CN113481623B - Fine-denier semi-aromatic polyamide fiber with excellent uniformity and preparation method thereof - Google Patents
Fine-denier semi-aromatic polyamide fiber with excellent uniformity and preparation method thereof Download PDFInfo
- Publication number
- CN113481623B CN113481623B CN202110810162.1A CN202110810162A CN113481623B CN 113481623 B CN113481623 B CN 113481623B CN 202110810162 A CN202110810162 A CN 202110810162A CN 113481623 B CN113481623 B CN 113481623B
- Authority
- CN
- China
- Prior art keywords
- aromatic polyamide
- semi
- polyamide fiber
- fine denier
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Polyamides (AREA)
Abstract
The invention belongs to the field of high-molecular materials, and particularly relates to a fine-denier semi-aromatic polyamide fiber with excellent uniformity and a preparation method thereof. The invention provides a preparation method of a fine denier semi-aromatic polyamide fiber, which comprises the following steps: 1) pre-treating; 2) slicing and heat treatment; 3) and (4) melt spinning. The semi-aromatic polyamide fiber with fine titer is prepared by pretreating, slicing, thermally treating and melt spinning semi-aromatic polyimide and a copolymer thereof; the fineness of the obtained fiber is 0.9-4.5dtex, the elongation at break is as follows: 10-97%; the mechanical strength is 1.1-4.8 cN/dtex, the fiber diameter unevenness (CV value) of the drawn yarn is less than 1.0%, and the heat resistance is 170-240 ℃; and has chemical resistance to organic solvents except concentrated sulfuric acid and trifluoroacetic acid.
Description
Technical Field
The invention belongs to the field of high-molecular materials, and particularly relates to a fine-denier semi-aromatic polyamide fiber with excellent uniformity and a preparation method thereof.
Background
Conventionally, nylon 6, nylon 66, and the like are known as polyamide fibers, and they are used for various industrial material applications because they have high strength, high toughness, and excellent durability. However, these conventional polyamide fibers still have low dimensional stability due to insufficient heat resistance and chemical resistance. In particular, in applications such as automobile parts and electric/electronic parts, chemical resistance such as heat resistance and acid resistance is required for use at high temperatures. The semi-aromatic polyamide has the advantages that the heat resistance, the corrosion resistance and the mechanical property of the semi-aromatic polyamide are improved due to the introduction of the aromatic ring in the structure of the aliphatic chain polyamide molecular chain. However, in order to improve the heat resistance when the semi-aromatic polyamide is used at a high temperature, it is generally necessary to set the melting point temperature of the resin to 290 ℃ or higher, and when the semi-aromatic polyamide is melt-spun into a semi-aromatic polyamide fiber, the spinning temperature is close to the decomposition temperature of the polyamide main chain, so that the deterioration of the resin is likely to occur, and there is a problem in the spinning stability. Further, since the melting point of the resin is high, it is difficult to spin the resin in a high viscosity state, particularly to spin a fine fiber of a single yarn.
In patent CN111902575A, when melt spinning is performed by using a combination of heat-resistant plasticizers, the spinning temperature of the highly heat-resistant semi-aromatic polyamide resin can be lowered, and the deterioration of the semi-aromatic polyamide resin during melt spinning is suppressed, and the spinning stability can be significantly improved, thereby obtaining a semi-aromatic polyamide fiber; however, in this method, an auxiliary agent needs to be introduced, and the auxiliary agent will migrate during the use of the high-temperature resistant semi-aromatic polyamide fiber, thereby affecting the performance during the use. Therefore, from the viewpoint of controlling the molding process of the semi-aromatic polyamide fiber, it would be a general and simple method to develop a single-component semi-aromatic polyamide fine denier fiber with stable performance.
Disclosure of Invention
In view of the above-mentioned drawbacks, the present invention provides a method for preparing a fine denier single-component semi-aromatic polyamide fiber, which solves the problems of unstable spinning process, large fiber denier, and non-uniform diameter distribution of the semi-aromatic polyamide fiber, and prepares a high temperature resistant, corrosion resistant, fine denier (0.9 to 4.5dtex) polyamide fiber, which can be applied to vehicle parts, electric/electronic parts, and the like.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the present invention is to provide a method for preparing a fine denier semi-aromatic polyamide fiber, comprising the steps of:
1) pretreatment: soaking semi-aromatic polyamide and a copolymer thereof in deionized water at 70-100 ℃ for 12-72 h, and then drying;
2) slicing and heat treatment: preserving heat of the pretreated semi-aromatic polyamide and the copolymer thereof at 85-90 ℃ for 10-12 h, then raising the temperature at the speed of 0.5-5 ℃/min to 100-130 ℃ for 1-3 h, finally rapidly lowering the temperature at the speed of 10-50 ℃/min to 60-80 ℃, and keeping the temperature for 8-10 h to obtain semi-aromatic polyamide and copolymer resin slices thereof;
3) melt spinning: and (3) carrying out melt spinning on the semi-aromatic polyamide and the semi-aromatic polyamide copolymer chips to obtain the fine-denier semi-aromatic polyamide fiber.
