CN114232109A - Method for preparing polyether ketone fiber based on nondestructive dissolution wet method - Google Patents
Method for preparing polyether ketone fiber based on nondestructive dissolution wet method Download PDFInfo
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- CN114232109A CN114232109A CN202111401064.9A CN202111401064A CN114232109A CN 114232109 A CN114232109 A CN 114232109A CN 202111401064 A CN202111401064 A CN 202111401064A CN 114232109 A CN114232109 A CN 114232109A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
- D01F6/665—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers from polyetherketones, e.g. PEEK
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention discloses a method for preparing polyether ketone fiber based on a nondestructive dissolution wet method. The preparation method comprises the following steps: 1. dissolving polyether ketone in a fluorine-based or chlorine-based polar solvent at room temperature without damage to obtain uniform polyether ketone solution spinning solution; 2. carrying out wet spinning on the spinning solution, injecting the spinning solution into a coagulating bath through a needle with narrow diameter and large length-diameter ratio for forming, and then drafting, drying and winding to obtain a primary spinning polyether ketone fiber; 3. and (3) winding and collecting the primary spinning polyether ketone fiber after multi-stage hot drawing, and performing high-temperature treatment and shaping to obtain the high-performance polyether ketone fiber. The method adopts fluorine-based or chlorine-based polar solvent to realize the lossless dissolution of the polyether ketone, so as to form uniform and stable colloidal solution; in the spinning process, the polyether ketone forms a firm network structure under the shearing action, and the shape and the volume of the fiber can be kept unchanged; the obtained polyether ketone fiber has the excellent characteristics of light weight, high strength, high temperature resistance, flame retardance and the like.
Description
Technical Field
The invention relates to a method for preparing polyether ketone fiber based on a nondestructive dissolution wet method, and belongs to the technical field of preparation of functional thermal fiber.
Background
The polymer fiber is an important component of polymer materials, and plays an important role in social life and industrial production. Among them, as one of the specialty fibers, high temperature resistant fibers capable of being used for a long period of time at 180 ℃ or more or maintaining good physical properties for a certain period of time at higher temperatures have received high attention.
With the rapid development of the fields of aerospace, fire protection, nuclear industry and the like in China, the demand for high-temperature resistant special fibers is increasing day by day, and the comprehensive performance needs to be further optimized; the existing thermosetting resin has the problems of insufficient toughness, high fiberization difficulty of high-temperature resistant thermoplastic resin and the like, and the development of high-temperature resistant special fibers is limited.
Among the thermoplastic special engineering plastics which are commercialized at present, the polyaryletherketone polymer has the highest heat-resistant grade. Polyaryletherketones are semi-crystalline thermoplastics with the advantages of low density, high mechanical properties, high temperature thermal stability, electrical insulation, chemical resistance, and the like. Of the family of polyaryletherketones, polyetheretherketone and polyetherketoneketone are most widely used. In comparison, polyetherketoneketone contains more ketone bonds, has a molecular structure with a difference of the proportion of benzene to benzene, has higher glass transition temperature and melting temperature, wider thermal regulation window and better mechanical property, and has attracted more attention in recent years. The development of high-temperature special fibers with high mechanical properties based on polyether ketone has a slight significance for transformation upgrading of the high-performance fiber industry in China, and also has a wide application space in various fields.
