulfide/modified halloysite nanotube hybrid composite slice into melt spinning equipment, wherein the spinning temperature is 325 ℃, carrying out melt spinning, winding and stretching at the spinning speed of 600m/min to obtain a primary yarn, wherein the winding speed is 600m/min, and carrying out secondary drafting, wherein the total drafting multiple is 3.8 times, so as to obtain the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber.
Through the characterization, the breaking strength of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is 3.02cN/dtex, and the retention rate of the breaking strength of the fiber is 92.3% after the fiber is processed at the high temperature of 230 ℃ for 72 hours.
Claims (8)
1. The polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is characterized by comprising 98.5-99.5 wt% of polyphenylene sulfide (PPS) resin and 0.5-1.5 wt% of modified halloysite nanotube, wherein the modified halloysite nanotube has a large inner cavity structure, the inner diameter of the tube is 23.6-38.5nm, the Si/Al mass ratio is 1.33-6.27, the surface of the modified halloysite nanotube is coated with a rough and compact silicon dioxide layer, the diameter of a nano silicon dioxide particle on the layer is 5-20nm, and the surface hydroxyl content is 1.5-3OH/nm2。
2. The polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber according to claim 1, wherein the purity of the modified halloysite nanotube is higher than 99.5%, the length is 500-1000nm, and the aspect ratio is 8.8-9.7.
3. The preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber according to any one of claims 1-2, which comprises:
step 1: adding the halloysite nanotube and a sulfuric acid solution into a three-neck flask, stirring at 50-80 ℃ for reaction, centrifuging, washing the obtained solid to neutrality, centrifuging and drying to obtain the acid-leached and etched halloysite nanotube;
step 2: placing deionized water, absolute ethyl alcohol and the acid-leached halloysite nanotube prepared in the step 1 into a container, performing ultrasonic dispersion, then adding a catalyst, stirring, adding a silicon source, stirring for reaction, after the reaction is finished, obtaining a product through centrifugation, washing, centrifuging and drying to obtain the modified halloysite nanotube;
and step 3: and extruding and granulating the modified halloysite nanotube and polyphenylene sulfide, and carrying out melt spinning to obtain the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber.
4. The preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber as claimed in claim 3, wherein the stirring time after adding the catalyst in step 2 is 30-60min, and the stirring time after adding the silicon source is 6-10 h.
5. The preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber according to claim 3, wherein the ratio of the deionized water to the absolute ethyl alcohol is 1-3: 1.
6. the preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber as claimed in claim 3, wherein the catalyst is ammonia water, and the dosage of the catalyst is 0.2-2% of the system.
7. The preparation method of the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber according to claim 3, wherein the silicon source is tetraethoxysilane, and the dosage of the tetraethoxysilane is 0.1-1% of the system.
8. The method for preparing the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber according to claim 3, wherein the melt spinning process in the step 3 has a spinning temperature of 325 ℃, a spinning speed of 600m/min, and the polyphenylene sulfide/modified halloysite nanotube hybrid composite fiber is prepared by secondary drafting with a total draft multiple of 3.8.
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| CN102220659A (en) * | 2011-06-21 | 2011-10-19 | 太原理工大学 | Preparation method of heat-resistant polyphenylene sulfide fiber |
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| WO2013085630A1 (en) * | 2011-12-10 | 2013-06-13 | The Boeing Company | Fiber with gradient properties and method of making the same |
| CN103160941A (en) * | 2011-12-10 | 2013-06-19 | 波音公司 | Hollow fiber with gradient properties and method of making the same |
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