Further, the structural formula of the semi-aromatic polyimide copolymer is as follows:
further, the semi-aromatic polyamide copolymer is prepared by the following method: sequentially adding a monomer, a catalyst and deionized water into a reactor, and heating to 80-100 ℃ under the protection of inert gas (such as nitrogen); heating to 200-280 ℃ within 0.5-1 h, and reacting for 3-5 h; repeating the steps for 3-5 times according to the sequence of discharging gas → vacuumizing to 0.07-0.09 MPa → charging inert gas until the pressure in the reactor is 0.5-1.5 MPa; then cooling and discharging; and finally, reacting and extruding at 180-320 ℃ to obtain the semi-aromatic polyamide copolymer.
Further, the catalyst is selected from: at least one of pyrophosphoric acid, polyphosphoric acid, phosphorous acid, sodium tripolyphosphate, sodium hypophosphite, propionic acid, and butyric acid.
Further, the mass ratio of the monomer to the catalyst to the deionized water is as follows: 200-800 parts of monomer, 1-10 parts of catalyst and 50-200 parts of deionized water.
Further, in the step 1), the process of soaking the semi-aromatic polyamide and the semi-aromatic polyamide copolymer in deionized water at the temperature of 70-100 ℃ for 12-72 hours needs to be repeated for 2-5 times.
Further, in step 1), the drying treatment refers to: and (3) drying the extracted semi-aromatic polyamide and the copolymer thereof in a vacuum drying oven at the temperature of 95-115 ℃ for 24-72 h.
Further, in step 3), the melt spinning process comprises: the semi-aromatic polyamide and the copolymer chips thereof are processed by a melt spinning machine through feeding → screw extrusion → spinning box → initial filament preparation link of spinneret spinning, and finally, the fine denier semi-aromatic polyamide fiber is prepared through filament cooling → winding → stretching → sizing.
Further, in the step 3), the melt spinning process parameters are as follows: the spinning temperature is 280-335 ℃, the roller temperature is 30-150 ℃, the winding speed is 1000-3000 m/min, and the drafting speed is 3-6.
Further, in the step 3), spinneret holes on a spinneret plate used for melt spinning are circular, polygonal or hollow spinneret holes, and the number of the spinneret holes is 48-256.
The second technical problem to be solved by the present invention is to provide a fine denier semi-aromatic polyamide fiber, which is produced by the above method.
Further, the fineness of the fine-fineness semi-aromatic polyamide fiber is 0.9 to 4.5dtex, and the fiber diameter unevenness rate is less than 1.0%. In the present invention, the fiber diameter unevenness is an index of the average diameter of the fiber and its dispersion, and means a coefficient of variation CV, and the standard deviation between the fiber diameter and the average diameter is generally expressed by this value.
Further, the fine denier semi-aromatic polyamide fiber has a mechanical strength of 1.1 to 4.8 cN/dtex.
The invention has the beneficial effects that:
the semi-aromatic polyimide copolymer is subjected to pretreatment, slicing, heat treatment and melt spinning to prepare the semi-aromatic polyamide fiber with fine titer; the fineness of the obtained fiber is 0.9-4.5dtex, the elongation at break is as follows: 10-97%; the mechanical strength is 1.1-4.8 cN/dtex, the fiber diameter unevenness (CV value) of the drawn yarn is less than 1.0%, and the heat resistance is 170-240 ℃; and has chemical resistance to organic solvents except concentrated sulfuric acid and trifluoroacetic acid.
