CN113737317A - Preparation method of phenolic-group activated carbon fiber with flexibility - Google Patents
Preparation method of phenolic-group activated carbon fiber with flexibility Download PDFInfo
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- CN113737317A CN113737317A CN202111118112.3A CN202111118112A CN113737317A CN 113737317 A CN113737317 A CN 113737317A CN 202111118112 A CN202111118112 A CN 202111118112A CN 113737317 A CN113737317 A CN 113737317A
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- -1 phenolic-group activated carbon fiber Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920006282 Phenolic fiber Polymers 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 29
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 19
- 239000005011 phenolic resin Substances 0.000 claims abstract description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 9
- 239000002657 fibrous material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000004917 carbon fiber Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000002074 melt spinning Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000578 dry spinning Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 239000007790 solid phase Substances 0.000 claims 1
- 229920005992 thermoplastic resin Polymers 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 238000001994 activation Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000012190 activator Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010042 air jet spinning Methods 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WTDFFADXONGQOM-UHFFFAOYSA-N formaldehyde;hydrochloride Chemical compound Cl.O=C WTDFFADXONGQOM-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- 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
- D01F6/88—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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention relates to a preparation method of phenolic fiber and activated carbon fiber thereof, which mainly comprises the steps of spinning, crosslinking, carbonization-activation. The method comprises the following specific steps: (1) the phenolic fiber precursor is prepared by fully mixing thermoplastic phenolic resin and Hexamethylenetetramine (HMTA) in a certain ratio and a certain mode and then using a specific spinning method. (2) And placing the obtained phenolic fiber protofilament in an acid atmosphere at a certain temperature, and crosslinking for a period of time to obtain the phenolic fiber with sufficient mechanical properties. (3) KOH is used as an activating agent, and carbonization-activation is adopted to obtain the phenolic activated carbon fiber material. The invention has the advantages that the preparation process of the phenolic fiber is simplified, so that the production process of the phenolic fiber is green and efficient; the phenolic aldehyde group activated carbon fiber with high flexibility and high specific surface area and the flexible fabric material thereof can be obtained, and the obtained activated carbon fiber material has wide application prospect in the fields of adsorption separation, electrochemistry and the like.
Description
Technical Field
The invention belongs to the technical field of special fibers, and relates to a preparation method of phenolic fibers and activated carbon fibers thereof.
Background
Phenolic fiber was first developed in 1968 by Economy et al of carbon fiber, and gradually became a research hotspot due to low cost of raw materials and excellent heat resistance, and the phenolic fiber is a non-crystalline high-temperature resistant fiber with a three-dimensional structure, which is prepared by taking thermoplastic phenolic resin as a raw material through melt spinning and chemical crosslinking. The high-temperature-resistant and high-temperature-resistant composite material is applied to the fields of fire fighting, high-temperature gas filtration, corrosive liquid purification and the like due to excellent high-temperature stability, chemical stability and friction resistance; the crosslinked phenolic fiber has the characteristics of less harmful gas overflow during carbonization, high carbonization efficiency and the like, so the crosslinked phenolic fiber is an excellent material for preparing the activated carbon fiber and has wide application prospect in the fields of adsorption, energy and the like. But the phenolic aldehyde-based activated carbon fiber prepared at the present stage is difficult to be produced in a large scale all the time due to the reasons of poor mechanical property, complex preparation process, complex crosslinking process and the like.
Compared with other activated carbon fiber precursors, the activated carbon fiber prepared from the phenolic fiber has remarkable advantages, the phenolic activated carbon fiber has small strength loss in the carbonization and activation processes because the precursor is a non-crystalline material, and protofilaments with higher strength modulus and crystallinity, such as viscose, polyacrylonitrile, asphalt and the like, are easy to crystallize and crack in the carbonization and activation processes, so that the strength is remarkably reduced; on the other hand, the phenolic-based activated carbon fiber has high specific surface area (generally 1000-3000 m)2And/g), good conductivity, high carbon content of the activated phenolic carbon fiber, low heteroatom content, and obvious advantages in the application fields of adsorption filtration, electrochemistry and the like.