From the perspective of polymer spinnability, the polyaryletherketone polymer generally has the problems of strong solvent resistance, high melting temperature, poor melt fluidity and the like, so that wet spinning is difficult to realizeThe use of filaments, and also the direct use of melt spinning techniques, has faced a number of difficulties. The main solution at present is to improve the processability by blending polyaryletherketone with inorganic lubricant, polyester and the like to reduce the melt viscosity, but the mechanical properties of the fiber are also reduced by blending. The other method aims at the characteristic of difficult dissolution, improves the dissolving capacity by means of sulfonation, chloromethylation, ring-opening polymerization, multicomponent copolymerization and the like, and adopts a solution method for spinning. However, the chemical modification of the polymer destroys the original structure, resulting in a significant decrease in the heat resistance, mechanical properties or chemical resistance of the polymer. Therefore, for a long time, the preparation method of the polyaryletherketone fiber still mainly adopts melt extrusion and a derivative process (such as melt electrostatic spinning) (document 1: M.H.G.Deeg.Process of manufacturing an artificial polyether ketone fiber product. US patent 1985, US 47988; document 2: Wangbin, Zhaibo, Arthrofu, Zyun, Guanshao, Hezhenhua, Zhaoling, Wuloy. spinning grade polyetheretherketone resin special material and a preparation method thereof. Chinese invention patent ZL200810050213. X; document 3: Wangbin, Guanguanguan, Zhailing, Zhaohua, Jianzhenghua, Guanson, Guanyun, Zhaibo, Yanghua, loyalty, Wahle. polyether ketone fiber melt drawing and hot setting preparation method thereof. Chinese invention patent 200810050363.0; document 4: R.I.Sheskan, Sheskan, Shuqing, Kinghua, Yoghou, Ku. K.112, Ku patent No. K.P.112, Ku patent No. PEEK.D.42.
M.Skrifvars,S.
P.
The effect of melt processing parameters on The bioactivity of polyethetherketone, J.appl.Polym.Sci.2012,126(5), 1564; document 6: dundebeng, lislon, jiayuanqian, royal sea, zhangqing, liu yong, electrostatic spinning for preparing polyetherketoneketone superfine fiber, engineering plastics application 2016,44(4), 44; document 7: koelreuteria paniculata (Koelreuteria paniculata and Koelreuteria paniculata)The invention relates to a polyether-ether-ketone staple fiber yarn and a preparation method thereof, wherein the yarn is prepared from Wuzhiping, Wangzgui guest, Zhang Mei, Zshuling, Liyonggong, Su xu Bian, Yan inkstone and Maleli.
In addition, regarding the polyetherketoneketone fiber and the polyetherketoneketone composite fiber, only akma france company, arkema corporation (usa) and imperial aramid company limited (netherlands) have applied for related invention patents in china, in which: patent CN102333910A discloses a method for preparing polyetherketoneketone composite fiber by using melt spinning, in which multiwall nanotubes containing carbon, nitrogen, boron, phosphorus, silicon, tungsten and other elements are dispersed in polyetherketoneketone matrix, and the polyetherketoneketone composite fiber is prepared by using melt spinning; granted patent 201080007055.5 provides a method for preparing composite fiber containing polyetherketoneketone and mineral nanotubes, which comprises mixing various mineral nanotubes with polyetherketoneketone matrix by melt compounding, and preparing composite fiber by melt spinning; the patent CN110249083A is the only Chinese invention patent for preparing polyether ketone fiber by wet spinning at present, which is the application of PCT international patent WO 2018/087121 in China, concentrated sulfuric acid is adopted to dissolve polyether ketone to obtain spinning solution, and the spinning solution enters a coagulating bath through a spinneret to prepare the polyether ketone fiber. However, the method still has a series of technical problems which limit the development and application of the method: 1) dissolution of polyetherketoneketone in concentrated sulfuric acid is actually a sulfonation process of the polymer (document 1: huang, P.Shao, C.M.Burns, X.Feng.Sulfonation of poly (ether ether ketone) (PEEK) Kinetic study and characterization. J.appl.Polym.Sci.2001,82(11), 2651; document 2: li, T.Liu, Z.C.W.Tang, J.Jia, W.H.ZHong.novel moisture induced flexible sulfonated poly (ethylene ketone) foam with super dielectric properties J.Mater.Chem.2011,21(35),13546), wherein the polyether ketone has already undergone sulfonation reaction in the dissolving process, so that the performance of the fiber obtained by spinning is greatly influenced; 2) the dissolution of polyetherketoneketone in concentrated sulfuric acid requires the addition of a mechanical mixing process, for example, the patent recommends the use of kneaders or extruders to facilitate the mixing process, which means that it is still difficult to achieve uniform mixing or dissolution; 3) the spinning solution is preferably carried out at a temperature of 50 to 90 ℃, on one hand, the temperature region can further promote the sulfonation of the polyetherketoneketone, and on the other hand, additional temperature control equipment is needed, which brings difficulty to the stability of wet spinning; 4) residual acid exists in the polyether ketone fiber obtained by wet spinning, and the neutralization is promoted by increasing the pH value of a coagulating bath; 5) the obtained fiber has poor structural uniformity and mechanical strength lower than 80MPa, and is difficult to be widely applied. Based on the above problems, there is a need to develop efficient and stable wet spinning to prepare high performance polyetherketoneketone fiber.