Description of the drawings:
FIG. 1 is an SEM photograph of a copolymerized semi-aromatic polyamide fiber obtained in example 1 of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
351g of monomer (126g of terephthalic acid, 73g of adipic acid and 152g of hexamethylene diamine), 4g of sodium tripolyphosphate and 100g of deionized water are added into a reactor, and the temperature is raised to 90 ℃ for reaction under the protection of nitrogen; heating to 260 ℃ within 1h for reaction; exhausting gas within 1.5h, vacuumizing to 0.09MPa, filling an inert body to 1.5MPa, repeatedly operating for 4 times, cooling and discharging; finally, reacting and extruding at 220 ℃ to obtain semi-aromatic polyamide resin PA 6T-1; the copolymerized semi-aromatic polyamide resin PA6T-1 (the glass transition temperature of the copolymerized semi-aromatic polyamide resin is 85 ℃, the melting temperature of the copolymerized semi-aromatic polyamide resin is 295 ℃), and is soaked in water at the temperature of 90 ℃ for 24 hours and repeated for 3 times; then, drying the resin at 110 ℃ for 36 h; PA6T-1 was then sliced and heat treated: keeping the temperature at 85 ℃ for 10, then heating up to 120 ℃ at the speed of 2 ℃/min, keeping the temperature for 2h, finally quickly cooling to 70 ℃ at the speed of 30 ℃/min, and keeping the temperature for 9h to obtain the semi-aromatic polyamide and the copolymer resin slice thereof.
Passing the obtained section through a tube at 20cm3And a metering pump of the yarn/min is fed into a single screw extruder, melt spinning is carried out on a spinneret plate with the melting temperature of 315 ℃, the aperture of the spinneret plate of 0.025mm, the spinneret plate with 96 holes and a round hole, the roller temperature is 80 ℃, the oil amount is 8mL/min, stretching and solidification are carried out, the drawing ratio multiple is 5 times, and the winding speed is 2400 m/min.
The performance indexes of the obtained copolymerized semi-aromatic polyamide fiber are as follows: fineness of 1.8dtex (fineness in the inventive example was tested according to GBT 1797-2008), breaking strength of 2.6 cN/dtex; elongation at break 60%; the use temperature was 220 ℃. Wherein the molecular structural formula of the copolymerized semi-aromatic polyamide resin PA6T-1 is as follows:
example 2
248g of monomers (67g of terephthalic acid, 73g of adipic acid and 108g of hexamethylenediamine), 6g of polyphosphoric acid and 70g of deionized water are added into a reactor, and the temperature is increased to 100 ℃ for reaction under the protection of nitrogen; and the temperature is raised to 230 ℃ within 0.8h for reaction; exhausting gas within 2h, vacuumizing to 0.07MPa, filling inert gas to 1.2MPa, repeatedly operating for 3 times, cooling and discharging; finally, the semi-aromatic polyamide resin PA6T-2 is obtained by reaction extrusion at the temperature of 260 ℃. Soaking the copolymerized semi-aromatic polyamide resin PA6T-2 (the glass transition temperature of the copolymerized semi-aromatic polyamide resin is 90 ℃ and the melting temperature of the copolymerized semi-aromatic polyamide resin is 289 ℃) in water at the temperature of 100 ℃ for 30 hours, and repeating for 2 times; then, drying the resin at 110 ℃ for 36 h; PA6T-2 was then sliced and heat treated: keeping the temperature at 90 ℃ for 10h, then heating up to 130 ℃ at the speed of 5 ℃/min, keeping the temperature for 3h, finally quickly cooling to 80 ℃ at the speed of 25 ℃/min, and keeping the temperature for 10h to obtain the PA6T-2 resin slice.
Passing the obtained section through a tube at 25cm3And/min metering pump is fed into a single screw extruder, and the melt spinning is carried out on a spinneret plate with the melting temperature of 310 ℃, the spinneret plate aperture of 0.04mm, the spinneret plate with 64 holes and a round hole, the roller temperature of 60 ℃, the oil dosage of 10mL/min, the stretching and solidification are carried out, the drawing ratio multiple is 4 times, and the winding speed is 2100 m/min.
The performance indexes of the obtained copolymerized semi-aromatic polyamide fiber are as follows: fineness number: 2.3dtex, breaking strength 2 cN/dtex; elongation at break of 50%; the use temperature is 230 ℃. Wherein the molecular structural formula of the copolymerized semi-aromatic polyamide resin PA6T-1 is as follows:
comparative example 1
The preparation process is the same as example 1, except that: without the pretreatment process of soaking in water at 90 ℃ for 24h, the performance indexes of the obtained fiber are as follows: fineness number: 10.9dtex, breaking strength 1.9 cN/dtex; elongation at break 251%; the drawn yarn had a fiber diameter variation (CV value) of 7.0% and a use temperature of 220 ℃.