At present, the research on the phenolic activated carbon fiber is mainly based on physical activation, but the method is long in time consumption, complex in preparation process, free of forming a mature process route and less in research on the structure and the activation mechanism of the phenolic activated carbon fiber. Researchers use KOH and ZnCl2 as activators to prepare phenolic-based activated carbon fibers by a chemical activation method, for example, Tang political and other people use phenolic resin as a carbon source and KOH as an activator, and study the influence of the activation temperature, the activation time and the KOH/phenolic resin ratio on the pore diameter and the pore diameter distribution of the phenolic resin activated carbon material, so that the final specific surface area is 1400m2Activated carbon material with a mesopore ratio of 76.4% and an average pore diameter of 2.43nm, ZnCl as a peak of university2The phenolic fiber base felt cloth is prepared for the activating agent, and the application of the phenolic fiber base felt cloth in the field of gas adsorption is explored. The application of the chemical activation method in the aspect of preparing the activated carbon fiber is gradually mature, but as the phenolic fiber precursor with better performance is difficult to obtain,at present, a larger gap still exists in the preparation and application of the phenolic activated carbon fiber.
In view of the above disadvantages, it is actually necessary to provide a method for preparing phenolic activated carbon fiber, which is green and environment-friendly and can be continuously produced.
Disclosure of Invention
The invention aims to provide a preparation method of phenolic fiber and flexible activated carbon fiber thereof, which comprises the following steps: on one hand, the method aims at solving the problems of complex preparation process, great harm of acid-aldehyde bath to human bodies and environment, overlong crosslinking time and discontinuous production process in the existing phenolic fiber preparation process. According to the invention, hexamethylenetetramine is used as a cross-linking agent, and is uniformly mixed with the thermoplastic phenolic resin according to a certain proportion and spun to prepare fiber precursor, and then the cross-linked phenolic fiber with better mechanical property and meeting the industrial production requirement is prepared by a method of uniformly heating and cross-linking in an acidic gas atmosphere. HMTA is used as a cross-linking agent instead of formaldehyde-hydrochloric acid solution, so that the problems of easy volatilization and high toxicity of the traditional acid-aldehyde bath are solved; meanwhile, the method for preparing the crosslinked phenolic fiber by the crosslinking method simplifies the preparation process of the phenolic fiber, shortens the preparation flow and further improves the production efficiency. On the other hand, by adopting the chemical activation method, the pore size distribution and the specific surface area of the activated carbon fiber can be better regulated and controlled by controlling the activation temperature, the amount of the activating agent and the activation time. Finally, the phenolic fiber-based activated carbon material with high flexibility and certain mechanical property is obtained.
The invention mainly aims to prepare phenolic fiber precursor by using HMTA as a cross-linking agent and adopting a blending method, prepare phenolic fiber by a thermal cross-linking treatment method, and prepare a phenolic-based flexible activated carbon fiber material by a chemical activation method. The preparation method is suitable for various spinning methods for preparing the phenolic fiber. The embodiment of the invention adopts the following technical scheme:
the invention provides a preparation method for preparing flexible phenolic-based activated carbon fibers, which comprises the following steps:
step one, using the molecular weight of M not less than 800 in the marketWThermoplastic phenolic aldehyde of less than or equal to 3000The phenolic fiber filament, the phenolic fiber cotton and the phenolic fiber aggregate are respectively obtained by using the resin as a raw material by adopting melt spinning, melt centrifugal spinning and air jet spinning methods.
The air-jet spinning method belongs to one of dry spinning methods, namely, a mixed solution with 15-35% of solute is prepared from thermoplastic phenolic resin and one or more soluble high polymer mixtures such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVB), polyethylene glycol (PEG) and the like, and then HMTA with 8-18% of phenolic resin is added and uniformly mixed. The solvent is one or a mixture of any of ethanol, methanol and DMF, and when the molecular weight of the high polymer is larger, the mass fraction of the high polymer is smaller, so that the mass ratio of the resin to the high polymer is ensured to be more than 1.
And step two, heating the phenolic fiber protofilament obtained in the step one to a certain temperature in an acid gas atmosphere, and carrying out heat preservation and crosslinking to obtain the crosslinked phenolic fiber material. The acid gas is one of hydrochloric acid, formic acid, acetic acid and acetic acid.
The high polymer-phenolic resin matrix mixed fiber aggregate obtained by adopting the air jet spinning method is subjected to heat treatment in water or alcohol for a period of time, so that the high polymer component is dissolved, and the phenolic resin aggregate is obtained.
And step three, respectively adopting a one-step method and a two-step method to place the phenolic fiber material into an activator solution, determining the mass ratio of the activator to the phenolic fiber material to be 4: 1, using KOH as the activator, and controlling the soaking time to be 1-4 h.
The one-step method is to directly place the crosslinked phenolic fiber in an activator solution for soaking, and then carry out a carbonization step.
And step four, placing the soaked phenolic fiber or phenolic-based carbon fiber in an inert gas environment, heating to 900 ℃ at the speed of 5-10 ℃/min, and activating for 1-2 h.