Disclosure of Invention
The technical problem solved by the invention is as follows: at present, there is only a related art for preparing polyetherketoneketone (composite) fibers by melt spinning, while wet spinning using concentrated sulfuric acid is a sulfonation means based on polyetherketoneketone polymers, and is dissolved as sulfonated polyetherketoneketone, and thus there is no related art for wet spinning by non-destructive dissolution of polyetherketoneketone. In addition, the spinning method is carried out at high temperature or needs to introduce a mechanical mixing process, so that the steps are complicated, the cost is high, and the obtained fiber mechanics also has the problems of poor structural uniformity, low strength, poor performance and the like.
In order to solve the technical problem, the invention provides a method for preparing polyether ketone fiber based on nondestructive dissolution, which comprises the following steps:
step 1: adopting fluorine-based or chlorine-based polar solvent to dissolve polyether ketone without damage to obtain spinning stock solution;
step 2: carrying out wet spinning on the spinning solution obtained in the step 1, injecting the spinning solution into a coagulating bath for coagulation forming, and then carrying out pre-drafting, drying and winding to obtain a primary spinning polyether ketone fiber;
and step 3: and (3) winding and collecting the primary spinning polyether ketone fiber obtained in the step (2) after multi-stage hot drawing, and performing heat treatment setting to obtain the polyether ketone fiber.
Preferably, in the polyether ketone in the step 1, the molar ratio of the para-position structure to the ortho-position structure (para-position to ortho-position structure ratio for short, or T/I ratio) is 50:50, 60:40, 70:30, 80:20 or 100:0, and the polyether ketone is powder with the particle size of less than or equal to 300 μm.
Preferably, the fluorine-based polar solvent in the step 1 is trifluoroacetic acid and/or 3,3, 3-trifluoro-2, 2-dimethylpropionic acid; the chlorine-based polar solvent is at least one of p-chlorophenol, dichloroacetic acid and dichloropropionic acid.
More preferably, the fluorine-based polar solvent is trifluoroacetic acid, and the chlorine-based polar solvent is p-chlorophenol.
Preferably, the process parameters for dissolution in step 1 are as follows: stirring speed is 1200-1800 rpm, stirring time is 6-12 h, and stirring temperature is 25-50 ℃; the concentration of the polyether ketone in the spinning solution is 5-22 wt%.
Preferably, the wet spinning in the step 2 adopts a needle head with a narrow diameter and a large length-diameter ratio, wherein the inner diameter of the needle head is 0.1-0.5 mm, and the length of the needle head is 50-100 mm; the injection process parameters are as follows: the extrusion rate is 0.05-2 mL/min, and the extrusion temperature is 25-30 ℃.
Preferably, the coagulating bath in the step 2 is water or ethanol, wherein, when trifluoroacetic acid, 3,3, 3-trifluoro-2, 2-dimethylpropionic acid, dichloroacetic acid and dichloropropionic acid are used as solvent, water is preferred, and when p-chlorophenol is used as solvent, ethanol is preferred.
Preferably, the temperature of the coagulating bath in the step 2 is 5-40 ℃, and the time required by the forming is 0.5-2 min.
More preferably, the temperature of the coagulating bath is 25-30 ℃.