Comparative example 2
The preparation process is the same as example 1, except that: without "heat treatment: keeping the temperature at 90 ℃ for 10 h; and (3) performing heat treatment at 110 ℃ for 2h and at 80 ℃ for 9h, wherein the performance indexes of the obtained fiber are as follows: fineness number: 6.8dtex, breaking strength 2.6 cN/dtex; elongation at break 92%; the drawn yarn had a fiber diameter variation (CV value) of 2.0% and a use temperature of 210 ℃.
Claims (13)
1. A method for producing a fine denier semi-aromatic polyamide fiber, characterized by comprising the steps of:
1) pretreatment: soaking the semi-aromatic polyamide copolymer in deionized water at 70-100 ℃ for 12-72 h, and then drying;
2) slicing and heat treatment: preserving the temperature of the pretreated semi-aromatic polyamide copolymer at 85-90 ℃ for 10-12 h, then raising the temperature at the speed of 0.5-5 ℃/min to 100-130 ℃ for 1-3 h, finally rapidly lowering the temperature at the speed of 10-50 ℃/min to 60-80 ℃, and keeping the temperature for 8-10 h to obtain semi-aromatic polyamide copolymer resin slices;
3) melt spinning: and (3) carrying out melt spinning on the semi-aromatic polyamide copolymer chips to obtain the fine-denier semi-aromatic polyamide fibers.
2. The method for producing fine denier semi-aromatic polyamide fiber according to claim 1, wherein the structural formula of the semi-aromatic polyamide copolymer is as follows:
3. the method for producing fine denier semi-aromatic polyamide fiber according to claim 2, wherein the semi-aromatic polyamide copolymer is produced by the following method: sequentially adding a monomer, a catalyst and deionized water into a reactor, and heating to 80-100 ℃ under the protection of inert gas; heating to 200-280 ℃ within 0.5-1 h, and reacting for 3-5 h; repeating the steps for 3-5 times according to the sequence of discharging gas → vacuumizing to 0.07-0.09 MPa → charging inert gas until the pressure in the reactor is 0.5-1.5 MPa; then cooling and discharging; and finally, reacting and extruding at 180-320 ℃ to obtain the semi-aromatic polyamide copolymer.
4. The method for producing fine denier semi-aromatic polyamide fibers according to claim 3, wherein the catalyst is selected from the group consisting of: at least one of pyrophosphoric acid, polyphosphoric acid, phosphorous acid, sodium tripolyphosphate, sodium hypophosphite, propionic acid, and butyric acid.
5. The method of preparing fine denier semi-aromatic polyamide fiber according to claim 3, wherein the monomer, catalyst and deionized water are: 200-800 parts of monomer, 1-10 parts of catalyst and 50-200 parts of deionized water.
6. The method for preparing the fine denier semi-aromatic polyamide fiber according to any one of claims 1 to 3, wherein in the step 1), the semi-aromatic polyamide copolymer is soaked in deionized water at 70-100 ℃ for 12-72 hours, and the soaking time is 2-5 times.
7. The method for producing a fine denier semi-aromatic polyamide fiber according to any one of claims 1 to 3, wherein in the step 1), the drying treatment is: and (3) drying the extracted semi-aromatic polyamide copolymer in a vacuum drying oven at the temperature of 95-115 ℃ for 24-72 h.
8. The method for producing a fine denier semi-aromatic polyamide fiber according to any one of claims 1 to 5, wherein in the step 3), the melt spinning step is: the semi-aromatic polyamide copolymer chips are processed by a melt spinning machine through feeding → screw extrusion → spinning box → primary yarn preparation link of spinneret spinning, and finally, the fine denier semi-aromatic polyamide fiber is prepared through strand cooling → winding → stretching → sizing.
9. The method for preparing fine denier semi-aromatic polyamide fiber according to claim 8, wherein the melt spinning process parameters are as follows: the spinning temperature is 280-335 ℃, the roller temperature is 30-150 ℃, the winding speed is 1000-3000 m/min, and the drafting speed is 3-6.
10. The method for preparing fine denier semi-aromatic polyamide fiber according to any one of claims 1 to 5, wherein in step 3), the spinneret holes on the spinneret plate for melt spinning are circular, polygonal or hollow, and the number of the spinneret holes is 48 to 256.
11. A fine denier semi-aromatic polyamide fiber, characterized in that the semi-aromatic polyamide fiber is produced by the method of any one of claims 1 to 10.