Advantageous effects
The invention discloses a method for preparing crosslinked phenolic aldehyde, which can prepare an active carbon fiber material with high flexibility and mechanical stretch resistance at the same time, and has the following specific advantages:
(1) the method has the advantages that hexamethylenetetramine is used as a cross-linking agent to replace formaldehyde, the phenolic fiber is prepared by adopting a gas-phase heating method, the problem that the liquid-phase cross-linking agent formaldehyde volatilizes or reacts to generate toxicity in the traditional phenolic fiber preparation process is solved, meanwhile, the gas-phase heating cross-linking method greatly shortens the cross-linking time, simplifies the preparation process, improves the production efficiency, enables the production process to be more efficient, continuous and environment-friendly, and the breaking strength of the prepared cross-linked phenolic fiber filament is 2-3.63 cN/dTex.
(2) The production process method which can realize crosslinking by blending the crosslinking agent (HMTA) and the phenolic resin to prepare the fiber protofilament is suitable for most spinning modes, and different spinning methods can be adopted according to different production requirements to prepare the phenolic fiber materials meeting different use requirements.
(3) The phenolic aldehyde group activated carbon fiber prepared by the chemical activation method has the characteristics of low cost and high efficiency, and the pore size and the distribution of the activated carbon fiber can be adjusted by controlling the reaction conditions, so that the phenolic aldehyde group activated carbon fiber with high flexibility and certain mechanical property is finally obtained.
Drawings
Fig. 1(a), (b), and (c) are schematic diagrams showing a phenolic fiber raw yarn, a crosslinked phenolic fiber filament, and a phenolic fiber felt.
Fig. 2(a), (b), and (c) are diagrams showing activated products of a phenolic activated carbon fiber, an activated carbon fiber felt, and a fiber aggregate obtained by an air-jet spinning method, respectively.
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.
Example 1
A preparation method of phenolic-based flexible activated carbon fiber filaments comprises the following steps:
step one, using commercial thermoplastic phenolic resin as raw material and having molecular weight MW2000-90 ℃, the softening point is 80-90 ℃, a melt spinning machine self-made by a laboratory is adopted, phenolic resin with the mass ratio of 85: 15 and HMTA are fully mixed, then the mixture is placed in a charging barrel to be heated uniformly and then pressurized and extruded, the mixture is solidified into filaments in the air, and the filaments are drawn and coiled to obtain the phenolic nascent fiber, as shown in figure 1 (a). The temperature of the material barrel is determined to be 100-120 ℃, the temperature of the spinneret plate is 98-1 ℃, the diameter of the spinneret orifice is 0.2mm, and the winding speed of the take-up roller is 150 m/min.
And step two, placing the phenolic aldehyde fiber primary phenolic fiber obtained in the step one in acid gas of hydrochloric acid, heating to 150 ℃ at the speed of 5 ℃/min, and preserving heat for 1h to obtain the cross-linked phenolic fiber, wherein the fiber diameter is 10-20 mu m, the breaking strength is 2-3.26CN/dTex, and the physical diagram is shown in figure 1 (b).
And step three, heating the crosslinked phenolic fiber obtained in the step two to 900 ℃ at the speed of 10 ℃/min in a nitrogen environment, preserving the temperature for 1h to obtain phenolic-based carbon fiber, soaking the obtained carbon fiber in a KOH solution for 4h, taking out, drying, heating to 800 ℃ at the speed of 10 ℃/min in the nitrogen environment to obtain the phenolic-based active carbon fiber filament, wherein the step is shown in figure 2 (a).
Example 2
A preparation method of phenolic-based flexible activated carbon fiber felt comprises the following steps:
step one, using commercial thermoplastic phenolic resin as raw material, the molecular weight is more than 1000MWLess than 3000, the softening point of 102-110 ℃, fully mixing the resin and the HMTA according to the mass ratio of 95: 15, and preparing the phenolic aldehyde primary fiber cotton by adopting a melting centrifugal spinning machine, wherein the spinning temperature is 180 ℃, and the rotating speed of a centrifugal machine is 900 r/min.
And step two, heating the phenolic fiber phenolic aldehyde obtained in the step one to 150 ℃ at the speed of 15 ℃/min in acid gas, and preserving heat for 0.5h to finally obtain the crosslinked phenolic fiber cotton.
And step three, taking the phenolic fiber obtained in the step two as a raw material, and preparing the phenolic fiber felt cloth by adopting opening, carding and two spunlace processes, as shown in figure 1 (c).
And step four, soaking the crosslinked phenolic fiber felt cloth obtained in the step three in a KOH solution for 4 hours, taking out and drying the crosslinked phenolic fiber felt cloth, and then heating the crosslinked phenolic fiber felt cloth to 700 ℃ at the speed of 5 ℃/min in a nitrogen environment to finally obtain the phenolic activated carbon fiber felt cloth, wherein the prepared activated carbon fiber felt cloth can bear certain stretching and has good flexibility, as shown in fig. 2 (b).
Example 3
A preparation method of a phenolic-based flexible activated carbon nano air-jet film comprises the following steps:
step one, the low molecular weight of commercially available molecular weight is more than 800 and less than MW< 3000 resol to form an organic solution of phenolic resin, said resol being a thermoplastic phenolic resin, said solvent being N, N dimethyl-formamide (DMF).
And step two, adding 6-8% of high molecular weight linear polymer into the solution obtained in the step one, and stirring until the linear high molecular weight polymer is completely dissolved, wherein the linear high molecular weight polymer is polyvinylpyrrolidone (PVP) and has the molecular weight of 400-800 ten thousand.
And step three, adding an aqueous solution of HMTA into the mixed solution obtained in the step two, wherein the amount of the added HMTA is 10% of the mass fraction of the resin.
Step four, preparing the mixed fiber aggregate with a certain thickness from the mixed solution obtained in the step three by adopting an air jet spinning method, wherein the relative humidity of the environment is RH 30%, the temperature is 30 ℃, the air pressure is 0.05MPa, the distance between a needle head and a substrate is 25cm, and the feeding amount of an injection pump is 10 ml/h.
And fifthly, placing the obtained phenolic fiber film into hydrochloric acid gas, heating to 150 ℃ at the speed of 10 ℃/min, and preserving heat for 1.5 hours until the mixed fiber film is crosslinked.
And sixthly, placing the prepared mixed fiber aggregate in a hot water bath for 5-12h, and drying to finally obtain the phenolic-based fiber aggregate.
And step seven, soaking the crosslinked phenolic fiber film obtained in the step six in a KOH solution for 2h, taking out, drying, and then heating to 800 ℃ at the speed of 5 ℃/min in a nitrogen environment to obtain the phenolic group activated carbon fiber aggregate material, wherein the obtained material has good flexibility and certain mechanical property, as shown in the step 2 (c).
Claims (7)
1. A preparation method of phenolic aldehyde group activated carbon fiber with flexibility is characterized by comprising the following steps:
the method comprises the following steps: mixing commercially available thermoplastic phenolic resin with low molecular weight of more than 800 and less than 3000 and melting point of 80-109 ℃ with Hexamethylenetetramine (HMTA) according to a certain proportion and a certain mode, and then preparing the phenolic fiber precursor by different spinning technologies.
Step two: and (3) heating the phenolic fiber protofilament obtained in the step one to a certain temperature in an acid gas atmosphere for crosslinking, and endowing the fiber with certain mechanical strength. The acid gas is one of hydrochloric acid, formic acid, acetic acid and acetic acid.
Step three: and (3) carrying out alkali chemical activation on the prepared crosslinked phenolic fiber material to obtain the flexible phenolic group activated carbon material.
2. The method for preparing phenolic-based flexible carbon fiber according to claim 1, wherein: in the first step, the mass fraction of the phenolic resin and the cross-linking agent HMTA is as follows: 82-92% of phenolic resin and 8-18% of HMTA.
3. The method for preparing phenolic-based flexible carbon fiber according to claim 1, wherein: the melt centrifugal spinning temperature in the first step is 90-120 ℃.
4. The method for preparing phenolic-based flexible carbon fiber according to claim 1, wherein: in the first step, the mixing mode of the thermoplastic resin and the HMTA comprises solid phase mixing and liquid phase mixing; the spinning method comprises screw extrusion melt spinning, melt centrifugal spinning and solution air-jet dry spinning.
5. The method for preparing phenolic-based flexible carbon fiber according to claim 1, wherein: in the second step, the temperature programming rate is 2-20 ℃/min.
6. The method for preparing phenolic-based flexible carbon fiber according to claim 1, wherein: in the second step, the crosslinking temperature is 150-180 ℃.
7. The method for preparing phenolic-based flexible carbon fiber according to claim 1, wherein: and the crosslinking time in the second step is 1-2 h.
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| CN202111118112.3A CN113737317A (en) | 2021-09-24 | 2021-09-24 | Preparation method of phenolic-group activated carbon fiber with flexibility |
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| CN112267164A (en) * | 2020-09-24 | 2021-01-26 | 彤程化学（中国）有限公司 | Phenolic aldehyde based blend fiber and preparation method thereof |
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