Preferably, the pre-drafting in step 2 is specifically: and (3) drawing the polyether ketone fiber obtained by solidification forming through 3-5 guide rails after the polyether ketone fiber is led out of the solidification bath, wherein the drawing multiple is 1-2 times, and the drawing time is 1-5 min, so that the fiber is naturally dried, pre-drawn and wound for collection.
Preferably, the hot drawing in the step 3 is to perform hot drawing on the primary spun polyether ketone fiber obtained in the step 2 by using a horizontal tube furnace, the furnace body length of the horizontal tube furnace is 50-90 cm, the hot drawing adopts three-stage hot drawing, and the specific process parameters are as follows: the first stage drafting temperature is 200-220 ℃, the drafting multiple is 2-3.5 times, the second stage drafting temperature is 230-250 ℃, the drafting multiple is 1.5-2 times, the third stage drafting temperature is 240-260 ℃, and the drafting multiple is 1.5-2 times.
Preferably, the temperature of the heat treatment setting in the step 3 is 240-300 ℃, and the time is 1-5 h.
More preferably, the temperature of the heat treatment setting is 250-280 ℃ and the time is 1.5-2 h.
The invention also provides the polyether ketone fiber prepared by the method for preparing the polyether ketone fiber based on the nondestructive dissolution, and the mass density of the polyether ketone fiber is lower than 0.9g/cm3The porosity is higher than 30%, the tensile breaking strength is higher than 600MPa, the thermal weight loss temperature is higher than 450 ℃, and the flame retardant grade is V-0 grade.
The design idea of the invention is as follows:
(1) the polyether ketone is dissolved in a fluorine-based or chlorine-based polar solvent without damage, so that the polyether ketone is dissolved in the true sense, and the sulfonation reaction caused by dissolving the polyether ketone by adopting concentrated sulfuric acid is avoided, so that the excellent physical properties of the polyether ketone are fully maintained in the fiber;
(2) the polyether ketone solution forms a firm network structure under the shearing action in the wet spinning process, and the rigidity of the molecules of the polyether ketone solution is combined, so that the shape and the volume of the polyether ketone fiber can be kept unchanged in the forming process (the phase separation of a solvent and polyether ketone occurs in the forming process), and the generation of a phase separation induced microporous structure is facilitated;
(3) polymer molecules in the polyether ketone fiber not only construct a compact network structure, but also form a rich microporous structure, so that organic integration of various properties such as light weight, high strength, high temperature resistance, flame retardance and the like is realized.
Compared with the prior art, the invention has the following beneficial effects:
1. the polyether ketone is dissolved in a fluorine-based or chlorine-based polar solvent in a lossless manner, a spinning stock solution concentration, a needle specification, an extrusion rate, a coagulation bath type and a pre-drafting rate in a wet spinning process are regulated to prepare a primary-spinning polyether ketone fiber, and a high-performance polyether ketone fiber is obtained through hot-drafting and high-temperature heat setting treatment, wherein the specific molecular rigidity and entanglement characteristics of polyether ketone enable the fiber volume to be kept unchanged in a fiber forming phase separation process, so that a rich microporous structure is constructed in the fiber, and further optimized regulation and control are obtained in the hot-drafting process, which is different from the fact that the fiber volume can be obviously shrunk in other polymer wet spinning processes; the polyether ketone fiber prepared by the method has the excellent characteristics of light weight, high strength, high temperature resistance, flame retardance and the like.
2. The polyaryletherketone polymer is generally difficult to dissolve, so that the related wet spinning process is very deficient, and the high melting temperature of the polyaryletherketone polymer also brings many difficulties for melt spinning.
Drawings
FIG. 1 shows the dope obtained in step 1 of example 1;
FIG. 2 shows as-spun polyetherketoneketone fibers obtained in step 3 of example 1;
FIG. 3 shows a heat-set polyetherketoneketone fiber obtained in step 5 of example 1;
FIG. 4 is a cross-sectional electron micrograph of a polyetherketoneketone fiber prepared in example 1;
FIG. 5 shows the results of mechanical tests on the polyetherketoneketone fibers prepared in example 1;
FIG. 6 shows the results of the thermogravimetric testing of the polyetherketoneketone fiber prepared in example 1 in air;
FIG. 7 shows the results of the flame retardancy test of the polyetherketoneketone fibers prepared in example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Example 1
The embodiment provides a method for preparing polyether ketone fiber based on a nondestructive wet dissolving method, which specifically comprises the following steps:
1) firstly, a polyetherketoneketone solution is prepared, and polyetherketoneketone (T/I ratio is 60:40) is dissolved in trifluoroacetic acid at room temperature (25 ℃) with the concentration of 12.5 wt%, the stirring speed is 1500rpm, and the stirring time is 6h, so that a uniform and stable spinning solution is obtained, as shown in figure 1.
2) The polyetherketoneketone solution was injected into a pure water coagulation bath at room temperature using an injection needle having an inner diameter of 0.15mm and a length of 60cm at an extrusion rate of 0.2 mL/min. The time the fiber has elapsed in the coagulation bath was 50 s.
3) And (3) leading the coagulated and formed fiber out of a coagulation bath, passing through 5 guide rails, pre-drafting under the action of traction, wherein the drafting multiple is 1.2 times, the drafting time is 2min, and directly collecting the fiber on a winding drum after drafting to obtain the naturally dried as-spun polyether ketone fiber, as shown in figure 2.
4) And (3) leading the primary-spun polyether ketone fiber out of a winding drum, carrying out hot drawing treatment by a horizontal tube furnace, and collecting the primary-spun polyether ketone fiber on another winding drum. A tube furnace with the length of 80cm is adopted, and three-stage (secondary) hot drawing is adopted, wherein the first-stage drawing temperature is 210 ℃, the drawing multiple is 2 times, the second-stage drawing temperature is 240 ℃, the drawing multiple is 2 times, the third-stage drawing temperature is 260 ℃, and the drawing multiple is 1.5 times.
5) And putting the hot-stretched polyether ketone fiber and the winding drum into a hot oven for high-temperature heat setting treatment, wherein the heat setting temperature is 280 ℃ and the heat setting time is 1.5h, so as to obtain the heat-set polyether ketone fiber, as shown in figure 3.
The polyether ketone fiber obtained by the steps has uniform diameter of 52 mu m and mass density of 0.85g/cm3(corresponding to porosity of 34.6%), tensile breaking strength of 650MPa, thermal weight loss temperature of more than 455 ℃, and flame retardant grade V-0. FIGS. 4 to 7 show the cross-sectional electron microscope scanning photograph, the mechanical test curve, the weight loss test curve and the flame retardant test result of the fiber.
Example 2
The embodiment provides a method for preparing polyether ketone fiber based on a nondestructive wet dissolving method, which specifically comprises the following steps:
1) firstly, preparing a polyether ketone solution, dissolving polyether ketone (T/I ratio is 60:40) in trifluoroacetic acid at the temperature of 40 ℃, wherein the concentration is 22 wt%, the stirring speed is 1800rpm, and the stirring time is 6h, so as to obtain uniform and stable spinning solution.
2) The polyetherketoneketone solution was injected into a pure water coagulation bath at 40 ℃ at room temperature using an injection needle having an inner diameter of 0.5mm and a length of 50cm, at an extrusion rate of 2 mL/min. The time the fiber was in the coagulation bath was 2 min.
3) And (3) leading the coagulated and formed fiber out of a coagulation bath, passing through 5 guide rails, pre-drafting under the traction action, wherein the drafting multiple is 1.1 times, the drafting time is 2min, and directly collecting the fiber on a winding drum after drafting to obtain the naturally dried primary spinning polyether ketone fiber.
4) And (3) leading the primary-spun polyether ketone fiber out of a winding drum, carrying out hot drawing treatment by a horizontal tube furnace, and collecting the primary-spun polyether ketone fiber on another winding drum. A tube furnace with the length of 80cm is adopted, and three-stage (secondary) hot drawing is adopted, wherein the first-stage drawing temperature is 210 ℃, the drawing multiple is 3 times, the second-stage drawing temperature is 240 ℃, the drawing multiple is 2 times, the third-stage drawing temperature is 260 ℃, and the drawing multiple is 1.5 times.
5) And putting the hot-stretched polyether ketone fiber and the winding drum into a hot oven for high-temperature heat setting treatment, wherein the heat setting temperature is 280 ℃, and the heat setting time is 2 hours, so as to obtain the heat-set polyether ketone fiber.
The polyether ketone fiber obtained through the steps has the diameter of 160 mu m and the mass density of 0.87g/cm3(corresponding to porosity of 33.1%), tensile breaking strength of 605MPa, thermal weight loss temperature of more than 455 ℃, and flame retardant grade V-0.
Example 3
The embodiment provides a method for preparing polyether ketone fiber based on a nondestructive wet dissolving method, which specifically comprises the following steps:
1) preparing a polyetherketoneketone solution, dissolving polyetherketoneketone (T/I is 50:50) in p-chlorophenol at the temperature of 50 ℃, wherein the concentration is 8.5 wt%, the stirring speed is 1200rpm, and the stirring time is 12 hours, so as to obtain a uniform and stable wet spinning solution.
2) The same procedure as in step 2) of example 1 was followed, except that the coagulation bath was ethanol.
3) -5): same as in steps 3) -5 of example 1).
The polyether ketone fiber obtained through the steps has the diameter of 38 mu m and the mass density of 0.84g/cm3(corresponding to a porosity of 35.4%), tensile breaking strength 675MPa, thermal weight loss temperature higher than 455 ℃ and flame retardant grade V-0.
Example 4
The embodiment provides a method for preparing polyether ketone fiber based on a nondestructive wet dissolving method, which specifically comprises the following steps:
1) preparing a polyetherketoneketone solution, dissolving polyetherketoneketone (T/I ratio is 70:30) in p-chlorophenol at 50 ℃, wherein the concentration is 12 wt%, the stirring speed is 1800rpm, and the stirring time is 9 hours, so as to obtain a uniform and stable wet spinning solution.
2) The same procedure as in step 2) of example 1 was followed, except that the coagulation bath was ethanol.
3) -5): same as in steps 3) -5 of example 1).
The polyether ketone fiber obtained through the steps has the diameter of 59 mu m and the mass density of 0.86g/cm3(corresponding to porosity of 33.8%), tensile break strength of 685MPa, thermal weight loss temperature of more than 455 ℃, and flame retardant grade V-0.
Comparative example 1
1) Preparing a polyetherketoneketone solution, dissolving polyetherketoneketone (T/I ratio is 60:40) in trifluoroacetic acid at room temperature, wherein the concentration is 4.5 wt%, the stirring speed is 1200rpm, and the stirring time is 6h, so as to obtain uniform and stable spinning solution.
2) Continuous spinning could not be carried out by the same procedure as in step 2) of example 1, and segmented polyetherketoneketone staple fibers were obtained.
Comparative example 2
1) The operation was the same as in step 1) of example 1.
2) The same operation as in step 2) of example 1 was carried out except that the extrusion rate was 3mL/min, and at high-speed injection, the polyetherketoneketone fiber was crimped, and it was difficult to stably draw and continuous spinning could not be carried out.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing polyether ketone fiber based on nondestructive dissolution is characterized by comprising the following steps:
step 1: adopting fluorine-based or chlorine-based polar solvent to dissolve polyether ketone without damage to obtain spinning stock solution;
step 2: carrying out wet spinning on the spinning solution obtained in the step 1, injecting the spinning solution into a coagulating bath for coagulation forming, and then carrying out pre-drafting, drying and winding to obtain a primary spinning polyether ketone fiber;
and step 3: and (3) winding and collecting the primary spinning polyether ketone fiber obtained in the step (2) after multi-stage hot drawing, and performing heat treatment setting to obtain the polyether ketone fiber.
2. The method for preparing polyetherketoneketone fibers based on nondestructive dissolution according to claim 1, wherein in the polyetherketoneketone in the step 1, the molar ratio of para-phenyl structure to ortho-phenyl structure is 50:50, 60:40, 70:30, 80:20 or 100:0, and the polyetherketoneketone is selected from powder with a particle size of less than or equal to 300 μm.
3. The method for preparing polyetherketoneketone fiber based on nondestructive dissolution according to claim 1, wherein the fluorine-based polar solvent in the step 1 is trifluoroacetic acid and/or 3,3, 3-trifluoro-2, 2-dimethylpropionic acid; the chlorine-based polar solvent is at least one of p-chlorophenol, dichloroacetic acid and dichloropropionic acid.
4. The method for preparing polyetherketoneketone fiber based on non-destructive dissolution according to claim 1, wherein the process parameters of dissolution in step 1 are: stirring speed is 1200-1800 rpm, stirring time is 6-12 h, and stirring temperature is 25-50 ℃; the concentration of the polyether ketone in the spinning solution is 5-22 wt%.
5. The method for preparing polyetherketoneketone fiber based on nondestructive dissolution according to claim 1, wherein the wet spinning in the step 2 employs a needle having an inner diameter of 0.1 to 0.5mm and a length of 50 to 100 mm; the injection process parameters are as follows: the extrusion rate is 0.05-2 mL/min, and the extrusion temperature is 25-30 ℃.
6. The method for preparing polyetherketoneketone fibers based on non-destructive dissolution according to claim 1, wherein the coagulation bath in step 2 is water or ethanol.
7. The method for preparing polyetherketoneketone fiber based on nondestructive dissolution according to claim 1, wherein the temperature of the coagulation bath in the step 2 is 5 to 40 ℃, and the time required for the molding is 0.5 to 2 min; the pre-drafting comprises the following specific steps: and (3) drawing the polyether ketone fiber obtained by solidification forming through 3-5 guide rails after the polyether ketone fiber is led out of the solidification bath, wherein the drawing multiple is 1-2 times, and the drawing time is 1-5 min, so that the fiber is naturally dried, pre-drawn and wound for collection.
8. The method for preparing the polyetherketoneketone fiber based on the nondestructive dissolution according to claim 1, wherein the hot drawing in the step 3 is to perform hot drawing on the as-spun polyetherketoneketone fiber obtained in the step 2 by using a horizontal tube furnace, the furnace body length of the horizontal tube furnace is 50-90 cm, the hot drawing is performed by using three-stage hot drawing, and the specific process parameters are as follows: the first stage drafting temperature is 200-220 ℃, the drafting multiple is 2-3.5 times, the second stage drafting temperature is 230-250 ℃, the drafting multiple is 1.5-2 times, the third stage drafting temperature is 240-260 ℃, and the drafting multiple is 1.5-2 times.
9. The method for preparing polyetherketoneketone fiber based on nondestructive dissolution according to claim 1, wherein the temperature of heat treatment setting in the step 3 is 240 to 300 ℃ and the time is 1 to 5 hours.
10. Any of claims 1 to 9The polyether ketone fiber prepared by the method for preparing the polyether ketone fiber based on the nondestructive dissolution is characterized in that the mass density of the polyether ketone fiber is lower than 0.9g/cm3The porosity is higher than 30%, the tensile breaking strength is higher than 600MPa, the thermal weight loss temperature is higher than 450 ℃, and the flame retardant grade is V-0 grade.
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| CN114685971A (en) * | 2022-04-18 | 2022-07-01 | 东华大学 | Short carbon fiber/polyether ketone composite powder material and preparation method thereof |
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| CN114685971B (en) * | 2022-04-18 | 2023-08-29 | 东华大学 | Chopped carbon fiber/polyether ketone composite powder material and preparation method thereof |
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