12. The fine denier semi-aromatic polyamide fiber according to claim 11, wherein the fine denier semi-aromatic polyamide fiber has a denier of 0.9 to 4.5dtex and a fiber diameter unevenness of < 1.0%.
13. The fine denier semi-aromatic polyamide fiber according to claim 11 or 12, wherein the fine denier semi-aromatic polyamide fiber has a mechanical strength of 1.1 to 4.8 cN/dtex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110810162.1A CN113481623B (en) | 2021-07-18 | 2021-07-18 | Fine-denier semi-aromatic polyamide fiber with excellent uniformity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110810162.1A CN113481623B (en) | 2021-07-18 | 2021-07-18 | Fine-denier semi-aromatic polyamide fiber with excellent uniformity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113481623A CN113481623A (en) | 2021-10-08 |
| CN113481623B true CN113481623B (en) | 2022-03-29 |
Family
ID=77942010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110810162.1A Active CN113481623B (en) | 2021-07-18 | 2021-07-18 | Fine-denier semi-aromatic polyamide fiber with excellent uniformity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113481623B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3523316B2 (en) * | 1994-02-17 | 2004-04-26 | 株式会社クラレ | Production method of semi-aromatic polyamide |
| CN102532528B (en) * | 2012-02-10 | 2014-03-19 | 四川大学 | Method for preparing semi-aromatic polyamide |
| CN106609398A (en) * | 2015-10-22 | 2017-05-03 | 上海杰事杰新材料(集团)股份有限公司 | Bio-based semi-aromatic polyarmide fiber and preparation method thereof |
| WO2018221376A1 (en) * | 2017-05-29 | 2018-12-06 | 株式会社クラレ | Semi-aromatic polyamide fiber |
| CN110331459B (en) * | 2019-08-09 | 2020-05-26 | 四川大学 | High-temperature-resistant semi-aromatic polyamide superfine fiber and preparation method thereof |
-
2021
- 2021-07-18 CN CN202110810162.1A patent/CN113481623B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113481623A (en) | 2021-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2554725B1 (en) | Method for preparing carbon fiber and precursor fiber for carbon fiber | |
| EP2233616B1 (en) | Processes for producing flameproof fiber and carbon fiber | |
| KR101625739B1 (en) | Polyacrylonitrile Precursor for Carbon Fiber and Method for Preparing the Same | |
| CN109943914B (en) | Soft moisture-absorbing crimped staple fiber and preparation method and application thereof | |
| CN101550616B (en) | Method of preparing high strength carbon fibre | |
| CN103184591B (en) | Manufacturing method of 12K binary polyacrylonitrile-based carbon fiber | |
| CN112226851B (en) | Preparation method of polyacrylonitrile-based carbon fiber | |
| Li et al. | Polyacrylonitrile based carbon fibers: Spinning technology dependent precursor fiber structure and its successive transformation | |
| CN113481623B (en) | Fine-denier semi-aromatic polyamide fiber with excellent uniformity and preparation method thereof | |
| CN111945251A (en) | Ultrahigh-strength medium-modulus polyacrylonitrile-based carbon fiber and preparation method thereof | |
| CN111088558B (en) | Preparation method of polyacrylonitrile-based carbon fiber | |
| CN115323520A (en) | Production method of high-strength ultralow-shrinkage polyamide 66 high-denier fiber | |
| CN111088559A (en) | Preparation method of low-silicon-content polyacrylonitrile-based carbon fiber | |
| CN111088531B (en) | Method for manufacturing wet spinning polyacrylonitrile carbon fiber precursor | |
| CN110685041B (en) | Preparation method of polyacrylonitrile-based carbon fiber | |
| CN112941641A (en) | Processing method of functional flame-retardant polyester industrial yarn | |
| CN115074868B (en) | Preparation method of pre-oxidized fiber and pre-oxidized fiber | |
| KR101957061B1 (en) | Process for preparing carbon fiber having high strength | |
| CN115449070B (en) | Polyamide resin and preparation method, composition and fiber product thereof | |
| KR101470250B1 (en) | Method of manufacturing precursor for carbon fiber | |
| CN117364274B (en) | Full-biology-based high-strength nylon 510 fiber and preparation method and application thereof | |
| CN114606602B (en) | Preparation method of 25k carbon fiber and carbon fiber | |
| JP3986514B2 (en) | Process for producing polytrimethylene terephthalate | |
| CN111088535B (en) | Oiling method of low-silicon polyacrylonitrile protofilament | |
| JP2001164431A (en) | Flame resistant fiber and method for producing carbon fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |